García Calvo, José Luis; Sánchez Moreno, Mercedes; Alonso Alonso, María Cruz; Hidalgo López, Ana; García Olmo, Juan
2013-06-18
Low-pH cements are designed to be used in underground repositories for high level waste. When they are based on Ordinary Portland Cements (OPC), high mineral admixture contents must be used which significantly modify their microstructure properties and performance. This paper evaluates the microstructure evolution of low-pH cement pastes based on OPC plus silica fume and/or fly ashes, using Mid-Infrared and Near-Infrared spectroscopy to detect cement pastes mainly composed of high polymerized C-A-S-H gels with low C/S ratios. In addition, the lower pore solution pH of these special cementitious materials have been monitored with embedded metallic sensors. Besides, as the use of reinforced concrete can be required in underground repositories, the influence of low-pH cementitious materials on steel reinforcement corrosion was analysed. Due to their lower pore solution pH and their different pore solution chemical composition a clear influence on steel reinforcement corrosion was detected.
NASA Astrophysics Data System (ADS)
Cookenboo, H. O.; Bustin, R. M.
1999-01-01
The succession of sandstone cements in chert and volcanic lithic arenites and wackes from the northern Bowser Basin of British Columbia comprises a record of diagenesis in shallow marine, deltaic, and coastal plain siliciclastic sediments that pass through the oil window and reach temperatures near the onset of metamorphism. The succession of cements is consistent with seawater in the sandstones mixing with acid waters derived from dewatering of interbedded organic rich muds. Sandstone cement paragenesis includes seven discrete cement stages. From earliest to latest the cement stages are: (1) pore-lining chlorite; (2) pore-lining to pore-filling illite; (3) pore-filling kaolinite; (4) oil migration through some of the remaining connected pores; (5) chlorite dissolution; (6) quartz cement; and (7) calcite cement. These seven cement stages are interpreted as a record of the evolution of pore waters circulating through the sandstones after burial. The earliest cement stages, as well as the depositional environments, are compatible with seawater as the initial pore fluid. Seawater composition changed during transport through the sandstones, first by loss of Mg 2+ and Fe 2+ during chlorite precipitation (stage 1). Dewatering of interbedded organic-rich mudstones probably added Mg 2+ and Fe 2+ to partially buffer the loss of these cations to chlorite. Acids produced during breakdown of organic matter are presumed to have mixed into sandstone pore fluids due to further compaction of the muds, leading to reduction of initial alkalinity. Reduction in alkalinity, in turn, favours change from chlorite to illite precipitation (stage 2), and finally to kaolinite (stage 3). Pore waters likely reached their peak acidity at the time of oil migration (stage 4). Chlorite dissolution (stage 5) and quartz precipitation (stage 6) occurred when pores were filled by these hydrocarbon-bearing and presumably acidic fluids. Fluid inclusions in fracture-filling quartz cements contain petroleum, high-pressure methane, and methane-rich aqueous solutions. Homogenization temperatures from primary two-phase inclusions are consistent with quartz cementation during progressive heating between approximately 100 and 200°C. Following quartz precipitation, alkaline pore waters were re-established, as evidenced by late-stage calcite cement (stage 7).
DOE Office of Scientific and Technical Information (OSTI.GOV)
Sugama, T.; Pyatina, T.
2014-11-01
This study evaluates inorganic pigments for improving carbon steel (CS) brine-corrosion protection by the sodium metasilicate-activated calcium aluminate cement/Fly Ash blend at 300°C. Calcium borosilicate (CBS) and zinc phosphate, significantly improved CS corrosion-protection by decreasing cement’s permeability for corrosive ions and inhibiting anodic corrosion. An amorphous Na 2O-Al 2O 3-SiO 2-H 2O phase tightly attached to CS surface formed at 300oC in CBS-modified cement pore solution. The corrosion rate of the CS covered with this phase was nearly 4-fold lower than in the case of nonmodified cement pore solution where the major phase formed on the surface of CS wasmore » crystalline analcime.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Sugama, T.; Pyatina, T.
2014-11-14
This study evaluates inorganic pigments for improving carbon steel (CS) brine-corrosion protection by the sodium metasilicate-activated calcium aluminate cement/Fly Ash blend at 300°C. Calcium borosilicate (CBS) and zinc phosphate, significantly improved CS corrosion-protection by decreasing cement’s permeability for corrosive ions and inhibiting anodic corrosion. An amorphous Na 2O-Al 2O 3-SiO 2-H 2O phase tightly attached to CS surface formed at 300oC in CBS-modified cement pore solution. The corrosion rate of the CS covered with this phase was nearly 4-fold lower than in the case of nonmodified cement pore solution where the major phase formed on the surface of CS wasmore » crystalline analcime.« less
An ESEM investigation of latex film formation in cement pore solution
DOE Office of Scientific and Technical Information (OSTI.GOV)
Gretz, M.; Plank, J., E-mail: sekretariat@bauchemie.ch.tum.d
2011-02-15
Environmental scanning electron microscopy (ESEM) and complementary methods were employed to study the time dependent film formation of a latex dispersion in water and cement pore solution. First, a model carboxylated styrene/n-butyl acrylate latex dispersion possessing a minimum film forming temperature (MFFT) of 18 {sup o}C was synthesized in aqueous media via emulsion polymerization. Its film forming property was at a temperature of 40 {sup o}C, studied under an ESEM. The analysis revealed that upon removal of water, film formation occurs as a result of particle packing, particle deformation and finally particle coalescence. Film formation is significantly retarded when themore » latex dispersion is present in cement pore solution. This effect can be ascribed to adsorption of Ca{sup 2+} ions onto the surface of the anionic latex particles and to interfacial secondary phases. This layer of adsorbed Ca{sup 2+} ions hinders interdiffusion of the macromolecules and subsequent film formation of the latex polymer.« less
Stylolitization as source of cement in Mississippian Salem Limestone, west-central Indiana
DOE Office of Scientific and Technical Information (OSTI.GOV)
Finkel, E.A.; Wilkinson, B.H.
The Mississippian Salem Limestone of west-central Indiana is a homogeneous cross-bedded grainstone containing numerous stylolites with amplitudes ranging up to 25 cm. Petrographic and geochemical analyses of closely spaced samples from four 1-m thick stylolite-bounded units document spatial trends in grainstone texture and composition, which correlate with proximity to bounding solution seams. Textural data indicate that stylolitization was locally preceded by grain compaction and that seam solution preferentially occurred within layers where grain packing was tightest. Amount of cement largely corresponds to volume of available pore space, and remaining porosity varies inversely to stylolite proximity. Trace-element compositions demonstrate that intergranularmore » spar is enriched in Mn and depleted in Mg relative to grains, and suggest a significant contribution of carbonate cement to grainstone pores from bounding solution seams. Data on grainstone and stylolite insoluble contents indicate that stylolite amplitude records 43% of actual section shortening. On average, seam solution within the Salem Limestone could have provided no less than 47% and no more than 90% of the CaCO{sub 3}, Fe, and Mn mass now in grainstone pores as intergranular spar cement. As such, stylolitization has played an important role during burial diagenesis, porosity occlusion, and permeability reduction within this Mississippian grainstone sequence. 17 figs., 1 tab.« less
Liu, Jun; Tang, Kaifeng; Qiu, Qiwen; Pan, Dong; Lei, Zongru; Xing, Feng
2014-01-01
In this paper, the pore structure characterization of concrete exposed to deionised water and 5% NaCl solution was evaluated using mercury intrusion porosity (MIP), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The effects of calcium leaching, fly ash incorporation, and chloride ions on the evolution of pore structure characteristics were investigated. The results demonstrate that: (i) in ordinary concrete without any fly ash, the leaching effect of the cement products is more evident than the cement hydration effect. From the experimental data, Ca(OH)2 is leached considerably with the increase in immersion time. The pore structure of concrete can also be affected by the formation of an oriented structure of water in concrete materials; (ii) incorporation of fly ash makes a difference for the performance of concrete submersed in solutions as the total porosity and the pore connectivity can be lower. Especially when the dosage of fly ash is up to 30%, the pores with the diameter of larger than 100 nm show significant decrease. It demonstrates that the pore properties are improved by fly ash, which enhances the resistance against the calcium leaching; (iii) chlorides have a significant impact on microstructure of concrete materials because of the chemical interactions between the chlorides and cement hydrates. PMID:28788204
NASA Astrophysics Data System (ADS)
Aminul Islam, M.
2009-06-01
This study deals with the diagenesis and reservoir quality of sandstones of the Bhuban Formation located at the Titas Gas Field of Bengal Basin. Petrographic study including XRD, CL, SEM and BSE image analysis and quantitative determination of reservoir properties were carried out for this study. The sandstones are fine to medium-grained, moderately well to well sorted subfeldspathic arenites with subordinate feldspathic and lithic arenites. The diagenetic processes include clay infiltration, compaction and cementation (quartz overgrowth, chlorite, kaolinite, calcite and minor amount of pyrite, dolomite and K-feldspar overgrowth). Quartz is the dominant pore occluding cement and generally occurred as small euhedral crystals, locally as large pyramidal crystals in the primary pores. Pressure solution derived from grain contact is the main contributor of quartz overgrowths. Chlorite occurs as pore-lining and pore filling cement. In some cases, chlorite helps to retain porosity by preventing quartz overgrowth. In some restricted depth interval, pore-occlusion by calcite cement is very much intense. Kaolinite locally developed as vermiform and accelerated the minor porosity loss due to pore-occlusion. Kaolinite/chlorite enhances ineffective microporosity. Kaolinite is a by-product of feldspar leaching in the presence of acidic fluid produced during the maturation of organic matter in the adjacent Miocene or deeper Oligocene source rocks. The relation between diagenesis and reservoir quality is as follows: the initial porosity was decreased by compaction and cementation and then increased by leaching of the metastable grains and dissolution of cement. Good quality reservoir rocks were deposited in fluvial environment and hence quality of reservoir rocks is also environment selective. Porosity and permeability data exhibit good inverse correlation with cement. However, some data points indicate multiple controls on permeability. Reservoir quality is thus controlled by pore occluding cement, textural parameters (grain size, pore size and sorting) and depositional environment. The reservoir finally resumed partly its pre-cementation quality after development of secondary porosity.
NASA Astrophysics Data System (ADS)
Tabares Tamayo, Juan D.
The concrete industry increasingly emphasizes advances in novel materials that promote construction of more resilient infrastructure. Due to its potential to improve concrete durability, internal curing (IC) of concrete by means of superabsorbent polymers (SAP) has been identified as one of the most promising technologies of the 21st century. The addition of superabsorbent polymers into a cementitious system promotes further hydration of cement by providing internal moisture during the hardening and strength development periods, and thus limits self-desiccation, shrinkage, and cracking. This thesis presents the work performed on the series of cement pastes with varying alkalinity of their pore solutions to provide a better understanding of: (1) the influence of the chemistry of the pore solution (i.e. its level of alkalinity and the type of ionic species present) on the absorption capacity of SAP, and (2) the effectiveness of SAP with different absorption capacities as an internal curing agent. This research work was divided into three stages: (a) materials characterization, (b) measurement of absorption capacity of SAP in synthetic pore solutions, and (c) evaluation of the internal curing effectiveness of SAP. During the first stage (Materials Characterization), pore solutions were extracted from the fresh (5 minutes old) cement pastes prepared using cements with three different levels of alkalinity. The pH values of the extracted solutions were determined (using the pH meter) and their chemical analysis was performed by means of titration (concentration of hydroxyl), ion chromatography (sulfates and chlorides), atomic absorption (AA) and inductively coupled plasma optical emission spectrometry (ICP) (sodium, potassium and calcium). The commercial SAP adopted for this study was used with "as-supplied" gradation and with the finer gradation obtained by grinding the original polymer in the 6850 Cryomilling Freezer/Mill. The physical properties of these SAP's, such as the shape and size of the particles, were determined by optical microscopy combined with image analysis. The second stage, the absorption capacity of SAP's, involved determination of the swelling behavior and the absorption capacity of polymers exposed to artificial pore solutions with different levels of alkalinity. The swelling behavior was followed using the optical microscope while the absorption capacity was characterized using the tea bag method. It was found that changes in the chemical compositions of the pore solutions influence the adsorption kinetics and result in different absorption isotherms. In the third stage, the internal curing effects of inclusion of SAP in cement pastes were evaluated. Mixture proportions of pastes used in this stage of the study were selected based on the absorption capacity of the SAP determined in stage two. The testing of the pastes involved determination of their set times, heat of hydration, and autogenous shrinkage.
Hydration of calcium sulfoaluminate cements - Experimental findings and thermodynamic modelling
DOE Office of Scientific and Technical Information (OSTI.GOV)
Winnefeld, Frank, E-mail: Frank.Winnefeld@empa.c; Lothenbach, Barbara
Calcium sulfoaluminate cements (CSA) are a promising low-CO{sub 2} alternative to ordinary Portland cements and are as well of interest concerning their use as binder for waste encapsulation. In this study, the hydration of two CSA cements has been investigated experimentally and by thermodynamic modelling between 1 h and 28 days at w/c ratios of 0.72 and 0.80, respectively. The main hydration product of CSA is ettringite, which precipitates together with amorphous Al(OH){sub 3} until the calcium sulfate is consumed after around 1-2 days of hydration. Afterwards, monosulfate is formed. In the presence of belite, straetlingite occurs as an additionalmore » hydration product. The pore solution analysis reveals that straetlingite can bind a part of the potassium ions, which are released by the clinker minerals. The microstructure of both cements is quite dense even after 16 h of hydration, with not much pore space available at a sample age of 28 days. The pore solution of both cements is dominated during the first hours of hydration by potassium, sodium, calcium, aluminium and sulfate; the pH is around 10-11. When the calcium sulfate is depleted, the sulfate concentration drops by a factor of 10. This increases pH to around 12.5-12.8. Based on the experimental data, a thermodynamic hydration model for CSA cements based on cement composition, hydration kinetics of clinker phases and calculations of thermodynamic equilibria by geochemical speciation has been established. The modelled phase development with ongoing hydration agrees well with the experimental findings.« less
Influence of sodium borate on the early age hydration of calcium sulfoaluminate cement
DOE Office of Scientific and Technical Information (OSTI.GOV)
Champenois, Jean-Baptiste; Dhoury, Mélanie; Cau Dit Coumes, Céline, E-mail: celine.cau-dit-coumes@cea.fr
Calcium sulfoaluminate (CSA) cements are potential candidates for the conditioning of radioactive wastes with high sodium borate concentrations. This work thus investigates early age hydration of two CSA cements with different gypsum contents (0 to 20%) as a function of the mixing solution composition (borate and NaOH concentrations). Gypsum plays a key role in controlling the reactivity of cement. When the mixing solution is pure water, increasing the gypsum concentration accelerates cement hydration. However, the reverse is observed when the mixing solution contains sodium borate. Until gypsum exhaustion, the pore solution pH remains constant at ~ 10.8, and a poorlymore » crystallized borate compound (ulexite) precipitates. A correlation is established between this transient precipitation and the hydration delay. Decreasing the gypsum content in the binder, or increasing the sodium content in the mixing solution, are two ways of reducing the stability of ulexite, thus decreasing the hydration delay.« less
NASA Astrophysics Data System (ADS)
Sant, Gaurav Niteen
The increased use of high-performance, low water-to-cement (w/c) ratio concretes has led to increased occurrences of early-age shrinkage cracking in civil engineering structures. To reduce the magnitude of early-age shrinkage and the potential for cracking, mitigation strategies using shrinkage reducing admixtures (SRAs), saturated lightweight aggregates, expansive cements and extended moist curing durations in construction have been recommended. However, to appropriately utilize these strategies, it is important to have a complete understanding of the driving forces of early-age volume change and how these methods work from a materials perspective to reduce shrinkage. This dissertation uses a first-principles approach to understand the mechanism of shrinkage reducing admixtures (SRAs) to generate an expansion and mitigate shrinkage at early-ages, quantify the influence of a CaO-based expansive additive in reducing unrestrained shrinkage, residual stress development and the cracking potential at early-ages and quantify the influence of shrinkage reducing admixtures (SRAs) and cement hydration (pore structure refinement) on the reduction induced in the fluid transport properties of the material. The effects of shrinkage reducing admixtures (SRAs) are described in terms of inducing autogenous expansions in cement pastes at early ages. An evaluation comprising measurements of autogenous deformation, x-ray diffraction (Rietveld analysis), pore solution and thermogravimetric analysis and electron microscopy is performed to understand the chemical nature and physical effects of the expansion. Thermodynamic calculations performed on the measured liquid-phase compositions indicate the SRA produces elevated Portlandite super-saturations in the pore solution which results in crystallization stress driven expansions. The thermodynamic calculations are supported by deformation measurements performed on cement pastes mixed in solutions saturated with Portlandite or containing additional Sodium Hydroxide. Further, to quantify the influence of temperature on volume changes in SRA containing materials, deformation measurements are performed at different temperatures. The results indicate maturity transformations are incapable of simulating volume changes over any temperature regime due to the influence of temperature on salt solubility and pore solution composition, crystallization stresses and self-desiccation. The performance of a CaO-based expansive additive is evaluated over a range of additive concentrations and curing conditions to quantify the reduction in restrained and unrestrained volume changes effected in low w/c cement pastes. The results suggest, under unrestrained sealed conditions the additive generates an expansion and reduces the magnitude of total shrinkage experienced by the material. However, the extent of drying shrinkage developed is noted to be similar in all systems and independent of the additive dosage. Under restrained sealed conditions, the additive induces a significant compressive stress which delays tensile stress development in the system. However, a critical additive concentration (around four percent) needs to be exceeded to appreciably reduce the risk of cracking at early-ages. The influence of shrinkage reducing admixtures (SRAs) is quantified in terms of the effects of SRA addition on fluid transport in cement-based materials. The change in the cement paste's pore solution properties, i.e., the surface tension and fluid-viscosity, induced by the addition of a SRA is observed to depress the fluid-sorption and wetting moisture diffusion coefficients, with the depression being a function of the SRA concentration. The experimental results are compared to analytical descriptions of water sorption and a good correlation is observed. These results allow for the change in pore-solution and fluid-transport properties to be incorporated from a fundamental perspective in models which aim to describe the service-life of structures. Several experimental techniques such as chemical shrinkage, low temperature calorimetry and electrical impedance spectroscopy are evaluated in terms of their suitability to identify capillary porosity depercolation in cement pastes. The evidence provided by the experiments is: (1) that there exists a capillary porosity depercolation threshold around 20% capillary porosity in cement pastes and (2) low temperature calorimetry is not suitable to detect porosity depercolation in cement pastes containing SRAs. Finally, the influence of porosity depercolation is demonstrated in terms of the reduction effected in the transport properties (i.e., the fluid-sorption coefficient) of the material as quantified using x-ray attenuation measurements. The study relates the connectivity of the pore structure to the fluid transport response providing insights related to the development of curing technologies and the specification of wet curing regimes during construction.
Hydration of Portland cement with additions of calcium sulfoaluminates
DOE Office of Scientific and Technical Information (OSTI.GOV)
Le Saout, Gwenn, E-mail: gwenn.le-saout@mines-ales.fr; Lothenbach, Barbara; Hori, Akihiro
2013-01-15
The effect of mineral additions based on calcium aluminates on the hydration mechanism of ordinary Portland cement (OPC) was investigated using isothermal calorimetry, thermal analysis, X-ray diffraction, scanning electron microscopy, solid state nuclear magnetic resonance and pore solution analysis. Results show that the addition of a calcium sulfoaluminate cement (CSA) to the OPC does not affect the hydration mechanism of alite but controls the aluminate dissolution. In the second blend investigated, a rapid setting cement, the amorphous calcium aluminate reacts very fast to ettringite. The release of aluminum ions strongly retards the hydration of alite but the C-S-H has amore » similar composition as in OPC with no additional Al to Si substitution. As in CSA-OPC, the aluminate hydration is controlled by the availability of sulfates. The coupling of thermodynamic modeling with the kinetic equations predicts the amount of hydrates and pore solution compositions as a function of time and validates the model in these systems.« less
Stability of GO Modified by Different Dispersants in Cement Paste and Its Related Mechanism.
Long, Wu-Jian; Fang, Changle; Wei, Jingjie; Li, Haodao
2018-05-18
Graphene oxide (GO) is a potential material to be used as a nano-reinforcement in cement matrix. However, a prerequisite for GO to fulfill its function in the cement matrix is homogeneous dispersion. In this study, the effects of three different dispersing agents (DAs), including polycarboxylate-based high range water reducer (P-HRWR), naphthalene-based high range water reducer (N-HRWR), and air entraining agent (AEA) on the dispersion of GO in aqueous solution, simulated concrete pore solution (SCPS), and suspension of cement pastes were sequentially investigated. Results showed that the dispersion effect of GO in aqueous solutions was improved with different DAs. However, the homogeneous dispersion of GO in aqueous solution re-agglomerated in SCPS and suspension of cement pastes. It was concluded that as the cement content and pH of aqueous solutions increased, GOs re-agglomerated and precipitated in an alkaline solution. A possible mechanism was proposed in this study and it was believed that electrostatic interactions and steric hindrance provided by the P-HRWR further made GOs stable in aqueous solutions. The ions and pH of cement pastes increased with the increasing amount of cement, which caused the separation of P-HRWR from GOs. Therefore, GOs were re-agglomerated and absorbed on the surface of the cement particles, resulting in GOs sedimentation.
NASA Astrophysics Data System (ADS)
Jenni, A.; Gimmi, T.; Alt-Epping, P.; Mäder, U.; Cloet, V.
2017-06-01
Interactions between concrete and clays are driven by the strong chemical gradients in pore water and involve mineral reactions in both materials. In the context of a radioactive waste repository, these reactions may influence safety-relevant clay properties such as swelling pressure, permeability or radionuclide retention. Interfaces between ordinary Portland cement and Opalinus Clay show weaker, but more extensive chemical disturbance compared to a contact between low-pH cement and Opalinus Clay. As a consequence of chemical reactions porosity changes occur at cement-clay interfaces. These changes are stronger and may lead to complete pore clogging in the case of low-pH cements. The prediction of pore clogging by reactive transport simulations is very sensitive to the magnitude of diffusive solute fluxes, cement clinker chemistry, and phase reaction kinetics. For instance, the consideration of anion-depleted porosity in clays substantially influences overall diffusion and pore clogging at interfaces. A new concept of dual porosity modelling approximating Donnan equilibrium is developed and applied to an ordinary Portland cement - Opalinus Clay interface. The model predictions are compared with data from the cement-clay interaction (CI) field experiment in the Mt Terri underground rock laboratory (Switzerland), which represent 5 y of interaction. The main observations such as the decalcification of the cement at the interface, the Mg enrichment in the clay detached from the interface, and the S enrichment in the cement detached from the interface, are qualitatively predicted by the new model approach. The model results reveal multiple coupled processes that create the observed features. The quantitative agreement of modelled and measured data can be improved if uncertainties of key input parameters (tortuosities, reaction kinetics, especially of clay minerals) can be reduced.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Moeschner, Goeril; Lothenbach, Barbara; Figi, Renato
Citric acid can be used to retard the hydration of cement. Experiments were carried out to investigate the influence of citric acid on the composition of solid and liquid phases during cement hydration. Analyses of the solid phases showed that dissolution of alite and aluminate slowed down while analyses of the pore solution showed that citric acid was removed almost completely from the pore solution within the first hours of hydration. The complexation of the ions by citrate was weak, which could also be confirmed by thermodynamic calculations. Only 2% of the dissolved Ca and 0.001% of the dissolved Kmore » formed complexes with citrate during the first hours. Thus, citric acid retards cement hydration not by complex formation, but by slowing down the dissolution of the clinker grains. Thermodynamic calculations did not indicate precipitation of a crystalline citrate species. Thus, it is suggested that citrate sorbed onto the clinker surface and formed a protective layer around the clinker grains retarding their dissolution.« less
NASA Astrophysics Data System (ADS)
Asrah, Hidayati; Mirasa, Abdul Karim; Bolong, Nurmin
2018-02-01
This study investigated the mechanism of how POFA mitigated the ASR expansion. Two types of POFA; the UPOFA and GPOFA with different fineness were used to replace the cement at 20% and 40% and their effects on the mortar bar expansion, calcium hydroxide, alkali dilution, and calcium concentration were investigated. The results showed that UPOFA has a significant ability to mitigate the ASR, even at a lower level of replacement (20%) compared to GPOFA. The mechanism of UPOFA in mitigating the ASR expansion was through a reduction in the calcium hydroxide content, which produced low calcium concentration within the mortar pore solution. Low pore solution alkalinity signified that UPOFA had good alkali dilution effect. Meanwhile, a higher dosage of GPOFA was required to mitigate the ASR expansion. An increase in the pore solution alkalinity of GPOFA mortar indicated higher penetration of alkalis from the NaOH solution, which reduced the alkali dilution effect. However, this was compensated by the increase in the cement dilution effect at higher GPOFA replacement, which controlled the mortar bar expansion below the ASTM limit.
White, Claire E.; Olds, Daniel P.; Hartl, Monika; ...
2017-02-01
The long-term durability of cement-based materials is influenced by the pore structure and associated permeability at the sub-micrometre length scale. With the emergence of new types of sustainable cements in recent decades, there is a pressing need to be able to predict the durability of these new materials, and therefore nondestructive experimental techniques capable of characterizing the evolution of the pore structure are increasingly crucial for investigating cement durability. Here, small-angle neutron scattering is used to analyze the evolution of the pore structure in alkali-activated materials over the initial 24 h of reaction in order to assess the characteristic poremore » sizes that emerge during these short time scales. By using a unified fitting approach for data modeling, information on the pore size and surface roughness is obtained for a variety of precursor chemistries and morphologies (metakaolin- and slag-based pastes). Furthermore, the impact of activator chemistry is elucidatedviathe analysis of pastes synthesized using hydroxide- and silicate-based activators. It is found that the main aspect influencing the size of pores that are accessible using small-angle neutron scattering analysis (approximately 10–500 Å in diameter) is the availability of free silica in the activating solution, which leads to a more refined pore structure with smaller average pore size. Furthermore, as the reaction progresses the gel pores visible using this scattering technique are seen to increase in size.« less
NASA Astrophysics Data System (ADS)
Bede, Andrea; Ardelean, Ioan
2017-12-01
Varying the amount of water in a concrete mix will influence its final properties considerably due to the changes in the capillary porosity. That is why a non-destructive technique is necessary for revealing the capillary pore distribution inside hydrated cement based materials and linking the capillary porosity with the macroscopic properties of these materials. In the present work, we demonstrate a simple approach for revealing the differences in capillary pore size distributions introduced by the preparation of cement paste with different water-to-cement ratios. The approach relies on monitoring the nuclear magnetic resonance transverse relaxation distribution of cyclohexane molecules confined inside the cement paste pores. The technique reveals the whole spectrum of pores inside the hydrated cement pastes, allowing a qualitative and quantitative analysis of different pore sizes. The cement pastes with higher water-to-cement ratios show an increase in capillary porosity, while for all the samples the intra-C-S-H and inter-C-S-H pores (also known as gel pores) remain unchanged. The technique can be applied to various porous materials with internal mineral surfaces.
Influence of pore structure on compressive strength of cement mortar.
Zhao, Haitao; Xiao, Qi; Huang, Donghui; Zhang, Shiping
2014-01-01
This paper describes an experimental investigation into the pore structure of cement mortar using mercury porosimeter. Ordinary Portland cement, manufactured sand, and natural sand were used. The porosity of the manufactured sand mortar is higher than that of natural sand at the same mix proportion; on the contrary, the probable pore size and threshold radius of manufactured sand mortar are finer. Besides, the probable pore size and threshold radius increased with increasing water to cement ratio and sand to cement ratio. In addition, the existing models of pore size distribution of cement-based materials have been reviewed and compared with test results in this paper. Finally, the extended Bhattacharjee model was built to examine the relationship between compressive strength and pore structure.
Influence of Pore Structure on Compressive Strength of Cement Mortar
Zhao, Haitao; Xiao, Qi; Huang, Donghui
2014-01-01
This paper describes an experimental investigation into the pore structure of cement mortar using mercury porosimeter. Ordinary Portland cement, manufactured sand, and natural sand were used. The porosity of the manufactured sand mortar is higher than that of natural sand at the same mix proportion; on the contrary, the probable pore size and threshold radius of manufactured sand mortar are finer. Besides, the probable pore size and threshold radius increased with increasing water to cement ratio and sand to cement ratio. In addition, the existing models of pore size distribution of cement-based materials have been reviewed and compared with test results in this paper. Finally, the extended Bhattacharjee model was built to examine the relationship between compressive strength and pore structure. PMID:24757414
Enamel remineralization on teeth adjacent to Class II glass ionomer restorations.
Segura, A; Donly, K J; Stratmann, R G
1997-10-01
To examine the in vitro remineralization of incipient carious lesions on teeth adjacent interproximally to teeth with Class II glass ionomer cement restorations. Artificial carious lesions were created at the contact area of 30 teeth. Ten teeth had Class II glass ionomer cement/resin composite restorations placed, 10 teeth had Class II glass ionomer silver cermet restorations placed and 10 teeth had Class II amalgam restorations placed. Sections 100 microns thick were obtained longitudinally through the caries sites and polarized photomicrographs were taken in imbibition media of water and Thoulet's (R.I. 1.41 and 1.47) solutions, representing 5%, 10% and 25% pore volume respectively. Varnish was placed on the section, leaving only the external section site exposed, then sections were situated back into the original tooth. The restored teeth were abutted to the carious tooth so that the restorations came into contact with the adjacent restoration. The specimens were placed into closed environments of artificial saliva for 14 days, then were photographed again under polarized light and areas of the carious lesions were quantitated. An ANOVA indicated significant variance in adjacent tooth remineralization, when comparing the experimental groups, in imbibition media of water (P < 0.05), Thoulet's 1.41 solution (P < 0.008) and Thoulet's 1.47 solution (P < 0.006). Duncan's multiple range test demonstrated the glass ionomer cement/resin composite group to have significantly greater decrease in pore volume (P < 0.05) than the amalgam control group in water imbibition media and Thoulet's 1.47 media. There was no statistically significant difference between the glass ionomer cement/resin composite and glass ionomer silver cermet groups in these two imbibition media. The glass ionomer cement/resin composite group demonstrated significantly more (P < 0.05) decrease in pore volume than both the glass ionomer silver cermet group and amalgam control group in Thoulet's 1.47 imbibition media.
Relating the Electrical Resistance of Fresh Concrete to Mixture Proportions.
Obla, K; Hong, R; Sherman, S; Bentz, D P; Jones, S Z
2018-01-01
Characterization of fresh concrete is critical for assuring the quality of our nation's constructed infrastructure. While fresh concrete arriving at a job site in a ready-mixed concrete truck is typically characterized by measuring temperature, slump, unit weight, and air content, here the measurement of the electrical resistance of a freshly cast cylinder of concrete is investigated as a means of assessing mixture proportions, specifically cement and water contents. Both cement and water contents influence the measured electrical resistance of a sample of fresh concrete: the cement by producing ions (chiefly K + , Na + , and OH - ) that are the main source of electrical conduction; and the water by providing the main conductive pathways through which the current travels. Relating the measured electrical resistance to attributes of the mixture proportions, such as water-cement ratio by mass ( w/c ), is explored for a set of eleven different concrete mixtures prepared in the laboratory. In these mixtures, w/c , paste content, air content, fly ash content, high range water reducer dosage, and cement alkali content are all varied. Additionally, concrete electrical resistance data is supplemented by measuring the resistivity of its component pore solution obtained from 5 laboratory-prepared cement pastes with the same proportions as their corresponding concrete mixtures. Only measuring the concrete electrical resistance can provide a prediction of the mixture's paste content or the product w*c ; conversely, when pore solution resistivity is also available, w/c and water content of the concrete mixture can be reasonably assessed.
Relating the Electrical Resistance of Fresh Concrete to Mixture Proportions
Obla, K.; Hong, R.; Sherman, S.; Bentz, D.P.; Jones, S.Z.
2018-01-01
Characterization of fresh concrete is critical for assuring the quality of our nation’s constructed infrastructure. While fresh concrete arriving at a job site in a ready-mixed concrete truck is typically characterized by measuring temperature, slump, unit weight, and air content, here the measurement of the electrical resistance of a freshly cast cylinder of concrete is investigated as a means of assessing mixture proportions, specifically cement and water contents. Both cement and water contents influence the measured electrical resistance of a sample of fresh concrete: the cement by producing ions (chiefly K+, Na+, and OH-) that are the main source of electrical conduction; and the water by providing the main conductive pathways through which the current travels. Relating the measured electrical resistance to attributes of the mixture proportions, such as water-cement ratio by mass (w/c), is explored for a set of eleven different concrete mixtures prepared in the laboratory. In these mixtures, w/c, paste content, air content, fly ash content, high range water reducer dosage, and cement alkali content are all varied. Additionally, concrete electrical resistance data is supplemented by measuring the resistivity of its component pore solution obtained from 5 laboratory-prepared cement pastes with the same proportions as their corresponding concrete mixtures. Only measuring the concrete electrical resistance can provide a prediction of the mixture’s paste content or the product w*c; conversely, when pore solution resistivity is also available, w/c and water content of the concrete mixture can be reasonably assessed. PMID:29882546
NASA Astrophysics Data System (ADS)
Zerpa, L.; Gao, F.; Wang, S.
2017-12-01
There are two major types of natural gas hydrate distributions in porous media: pore filling and contact cementing. The difference between these two distribution types is related to hydrate nucleation and growth processes. In the pore filling distribution, hydrate nucleates from a gas-dissolved aqueous phase at the grain boundary and grows away from grain contacts and surfaces into the pore space. In the contact cementing distribution, hydrate nucleates and grows at the gas-water interface and at intergranular contacts. Previous attempts to correlate changes on porosity and permeability during hydrate formation/dissociation were based on the length difference between the pore body and pore throat, and only considered contact cementing hydrate distribution. This work consists of a study of mathematical models of permeability and porosity as a function of gas hydrate saturation during formation and dissociation of gas hydrates in porous media. In this work, first we derive the permeability equation for the pore filling hydrate deposition as a function of hydrate saturation. Then, a more comprehensive model considering both types of gas hydrate deposition is developed to represent changes in permeability and porosity during hydrate formation and dissociation. This resulted in a model that combines pore filling and contact cementing deposition types in the same reservoir. Finally, the TOUGH+Hydrate numerical reservoir simulator was modified to include these models to analyze the response of production and saturation during a depressurization process, considering different combinations of pore filling and contact cementing hydrate distributions. The empirical exponent used in the permeability adjustment factor model influences both production profile and saturation results. This empirical factor describes the permeability dependence to changes in porosity caused by solid phase formation in the porous medium. The use of the permeability exponent decreases the permeability of the system for a given hydrate saturation, which affects the hydraulic performance of the system. However, from published experimental work, there is only a rough estimation of this permeability exponent. This factor could be represented with an empirical equation if more laboratory and field data becomes available.
NASA Astrophysics Data System (ADS)
Bouniol, P.; Guillot, W.; Dauvois, V.; Dridi, W.; Le Caër, S.
2018-09-01
Blended cements with high content of blast furnace slag (CEM III/C) can be used for nuclear waste conditioning because of their low hydration heat as compared to ordinary Portland cements (CEM I). They however contain some sulfide, an impurity whose role needs to be investigated. Indeed, they can have an effect on the radiolytic H2 production under irradiation. To study the impact of sulfide species on H2 production, gamma irradiation, at a dose rate of 356 Gy h-1, was performed during 6 months in a closed system without O2 on a cement paste made with CEM III/C. At short time, the radiolytic H2 production rate is higher than that measured using CEM I. On the basis of reaction data collected in the literature on sulfur species, radiolysis simulations performed for both systems confirm this behavior. Moreover, they suggest that the sulfide concentration, initially imposed in pore solution by the slag is of the order of 180 mM, and is responsible for this H2 production. For the first two irradiation months, the following phenomena are then evidenced in CEM III/C: 1) conversion of sulfide into polysulfide anions; 2) pH increase; 3) production of H2 due to the H•+ H2S reaction having a very high rate constant. Nevertheless, in the medium term, the residual sulfide concentration is not sufficient any more for this mechanism to occur. It imposes a reducing environment, leading to a very efficient recombination of H2 in pore solution. The resulting equilibrium state is reinforced by the high liquid saturation level in the cement paste porosity. Therefore, even if the presence of sulfide species in blended cements momentarily increases the H2 production rate, it strongly reduces it at long times.
Porosity of different dental luting cements.
Milutinović-Nikolić, Aleksandra D; Medić, Vesna B; Vuković, Zorica M
2007-06-01
The aim of this in vitro study was to compare open porosity and pore size distribution of different types of luting cements (zinc phosphate and polycarboxylate produced by Harvard Cement, Great Britain, glass-ionomer product GC Fuji I, GC Corporation, Japan, and Panavia F, resin based composite cement, Kurraray Co. Ltd. Japan) using mercury intrusion porosimetry and use it as an additional parameter for ranging the quality of cements used in prosthetics. Samples were hand mixed in accordance with the manufacturer's instructions and formed in cylindrical test specimens. Density of samples was determined using a pycnometer while porous structure was estimated using high pressure mercury intrusion porosimeter enabling estimation of pore diameters in interval 7.5-15,000 nm. The polycarboxylate cement posses the highest porosity and specific pore volume among investigated cements. By comparison of the results obtained for zinc phosphate and glass-ionomer cement, it can be observed that according to some textural properties zinc phosphate cement is better choice (smaller specific pore volume and absence of macropores larger than 1 microm) while according to other textural properties the glass-ionomer has advantage (smaller porosity). The resin based composite cement poses the most desired porous structure for prosthetic application among the investigated cements (the lowest porosity and specific pore volume and all identified pores are smaller than 20 nm). Based on results of this study, it is possible to estimate the efficiency of luting cements to protect the interior of tooth from penetration of oral fluids, bacteria and bacterial toxins into unprotected dentine.
Alkali activated slag mortars provide high resistance to chloride-induced corrosion of steel
NASA Astrophysics Data System (ADS)
Criado, Maria; Provis, John L.
2018-06-01
The pore solutions of alkali-activated slag cements and Portland-based cements are very different in terms of their chemical and redox characteristics, particularly due to the high alkalinity and high sulfide content of alkali-activated slag cement. Therefore, differences in corrosion mechanisms of steel elements embedded in these cements could be expected, with important implications for the durability of reinforced concrete elements. This study assesses the corrosion behaviour of steel embedded in alkali-activated blast furnace slag (BFS) mortars exposed to alkaline solution, alkaline chloride-rich solution, water, and standard laboratory conditions, using electrochemical techniques. White Portland cement (WPC) mortars and blended cement mortars (white Portland cement and blast furnace slag) were also tested for comparative purposes. The steel elements embedded in immersed alkali-activated slag mortars presented very negative redox potentials and high apparent corrosion current values; the presence of sulfide reduced the redox potential, and the oxidation of the reduced sulfur-containing species within the cement itself gave an electrochemical signal that classical electrochemical tests for reinforced concrete durability would interpret as being due to steel corrosion processes. However, the actual observed resistance to chloride-induced corrosion was very high, as measured by extraction and characterisation of the steel at the end of a 9-month exposure period, whereas the steel embedded in white Portland cement mortars was significantly damaged under the same conditions.
Pore-scale Modeling of CO2 Local Trapping in Heterogeneous Porous Media with Inter-granular Cements
NASA Astrophysics Data System (ADS)
Wang, D.; Li, Y.
2017-12-01
Based on pore-scale modeling of CO2/brine multiphase flow in heterogeneous porous media with inter-granular cements, we numerically analyze the effects of cement-modified pore structure on CO2 local trapping. Results indicate: 1) small pore throat is the main reason for causing CO2 local trapping in front of low-porosity layers (namely dense layers) formed by inter-granular cements; 2) in the case of the same pore throat size, the smaller particle size can increase the number of flow paths for CO2 plume and equivalently enhances local permeability, which may counteract the impediment of high capillary pressure on CO2 migration to some extent and consequently disables CO2 local capillary trapping; 3) the isolated pores by inter-granular cements can lead to dramatic reduction of CO2 saturation inside the dense layers, whereas the change of connectivity of some pores due to the cements can increase CO2 accumulation in front of the dense layers by lowering the displacement area of CO2 plume.
OPC Paste Samples Exposed To Aggressive Solutions. Cementitious Barriers Partnership
DOE Office of Scientific and Technical Information (OSTI.GOV)
Langton, C.
2014-11-01
The study presented in this report focused on a low-activity wasteform containing a high-pH pore solution with a significant level of sulfate. The purpose of the study was to improve understanding of the complex concrete/wasteform reactive transport problem, in particular, the role of pH in sulfate attack. Paste samples prepared at three different water-to-cement ratios were tested. The mixtures were prepared with ASTM Type I cement, without additional admixtures. The samples were exposed to two different sodium sulfate contact solutions. The first solution was prepared at 0.15M Na 2SO 4. The second solution also incorporated 0.5M NaOH, to mimic themore » high pH conditions found in Saltstone. The data collected indicated that, in Na 2SO 4 solution, damage occurs to the pastes. In the case of the high-pH sulfate solution (Na 2SO 4 + NaOH), no signs of damage were observed on any of the paste mixtures. These results indicate that the high sulfate content found in the wasteform pore solution will not necessarily lead to severe damage to concrete. Good-quality mixtures could thus prove durable over the long term, and act as an effective barrier to prevent radionuclides from reaching the environment.« less
Wellbore Cement Porosity Evolution in Response to Mineral Alteration during CO 2 Flooding
Cheshire, Michael C.; Stack, Andrew G.; Carey, J. William; ...
2016-12-13
Mineral reactions during CO 2 sequestration will change the pore-size distribution and pore surface characteristics, complicating permeability and storage security predictions. In this study, we report a small/wide angle scattering study of wellbore cement that has been exposed to carbon dioxide for three decades. We have constructed detailed contour maps that describe local porosity distributions and the mineralogy of the sample and relate these quantities to the carbon dioxide reaction front on the cement. We find that the initial bimodal distribution of pores in the cement, 1–2 and 10–20 nm, is affected differently during the course of carbonation reactions. Initialmore » dissolution of cement phases occurs in the 10–20 nm pores and leads to the development of new pore spaces that are eventually sealed by CaCO 3 precipitation, leading to a loss of gel and capillary nanopores, smoother pore surfaces, and reduced porosity. This suggests that during extensive carbonation of wellbore cement, the cement becomes less permeable because of carbonate mineral precipitation within the pore space. Additionally, the loss of gel and capillary nanoporosities will reduce the reactivity of cement with CO 2 due to reactive surface area loss. Finally, this work demonstrates the importance of understanding not only changes in total porosity but also how the distribution of porosity evolves with reaction that affects permeability.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Cheshire, Michael C.; Stack, Andrew G.; Carey, J. William
Mineral reactions during CO 2 sequestration will change the pore-size distribution and pore surface characteristics, complicating permeability and storage security predictions. In this study, we report a small/wide angle scattering study of wellbore cement that has been exposed to carbon dioxide for three decades. We have constructed detailed contour maps that describe local porosity distributions and the mineralogy of the sample and relate these quantities to the carbon dioxide reaction front on the cement. We find that the initial bimodal distribution of pores in the cement, 1–2 and 10–20 nm, is affected differently during the course of carbonation reactions. Initialmore » dissolution of cement phases occurs in the 10–20 nm pores and leads to the development of new pore spaces that are eventually sealed by CaCO 3 precipitation, leading to a loss of gel and capillary nanopores, smoother pore surfaces, and reduced porosity. This suggests that during extensive carbonation of wellbore cement, the cement becomes less permeable because of carbonate mineral precipitation within the pore space. Additionally, the loss of gel and capillary nanoporosities will reduce the reactivity of cement with CO 2 due to reactive surface area loss. Finally, this work demonstrates the importance of understanding not only changes in total porosity but also how the distribution of porosity evolves with reaction that affects permeability.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Prinčič, Tina, E-mail: Tina.Princic@uni-lj.si; Štukovnik, Petra; Pejovnik, Stane
2013-12-15
Some carbonate aggregates used in concrete are unstable in a high alkaline solution, which is present also in pore solution of cement binder. This paper investigates the process of dedolomitization of carbonate aggregate rocks and mortar bars. Selected aggregates, limestone and dolostone are of high purity without reactive silica involvement confirmed by the XRD and the XRF. For the process of dedolomitization the effect of various temperatures, solutions and time was examined. In this investigation, measurements of expansion, optical and scanning electron microscopy (SEM), energy dispersive spectrometry (EDS) and X-ray diffraction were used. Te results indicate that the process ofmore » dedolomitization occurred not only in the NaOH solution but also in the water on the mortar bar with virgin dolostone aggregate. Elevated temperature, 60 °C, increased the rate of reaction. Furthermore, the rate of reaction significantly correlates with time, which has also been confirmed through the Rietveld analysis. -- Highlights: •The dedolomitization caused no expansion. •It occurs in the dolostone aggregate without reactive silica involvement. •It has taken place already with the presence of the cement binder. •A significant alteration occurred: formation of rims, new pores and phases.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Krupka, K.M.; Serne, R.J.
The US Nuclear Regulatory Commission is developing a technical position document that provides guidance regarding the performance assessment of low-level radioactive waste disposal facilities. This guidance considers the effects that the chemistry of the vault disposal system may have on radionuclide release. The geochemistry of pore waters buffered by cementitious materials in the disposal system will be different from the local ground water. Therefore, the cement-buffered environment needs to be considered within the source term calculations if credit is taken for solubility limits and/or sorption of dissolved radionuclides within disposal units. A literature review was conducted on methods to modelmore » pore-water compositions resulting from reactions with cement, experimental studies of cement/water systems, natural analogue studies of cement and concrete, and radionuclide solubilities experimentally determined in cement pore waters. Based on this review, geochemical modeling was used to calculate maximum concentrations for americium, neptunium, nickel, plutonium, radium, strontium, thorium, and uranium for pore-water compositions buffered by cement and local ground-water. Another literature review was completed on radionuclide sorption behavior onto fresh cement/concrete where the pore water pH will be greater than or equal 10. Based on this review, a database was developed of preferred minimum distribution coefficient values for these radionuclides in cement/concrete environments.« less
Effect of Nano-SiO₂ on the Hydration and Microstructure of Portland Cement.
Wang, Liguo; Zheng, Dapeng; Zhang, Shupeng; Cui, Hongzhi; Li, Dongxu
2016-12-15
This paper systematically studied the modification of cement-based materials by nano-SiO₂ particles with an average diameter of about 20 nm. In order to obtain the effect of nano-SiO₂ particles on the mechanical properties, hydration, and pore structure of cement-based materials, adding 1%, 3%, and 5% content of nano-SiO₂ in cement paste, respectively. The results showed that the reaction of nano-SiO₂ particles with Ca(OH)₂ (crystal powder) started within 1 h, and formed C-S-H gel. The reaction speed was faster after aging for three days. The mechanical properties of cement-based materials were improved with the addition of 3% nano-SiO₂, and the early strength enhancement of test pieces was obvious. Three-day compressive strength increased 33.2%, and 28-day compressive strength increased 18.5%. The exothermic peak of hydration heat of cement increased significantly after the addition of nano-SiO₂. Appearance time of the exothermic peak was advanced and the total heat release increased. Thermogravimetric-differential scanning calorimetry (TG-DSC) analysis showed that nano-SiO₂ promoted the formation of C-S-H gel. The results of mercury intrusion porosimetry (MIP) showed that the total porosity of cement paste with 3% nano-SiO₂ was reduced by 5.51% and 5.4% at three days and 28 days, respectively, compared with the pure cement paste. At the same time, the pore structure of cement paste was optimized, and much-detrimental pores and detrimental pores decreased, while less harmful pores and innocuous pores increased.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bossa, Nathan; Chaurand, Perrine; Levard, Clément
Nanomaterials are increasingly being used to improve the properties and functions of common building materials. A new type of self-cleaning cement incorporating TiO 2 nanomaterials (TiO 2-NMs) with photocatalytic properties is now marketed. This promising cement might provide air pollution-reducing properties but its environmental impact must be validated. During cement use and aging, an altered surface layer is formed that exhibits increased porosity. The surface layer thickness alteration and porosity increase with the cement degradation rate. The hardened cement paste leaching behavior has been fully documented, but the fate of incorporated TiO 2-NMs and their state during/after potential release ismore » currently unknown. In this study, photocatalytic cement pastes with increasing initial porosity were leached at a lab-scale to produce a range of degradation rates concerning the altered layer porosity and thickness. No dissolved Ti was released during leaching, only particulate TiO 2-NM release was detected. The extent of release from this batch test simulating accelerated worst-case scenario was limited and ranged from 18.7 ± 2.1 to 33.5 ± 5.1 mg of Ti/m 2 of cement after 168 h of leaching. TiO 2-NMs released into neutral aquatic media (simulate pH of surface water) were not associated or coated by cement minerals. The TiO 2-NM release mechanism is suspected to start from freeing of TiO 2-NMs in the altered layer pore network due to partial cement paste dissolution followed by diffusion into the bulk pore solution to the surface. The extent of TiO 2-NM release was not solely related to the cement degradation rate.« less
Early-age hydration and volume change of calcium sulfoaluminate cement-based binders
NASA Astrophysics Data System (ADS)
Chaunsali, Piyush
Shrinkage cracking is a predominant deterioration mechanism in structures with high surface-to-volume ratio. One way to allay shrinkage-induced stresses is to use calcium sulfoaluminate (CSA) cement whose early-age expansion in restrained condition induces compressive stress that can be utilized to counter the tensile stresses due to shrinkage. In addition to enhancing the resistance against shrinkage cracking, CSA cement also has lower carbon footprint than that of Portland cement. This dissertation aims at improving the understanding of early-age volume change of CSA cement-based binders. For the first time, interaction between mineral admixtures (Class F fly ash, Class C fly ash, and silica fume) and OPC-CSA binder was studied. Various physico-chemical factors such as the hydration of ye'elimite (main component in CSA cement), amount of ettringite (the main phase responsible for expansion in CSA cement), supersaturation with respect to ettringite in cement pore solution, total pore volume, and material stiffness were monitored to examine early-age expansion characteristics. This research validated the crystallization stress theory by showing the presence of higher supersaturation level of ettringite, and therefore, higher crystallization stress in CSA cement-based binders. Supersaturation with respect to ettringite was found to increase with CSA dosage and external supply of gypsum. Mineral admixtures (MA) altered the expansion characteristics in OPC-CSA-MA binders with fixed CSA cement. This study reports that fly ash (FA) behaves differently depending on its phase composition. The Class C FA-based binder (OPC-CSA-CFA) ceased expanding beyond two days unlike other OPC-CSA-MA binders. Three factors were found to govern expansion of CSA cement-based binders: 1) volume fraction of ettringite in given pore volume, 2) saturation level of ettringite, and 3) dynamic modulus. Various models were utilized to estimate the macroscopic tensile stress in CSA cement-based binders without taking into account the viscoelastic effects. For the first time, model based on poromechanics was used to calculate the macroscopic tensile stress that develops in CSA cement-based binders due to crystallization of ettringite. The models enabled a reasonable prediction of tensile stress due to crystallization of ettringite including the failure of an OPC-CSA binder which had high CSA cement content. Elastic strain based on crystallization stress was calculated and compared with the observed strain. A mismatch between observed and calculated elastic strain indicated the presence of early-age creep. Lastly, the application of CSA cement in concretes is discussed to link the paste and concrete behavior.
Effect of Nano-SiO2 on the Hydration and Microstructure of Portland Cement
Wang, Liguo; Zheng, Dapeng; Zhang, Shupeng; Cui, Hongzhi; Li, Dongxu
2016-01-01
This paper systematically studied the modification of cement-based materials by nano-SiO2 particles with an average diameter of about 20 nm. In order to obtain the effect of nano-SiO2 particles on the mechanical properties, hydration, and pore structure of cement-based materials, adding 1%, 3%, and 5% content of nano-SiO2 in cement paste, respectively. The results showed that the reaction of nano-SiO2 particles with Ca(OH)2 (crystal powder) started within 1 h, and formed C–S–H gel. The reaction speed was faster after aging for three days. The mechanical properties of cement-based materials were improved with the addition of 3% nano-SiO2, and the early strength enhancement of test pieces was obvious. Three-day compressive strength increased 33.2%, and 28-day compressive strength increased 18.5%. The exothermic peak of hydration heat of cement increased significantly after the addition of nano-SiO2. Appearance time of the exothermic peak was advanced and the total heat release increased. Thermogravimetric-differential scanning calorimetry (TG-DSC) analysis showed that nano-SiO2 promoted the formation of C–S–H gel. The results of mercury intrusion porosimetry (MIP) showed that the total porosity of cement paste with 3% nano-SiO2 was reduced by 5.51% and 5.4% at three days and 28 days, respectively, compared with the pure cement paste. At the same time, the pore structure of cement paste was optimized, and much-detrimental pores and detrimental pores decreased, while less harmful pores and innocuous pores increased. PMID:28335369
NASA Astrophysics Data System (ADS)
Perron, Stacey
Harsh Canadian winters cause many problems in reinforced concrete structures due to damaging freezing-thawing cycles which is exacerbated by the heavy use of de-icing salts on roadways. Evaluation of concrete durability with current ASTM methods may give unreliable results and are destructive to the structure. A relatively new and novel approach to evaluating the durability of concrete uses A. C. Impedance Spectroscopy (ACIS). Hydrated cement paste (hcp), mortar, brick and vycor glass were evaluated using ACIS during drying-rewetting and freezing-thawing cycles. Thermal mechanical analysis (TMA), and differential scanning calorimetry (DSC) tests were also conducted and used as references. Results indicate that ACIS can be used to successfully evaluate the pore structure of hcp. The results from the drying-rewetting cycles are consistent with the pore coarsening theory. ACIS revealed pore structure changes consistent with the mechanical strains and pore solution chemistry. Increased pore continuity with each drying-rewetting cycle was indicated by a reduction in sample resistance. Unique tests were conducted on hydrated cement paste, mortar, brick and vycor glass that measured the ACIS and mechanical strains simultaneously while undergoing temperature changes. The temperature was lowered from 5°C to -80°C and then raised to +20°C. The ACIS results indicate that durability of the material can be assessed using the parameters R, material resistance, and phi, indicative of the frequency dispersion angle. The resistance on freezing values correlates with the amount of pore water freezing. The phi values on freezing are representative of the pore size distribution of the test sample. Resistance and phi data from freezing-thawing tests can be analyzed to assess durability of the sample. A material that is durable to freezing-thawing cycles can be described as having a high resistance at room temperature, a low freezing resistance and small changes in phi. Results were consistent among all the materials tested. Freezing-thawing tests were also conducted on specimens resaturated with salt solutions (5%, 10%, 15%). The results of these tests indicated a lower incipient freezing temperature, increase in pore blockage temperatures, and increased mobility of the pore water during freezing (increase in the change to phi). A series of test were conducted to evaluate the electrode polarization effects associated with the permittivity values at low frequencies. Teflon sheets were used to minimize the electrode polarization effects. It is shown that electrode polarization effects dominate over bulk polarization effects. Effects vary with the porosity of the material.
Impact of spatially correlated pore-scale heterogeneity on drying porous media
NASA Astrophysics Data System (ADS)
Borgman, Oshri; Fantinel, Paolo; Lühder, Wieland; Goehring, Lucas; Holtzman, Ran
2017-07-01
We study the effect of spatially-correlated heterogeneity on isothermal drying of porous media. We combine a minimal pore-scale model with microfluidic experiments with the same pore geometry. Our simulated drying behavior compares favorably with experiments, considering the large sensitivity of the emergent behavior to the uncertainty associated with even small manufacturing errors. We show that increasing the correlation length in particle sizes promotes preferential drying of clusters of large pores, prolonging liquid connectivity and surface wetness and thus higher drying rates for longer periods. Our findings improve our quantitative understanding of how pore-scale heterogeneity impacts drying, which plays a role in a wide range of processes ranging from fuel cells to curing of paints and cements to global budgets of energy, water and solutes in soils.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bossa, Nathan, E-mail: bossanathan@gmail.com; INERIS, Parc Technologique Alata, BP2, 60550 Verneuil-en-Halatte; iCEINT, CNRS, Duke Univ. International Consortium for the Environmental Implications of Nanotechnology, Aix-en-Provence
2015-01-15
Pore structure of leached cement pastes (w/c = 0.5) was studied for the first time from micro-scale down to the nano-scale by combining micro- and nano-X-ray computed tomography (micro- and nano-CT). This allowed assessing the 3D heterogeneity of the pore network along the cement profile (from the core to the altered layer) of almost the entire range of cement pore size, i.e. from capillary to gel pores. We successfully quantified an increase of porosity in the altered layer at both resolutions. Porosity is increasing from 1.8 to 6.1% and from 18 to 58% at the micro-(voxel = 1.81 μm) andmore » nano-scale (voxel = 63.5 nm) respectively. The combination of both CT allowed to circumvent weaknesses inherent of both investigation scales. In addition the connectivity and the channel size of the pore network were also evaluated to obtain a complete 3D pore network characterization at both scales.« less
Tiruta-Barna, Ligia; Fantozzi-Merle, Catherine; de Brauer, Christine; Barna, Radu
2006-11-16
The aim of this paper is the investigation of the leaching behaviour of different porous materials containing organic pollutants (PAH: naphthalene and phenanthrene). The assessment methodology of long term leaching behaviour of inorganic materials was extended to cement solidified organic pollutants. Based on a scenario-approach considering environmental factors, matrix and pollutants specificities, the applied methodology is composed of adapted equilibrium and dynamic leaching tests. The contributions of different physical and chemical mechanisms were identified and the leaching behaviour was modelled. The physical parameters of the analysed reference and polluted materials are similar. A difference in the pore size distribution appears for higher naphthalene content. The solubility of the PAH contained in the material is affected by the ionic strength and by the presence of a co-solvent; the solution pH does not influence PAH solubility. The solubility of the major mineral species is not influenced by the presence of the two PAH nor by the presence of the methanol as co-solvent in the range of the tested material compositions. In the case of the leaching of a monolith material the main transport mechanism is the diffusion in the porous system. For both mineral and organic species we observed at least two dynamic domains. At the beginning of the leaching process the released flux is due to the surface dissolution and to the diffusion of the main quantity dissolved in the initial pore solution. The second period is governed by a stationary regime between dissolution in pore water and diffusion. The model, coupling transport and chemical phenomena in the pore solution, at the monolith surface and in the leachate simulates satisfactory the release for both mineral and organic species.
α-TCP cements prepared by syringe-foaming: Influence of Na2HPO4 and surfactant concentration.
Vásquez, A F; Domínguez, S; Loureiro Dos Santos, L A
2017-12-01
The lack of intrinsic open porosity in calcium phosphate cements slows down the resorption rate and bone ingrowth when implanted In Vivo. In this study, macroporous structures were obtained by mixing α-TCP cement with a foamed liquid phase containing different concentrations of sodium hydrogen phosphate and a nonionic surfactant. The cement paste was prepared by hand mixing in a novel system of two syringes connected by a tube. Two different liquid to powder (L/P) ratios were used to prepare the cement paste. The cement samples showed open macropores with diameters>100μm. The specimens prepared with lower L/P ratio showed smaller porosity, macroporosity and pore size distribution. The cohesion of the cement paste in liquid solutions was assessed by adding 2wt% sodium alginate to the liquid phase. This study suggests that the final macrostructure of the foamed cements can be controlled by varying the phosphate and surfactant concentrations in the liquid phase and the L/P ratio. Copyright © 2017 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Olmeda, Javier; Henocq, Pierre; Giffaut, Eric; Grivé, Mireia
2017-06-01
The present work describes a thermodynamic model based on pore water replacement cycles to simulate the chemical evolution of blended cement (BFS + FA) by interaction with external Callovo-Oxfordian (COx) pore water. In the framework of the radioactive waste management, the characterization of the radionuclide behaviour (solubility/speciation, adsorption) in cementitious materials needs to be done for several chemical degradation states (I to IV). In particular, in the context of the deep geological radioactive waste disposal project (Cigéo), cement-based materials will be chemically evolved with time in contact with the host-rock (COx formation). The objective of this study is to provide an equilibrium solution composition for each degradation state for a CEM-V cement-based material to support the adsorption and diffusion experiments reproducing any state of degradation. Calculations have been performed at 25 °C using the geochemical code PhreeqC and an up-to-date thermodynamic database (ThermoChimie v.9.0.b) coupled to SIT approach for ionic strength correction. The model replicates experimental data with accuracy. The approach followed in this study eases the analysis of the chemical evolution in both aqueous and solid phase to obtain a fast assessment of the geochemical effects associated to an external water intrusion of variable composition on concrete structures.
Rinehart, Alex J.; Dewers, Thomas A.; Broome, Scott T.; ...
2016-08-25
We characterize geomechanical constitutive behavior of reservoir sandstones at conditions simulating the “Cranfield” Southeast Regional Carbon Sequestration Partnership injection program. From two cores of Lower Tuscaloosa Formation, three sandstone lithofacies were identified for mechanical testing based on permeability and lithology. These include: chlorite-cemented conglomeratic sandstone (Facies A); quartz-cemented fine sandstone (Facies B); and quartz- and calcite-cemented very fine sandstone (Facies C). We performed a suite of compression tests for each lithofacies at 100 °C and pore pressure of 30 MPa, including hydrostatic compression and triaxial tests at several confining pressures. Plugs were saturated with supercritical CO 2-saturated brine. Chemical environmentmore » affected the mechanical response of all three lithofacies, which experience initial plastic yielding at stresses far below estimated in situ stress. Measured elastic moduli degradation defines a secondary yield surface coinciding with in situ stress for Facies B and C. Facies A shows measurable volumetric creep strain and a failure envelope below estimates of in situ stress, linked to damage of chlorite cements by acidic pore solutions. Furthermore, the substantial weakening of a particular lithofacies by CO 2 demonstrates a possible chemical-mechanical coupling during injection at Cranfield with implications for CO 2 injection, reservoir permeability stimulation, and enhanced oil recovery.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kunther, Wolfgang; Lothenbach, Barbara; Skibsted, Jørgen, E-mail: jskib@chem.au.dk
2015-03-15
The effect of the Ca/Si ratio of the calcium–silicate–hydrate (C–S–H) phase on the interaction with sulfate ions is investigated for C–S–H phases (Ca/Si = 0.83, 1.25, 1.50) and mortar samples of blended Portland cements. It is shown that leaching of calcium from C–S–H and portlandite affects the composition of the pore solution and contributes to the developing crystallization pressure of ettringite. Sulfate profiles show that sulfate binding before cracking is similar for different Ca/Si ratios whereas the highest expansion rates are observed for the mortars with the highest Ca/Si ratios. After leaching in sulfate solutions, the C–S–H samples have beenmore » characterized by {sup 29}Si MAS NMR, thermogravimetric analysis, and elemental solution analysis. Generally, the exposure to sulfate solutions results in decalcification of the C–S–H, which increases with decreasing Ca/Si ratio. The data are in good agreement with thermodynamic modeling, indicating that equilibrium is almost achieved in the leached systems. Finally, the expansion of mortar samples exposed to sulfate solutions was much less at lower Ca/Si ratios of the cement blends. This reduced expansion can be related to the decrease of the supersaturation of the pore solution with respect to ettringite at lower Ca/Si ratios of the C–S–H and in the absence of portlandite.« less
Cheng, An; Chao, Sao-Jeng; Lin, Wei-Ting
2013-01-01
Leaching of calcium ions increases the porosity of cement-based materials, consequently resulting in a negative effect on durability since it provides an entry for aggressive harmful ions, causing reinforcing steel corrosion. This study investigates the effects of leaching behavior of calcium ions on the compression and durability of cement-based materials. Since the parameters influencing the leaching behavior of cement-based materials are unclear and diverse, this paper focuses on the influence of added mineral admixtures (fly ash, slag and silica fume) on the leaching behavior of calcium ions regarding compression and durability of cemented-based materials. Ammonium nitrate solution was used to accelerate the leaching process in this study. Scanning electron microscopy, X-ray diffraction analysis, and thermogravimetric analysis were employed to analyze and compare the cement-based material compositions prior to and after calcium ion leaching. The experimental results show that the mineral admixtures reduce calcium hydroxide quantity and refine pore structure through pozzolanic reaction, thus enhancing the compressive strength and durability of cement-based materials. PMID:28809247
Properties of Cement Mortar Produced from Mixed Waste Materials with Pozzolanic Characteristics.
Yen, Chi-Liang; Tseng, Dyi-Hwa; Wu, Yue-Ze
2012-07-01
Waste materials with pozzolanic characteristics, such as sewage sludge ash (SSA), coal combustion fly ash (FA), and granulated blast furnace slag (GBS), were reused as partial cement replacements for making cement mortar in this study. Experimental results revealed that with dual replacement of cement by SSA and GBS and triple replacement by SSA, FA, and GBS at 50% of total cement replacement, the compressive strength (Sc) of the blended cement mortars at 56 days was 93.7% and 92.9% of the control cement mortar, respectively. GBS had the highest strength activity index value and could produce large amounts of CaO to enhance the pozzolanic activity of SSA/FA and form calcium silicate hydrate gels to fill the capillary pores of the cement mortar. Consequently, the Sc development of cement mortar with GBS replacement was better than that without GBS, and the total pore volume of blended cement mortars with GBS/SSA replacement was less than that with FA/SSA replacement. In the cement mortar with modified SSA and GBS at 70% of total cement replacement, the Sc at 56 days was 92.4% of the control mortar. Modifying the content of calcium in SSA also increased its pozzolanic reaction. CaCl(2) accelerated the pozzolanic activity of SSA better than lime did. Moreover, blending cement mortars with GBS/SSA replacement could generate more monosulfoaluminate to fill capillary pores.
Properties of Cement Mortar Produced from Mixed Waste Materials with Pozzolanic Characteristics
Yen, Chi-Liang; Tseng, Dyi-Hwa; Wu, Yue-Ze
2012-01-01
Abstract Waste materials with pozzolanic characteristics, such as sewage sludge ash (SSA), coal combustion fly ash (FA), and granulated blast furnace slag (GBS), were reused as partial cement replacements for making cement mortar in this study. Experimental results revealed that with dual replacement of cement by SSA and GBS and triple replacement by SSA, FA, and GBS at 50% of total cement replacement, the compressive strength (Sc) of the blended cement mortars at 56 days was 93.7% and 92.9% of the control cement mortar, respectively. GBS had the highest strength activity index value and could produce large amounts of CaO to enhance the pozzolanic activity of SSA/FA and form calcium silicate hydrate gels to fill the capillary pores of the cement mortar. Consequently, the Sc development of cement mortar with GBS replacement was better than that without GBS, and the total pore volume of blended cement mortars with GBS/SSA replacement was less than that with FA/SSA replacement. In the cement mortar with modified SSA and GBS at 70% of total cement replacement, the Sc at 56 days was 92.4% of the control mortar. Modifying the content of calcium in SSA also increased its pozzolanic reaction. CaCl2 accelerated the pozzolanic activity of SSA better than lime did. Moreover, blending cement mortars with GBS/SSA replacement could generate more monosulfoaluminate to fill capillary pores. PMID:22783062
NASA Astrophysics Data System (ADS)
Tunstall, Lori Elizabeth
Air voids are deliberately introduced into concrete to provide resistance against frost damage. However, our ability to control air distribution in both traditional and nontraditional concrete is hindered by the limited amount of research available on air-entraining agent (AEA) interaction with both the solid and solution components of these systems. This thesis seeks to contribute to the information gap in several ways. Using tensiometry, we are able to quantify the adsorption capacity of cement, fly ash, and fly ash carbon for four commercial AEAs. These results indicate that fly ash interference with air entrainment is due to adsorption onto the glassy particles tucked inside carbon, rather than adsorption onto the carbon itself. Again using tensiometry, we show that two of the AEA show a stronger tendency to micellize and to interact with calcium ions than the others, which seems to be linked to the freezing behavior in mortars, since mortars made with these AEA require smaller dosages to achieve similar levels of protection. We evaluate the frost resistance of cement and cement/fly ash mortars by measuring the strain in the body as it is cooled and reheated. All of the mortars show some expansion at temperatures ≥ -42 °C. Many of the cement mortars are able to maintain net compression during this expansion, but none of the fly ash mortars maintain net compression once expansion begins. Frost resistance improves with an increase in AEA dosage, but no correlation is seen between frost resistance and the air void system. Thus, another factor must contribute to frost resistance, which we propose is the microstructure of the shell around the air void. The strain behavior is attributed to ice growth surrounding the void, which can plug the pores in the shell and reduce or eliminate the negative pore pressure induced by the ice inside the air void; the expansion would then result from the unopposed crystallization pressure, but this must be verified by future work. If the shell has numerous, tiny pores it is more difficult to eliminate suction, since more ice is needed to plug all the pores.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhou Jian, E-mail: Jian.Zhou@tudelft.n; Ye Guang, E-mail: g.ye@tudelft.n; Magnel Laboratory for Concrete Research, Department of Structural Engineering, Ghent University, Technologiepark-Zwijnaarde 904 B-9052, Ghent
2010-07-15
Numerous mercury intrusion porosimetry (MIP) studies have been carried out to investigate the pore structure in cement-based materials. However, the standard MIP often results in an underestimation of large pores and an overestimation of small pores because of its intrinsic limitation. In this paper, an innovative MIP method is developed in order to provide a more accurate estimation of pore size distribution. The new MIP measurements are conducted following a unique mercury intrusion procedure, in which the applied pressure is increased from the minimum to the maximum by repeating pressurization-depressurization cycles instead of a continuous pressurization followed by a continuousmore » depressurization. Accordingly, this method is called pressurization-depressurization cycling MIP (PDC-MIP). By following the PDC-MIP testing sequence, the volumes of the throat pores and the corresponding ink-bottle pores can be determined at every pore size. These values are used to calculate pore size distribution by using the newly developed analysis method. This paper presents an application of PDC-MIP on the investigation of the pore size distribution in cement-based materials. The experimental results of PDC-MIP are compared with those measured by standard MIP. The PDC-MIP is further validated with the other experimental methods and numerical tool, including nitrogen sorption, backscanning electron (BSE) image analysis, Wood's metal intrusion porosimetry (WMIP) and the numerical simulation by the cement hydration model HYMOSTRUC3D.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Rupp, J.A.
Porosity preservation in the reservoir rocks within the Harrodsburg Limestone pool of the Newtonville Consolidated field, Spencer County, Indiana, is a function of both primary facies distribution and inhibited pore-filling sparry calcite cementation. Reservoir facies of the Harrodsburg mark the initial shallow-water phase in an overall shoaling-upward, prograding ramp succession beginning with deep basinal clastic sequences of shales and turbidites (early middle Mississippian) and culminating with sabkha and shallow marine carbonate deposits (middle middle Mississippian). Grainstones composed of bryozoans and pelmatozoan bioclasts were deposited oN the lower shoreface of a southwestward-deepening ramp in southern Indiana. Lateral distribution of coarse-grained, well-winnowed,more » southwestward and downdip-trending carbonate sequences was controlled by the undulatory and digitate nature of the ramp. Primary intragranular and minor intergranual porosity was preserved as early marine phreatic cementation created a rigid framework of grains resistant to further solution compaction. Fine-grained euhedral dolomite within proximal wackestones and mudstones formed as the product of a paleohydrologic system composed of plumes of fresh water that extended down through grainstone bodies and formed a periperhal zone of mixed meteoric and marine phreatic waters. Later coarse sparry calcite cement within peripheral grainstones resulted from burial cementation. Lack of significant water-filled porosity off the depositional structure indicates that the early presence of hydrocarbons within the primary pore system inhibited further cementation.« less
NASA Astrophysics Data System (ADS)
Lafond, E.; Cau dit Coumes, C.; Gauffinet, S.; Chartier, D.; Stefan, L.; Le Bescop, P.
2017-01-01
This work is devoted to the conditioning of ion exchange resins used to decontaminate radioactive effluents. Calcium silicate cements may have a good potential to encapsulate spent resins. However, certain combinations of cement and resins produce a strong expansion of the final product, possibly leading to its full disintegration. The focus is placed on the understanding of the behaviour of cationic resins in the Na+ form in Portland or blast furnace slag (CEM III/C) cement pastes. During hydration of the Portland cement paste, the pore solution exhibits a decrease in its osmotic pressure, which causes a transient expansion of small magnitude of the resins. At 20 °C, this expansion takes place just after setting in a poorly consolidated material and is sufficient to induce cracks. In the CEM III/C paste, swelling of the resins also occurs, but before the end of setting, and induces limited stress in the matrix which is still plastic.
Effective Permeability Change in Wellbore Cement with Carbon Dioxide Reaction
DOE Office of Scientific and Technical Information (OSTI.GOV)
Um, Wooyong; Jung, Hun Bok; Martin, Paul F.
2011-11-01
Portland cement, a common sealing material for wellbores for geological carbon sequestration was reacted with CO{sub 2} in supercritical, gaseous, and aqueous phases at various pressure and temperature conditions to simulate cement-CO{sub 2} reaction along the wellbore from carbon injection depth to the near-surface. Hydrated Portland cement columns (14 mm diameter x 90 mm length; water-to-cement ratio = 0.33) including additives such as steel coupons and Wallula basalt fragments were reacted with CO{sub 2} in the wet supercritical (the top half) and dissolved (the bottom half) phases under carbon sequestration condition with high pressure (10 MPa) and temperature (50 C)more » for 5 months, while small-sized hydrated Portland cement columns (7 mm diameter x 20 mm length; water-to-cement ratio = 0.38) were reacted with CO{sub 2} in dissolved phase at high pressure (10 MPa) and temperature (50 C) for 1 month or with wet CO{sub 2} in gaseous phase at low pressure (0.2 MPa) and temperature (20 C) for 3 months. XMT images reveal that the cement reacted with CO{sub 2} saturated groundwater had degradation depth of {approx}1 mm for 1 month and {approx}3.5 mm for 5 month, whereas the degradation was minor with cement exposure to supercritical CO{sub 2}. SEM-EDS analysis showed that the carbonated cement was comprised of three distinct zones; the innermost less degraded zone with Ca atom % > C atom %, the inner degraded zone with Ca atom % {approx} C atom % due to precipitation of calcite, the outer degraded zone with C atom % > Ca atom % due to dissolution of calcite and C-S-H, as well as adsorption of carbon to cement matrix. The outer degraded zone of carbonated cement was porous and fractured because of dissolution-dominated reaction by carbonic acid exposure, which resulted in the increase in BJH pore volume and BET surface area. In contrast, cement-wet CO{sub 2}(g) reaction at low P (0.2 MPa)-T (20 C) conditions for 1 to 3 months was dominated by precipitation of micron-sized calcite on the outside surface of cement, which resulted in the decrease in BJH pore volume and BET surface area. Cement carbonation and pore structure change are significantly dependent on pressure and temperature conditions as well as the phase of CO{sub 2}, which controls the balance between precipitation and dissolution in cement matrix. Geochemical modeling result suggests that ratio of solid (cement)-to-solution (carbonated water) has a significant effect on cement carbonation, thus the cement-CO{sub 2} reaction experiment needs to be conducted under realistic conditions representing the in-situ wellbore environment of carbon sequestration field site. Total porosity and air permeability for a duplicate cement column with water-to-cement ratio of 0.38 measured after oven-drying by Core Laboratories using Boyle's Law technique and steady-state method were 31% and 0.576 mD. A novel method to measure the effective liquid permeability of a cement column using X-ray micro-tomography images after injection of pressurized KI (potassium iodide) is under development by PNNL. Preliminary results indicate the permeability of a cement column with water-to-cement ratio of 0.38 is 4-8 mD. PNNL will apply the method to understand the effective permeability change of Portland cement by CO{sub 2}(g) reaction under a variety of pressure and temperature conditions to develop a more reliable well-bore leakage risk model.« less
Quartz cement in sandstones: a review
NASA Astrophysics Data System (ADS)
McBride, Earle F.
Quartz cement as syntaxial overgrowths is one of the two most abundant cements in sandstones. The main factors that control the amount of quartz cement in sandstones are: framework composition; residence time in the "silica mobility window"; and fluid composition, flow volume and pathways. Thus, the type of sedimentary basin in which a sand was deposited strongly controls the cementation process. Sandstones of rift basins (arkoses) and collision-margin basins (litharenites) generally have only a few percent quartz cement; quartzarenites and other quartzose sandstones of intracratonic, foreland and passive-margin basins have the most quartz cement. Clay and other mineral coatings on detrital quartz grains and entrapment of hydrocarbons in pores retard or prevent cementation by quartz, whereas extremely permeable sands that serve as major fluid conduits tend to sequester the greatest amounts of quartz cement. In rapidly subsiding basins, like the Gulf Coast and North Sea basins, most quartz cement is precipitated by cooling, ascending formation water at burial depths of several kilometers where temperatures range from 60° to 100° C. Cementation proceeds over millions of years, often under changing fluid compositions and temperatures. Sandstones with more than 10% imported quartz cement pose special problems of fluid flux and silica transport. If silica is transported entirely as H 4SiO 4, convective recycling of formation water seems to be essential to explain the volume of cement present in most sandstones. Precipitation from single-cycle, upward-migrating formation water is adequate to provide the volume of cement only if significant volumes of silica are transported in unidentified complexes. Modeling suggests that quartz cementation of sandstones in intracratonic basins is effected by advecting meteoric water, although independent petrographic, isotopic or fluid inclusion data are lacking. Silica for quartz cement comes from both shale and sandstone beds within the depositional basin, including possibly deeply buried rocks undergoing low-grade metamorphism, but the relative importance of potential sources remains controversial and likely differs for different formations. The most likely important silica sources within unmetamorphosed shales include clay transformation (chiefly illitization of smectite), dissolution/pressure solution of detrital grains, and dissolution of opal skeletal grains; the most likely important sources of silica within unmetamorphosed sandstones include pressure solution of detrital quartz grains at grain contacts and at stylolites, feldspar alteration/dissolution, and perhaps carbonate replacement of silicate minerals and the margins of some quartz grains. Silica released by pressure solution in many sandstones post-dates the episode of cementation by quartz; thus, this silica must migrate and cement shallower sandstones in the basin or escape altogether. Some quartz-cemented sandstones are separated vertically from potential silica source beds by a kilometer or more, requiring silica transport over long distances. The similarity of diagenetic sequences in sandstones of different composition and ages apparently is the result of the normal temperature and time-dependent maturation of sediments, organic matter and pore fluids during burial in sedimentary basins. Silica that forms overgrowths is released by one or more diagenetic processes that apparently are controlled by temperature and time. Most cementation by quartz takes place when sandstone beds were in the silica mobility window specific to a particular sedimentary basin. Important secondary controls are introduced by compartmentalized domains produced by faults (e.g., North Sea) or overpressure boundaries (e.g., Gulf Coast Tertiary). Shallow meteoric water precipitates only small amounts of silica cement (generally less than 5% in most fluvial and colian sandstones), except in certain soils and at water tables in high-flux sand aquifers. Soil silcretes are chiefly cemented by opal and microcrystalline quartz, whereas water-table silcretes have abundant normal syntaxial quartz overgrowths. Silica for silcrete cements and replacements comes from quartz, silicate minerals, and locally volcanic glass, in alluvium and bedrock.
Guerrero, A; Goñi, S; Allegro, V R
2009-06-15
The durability of class C fly ash belite cement (FABC-2-W) in simulated radioactive liquid waste (SRLW) rich in a mixed sodium chloride and sulphate solution is presented here. The effect of the temperature and potential synergic effect of chloride and sulfate ions are discussed. This study has been carried out according to the Koch-Steinegger test, at the temperature of 20 degrees C and 40 degrees C during a period of 180 days. The durability has been evaluated by the changes of the flexural strength of mortar, fabricated with this cement, immersed in a simulated radioactive liquid waste rich in sulfate (0.5M), chloride (0.5M) and sodium (1.5M) ions--catalogued like severely aggressive for the traditional Portland cement--and demineralised water, which was used as reference. The reaction mechanism of sulphate, chloride and sodium ions with the mortar was evaluated by scanning electron microscopy (SEM), porosity and pore-size distribution, and X-ray diffraction (XRD). The results showed that the chloride binding and formation of Friedel's salt was inhibited by the presence of sulphate. Sulphate ion reacts preferentially with the calcium aluminate hydrates forming non-expansive ettringite which precipitated inside the pores; the microstructure was refined and the mechanical properties enhanced. This process was faster and more marked at 40 degrees C.
Huang, Piao; Lv, Liming; Liao, Wei; Lu, Chunhua; Xu, Zhongzi
2018-05-11
Nanomaterials have been widely used in cement-based materials. Graphene has excellent properties for improving the durability of cement-based materials. Given its high production budget, it has limited its wide potential for application in the field of engineering. Hence, it is very meaningful to obtain low cost nanoplatelets from natural materials that can replace graphene nanoplatelets (GNPs) The purpose of this paper is to improve the resistance to chloride ion penetration by optimizing the pore structure of cement-based materials, and another point is to reduce investment costs. The results illustrated that low cost CaCO₃ nanoplatelets (CCNPs) were successfully obtained under alkali treatment of seashell powder, and the chloride ion permeability of cement-based materials significantly decreased by 15.7% compared to that of the control samples when CCNPs were incorporated. Furthermore, the compressive strength of cement pastes at the age of 28 days increased by 37.9% than that of the plain sample. Improvement of performance of cement-based materials can be partly attributed to the refinement of the pore structure. In addition, AFM was employed to characterize the nanoplatelet thickness of CCNPs and the pore structures of the cement-based composites were analyzed by MIP, respectively. CCNPs composite cement best performance could lay the foundation for further study of the durability of cement-based materials and the application of decontaminated seashells.
Lv, Liming; Liao, Wei; Lu, Chunhua; Xu, Zhongzi
2018-01-01
Nanomaterials have been widely used in cement-based materials. Graphene has excellent properties for improving the durability of cement-based materials. Given its high production budget, it has limited its wide potential for application in the field of engineering. Hence, it is very meaningful to obtain low cost nanoplatelets from natural materials that can replace graphene nanoplatelets (GNPs) The purpose of this paper is to improve the resistance to chloride ion penetration by optimizing the pore structure of cement-based materials, and another point is to reduce investment costs. The results illustrated that low cost CaCO3 nanoplatelets (CCNPs) were successfully obtained under alkali treatment of seashell powder, and the chloride ion permeability of cement-based materials significantly decreased by 15.7% compared to that of the control samples when CCNPs were incorporated. Furthermore, the compressive strength of cement pastes at the age of 28 days increased by 37.9% than that of the plain sample. Improvement of performance of cement-based materials can be partly attributed to the refinement of the pore structure. In addition, AFM was employed to characterize the nanoplatelet thickness of CCNPs and the pore structures of the cement-based composites were analyzed by MIP, respectively. CCNPs composite cement best performance could lay the foundation for further study of the durability of cement-based materials and the application of decontaminated seashells. PMID:29751666
In-situ Mechanical Manipulation of Wellbore Cements as a Solution to Leaky Wells
NASA Astrophysics Data System (ADS)
Kupresan, D.; Radonjic, M.; Heathman, J.
2013-12-01
Wellbore cement provides casing support, zonal isolation, and casing protection from corrosive fluids, which are essential for wellbore integrity. Cements can undergo one or more forms of failure such as debonding at cement/formation and cement/casing interface, fracturing and defects within cement matrix. Failures and defects within cement will ultimately lead to fluids migration, resulting in inter-zonal fluid migration and premature well abandonment. There are over 27,000 abandoned oil and gas wells only in The Gulf of Mexico (some of them dating from the late 1940s) with no gas leakage monitoring. Cement degradation linked with carbon sequestration can potentially lead to contamination of fresh water aquifers with CO2. Gas leaks can particularly be observed in deviated wells used for hydraulic fracking (60% leakage rate as they age) as high pressure fracturing increases the potential for migration pathways. Experimental method utilized in this study enables formation of impermeable seals at interfaces present in a wellbore by mechanically manipulating wellbore cement. Preliminary measurements obtained in bench scale experiments demonstrate that an impermeable cement/formation and cement/casing interface can be obtained. In post-modified cement, nitrogen gas flow-through experiments showed complete zonal isolation and no permeability in samples with pre-engineered microannulus. Material characterization experiments of modified cement revealed altered microstructural properties of cement as well as changes in mineralogical composition. Calcium-silicate-hydrate (CSH), the dominant mineral in hydrated cement which provides low permeability of cement, was modified as a result of cement pore water displacement, resulting in more dense structures. Calcium hydroxide (CH), which is associated with low resistance of cement to acidic fluids and therefore detrimental in most wellbore cements, was almost completely displaced and/or integrated in CSH as a result of mechanical manipulation (shear stress). The main advantage of this methodology is that mechanical manipulation of cement can induce healing of existing fractures, channels and microannulus seal in a wellbore without introducing new materials (e.g. cement squeeze jobs). Furthermore, this methodology is less sensitive to the influence of downhole conditions such as pressure, temperature and formation fluids, since it uses cement pore water as a medium to alter cement sheath. Based on lab experiments observation, it is possible to perceive that once tested at the industrial scale and if successful, the implementation of this method in the field can potentially mitigate leaky wells in CO2 sequestration projects, wellbores completed for hydraulic-fracturing and other conventional oil and gas producing wells. Key words: Wellbore cement integrity; Leaky wells; Cement microstructures; Casing expansion effect on cement mineralogy alterations.
Calcium leaching behavior of cementitious materials in hydrochloric acid solution.
Yang, Huashan; Che, Yujun; Leng, Faguang
2018-06-11
The calcium leaching behavior of cement paste and silica fume modified calcium hydroxide paste, exposed to hydrochloric acid solution, is reported in this paper. The kinetic of degradation was assessed by the changes of pH of hydrochloric acid solution with time. The changes of compressive strength of specimens in hydrochloric acid with time were tested. Hydration products of leached specimens were also analyzed by X-ray diffraction (XRD), differential scanning calorimetry (DSC), thermogravimetric (TG), and atomic force microscope (AFM). Tests results show that there is a dynamic equilibrium in the supply and consumption of calcium hydroxide in hydrochloric acid solution, which govern the stability of hydration products such as calcium silicate hydrate (C-S-H). The decrease of compressive strength indicates that C-S-H are decomposed due to the lower concentration of calcium hydroxide in the pore solution than the equilibrium concentration of the hydration products. Furthermore, the hydration of unhydrated clinker delayed the decomposition of C-S-H in hydrochloric acid solution due to the increase of calcium hydroxide in pore solution of cementitious materials.
NASA Astrophysics Data System (ADS)
Wismogroho, Agus Sukarto; Firmansyah, Trisna Bagus; Meidianto, Alwi; Widayatno, Wahyu Bambang; Amal, Muhamad Ikhlasul
2018-05-01
This paper reports the effect of aluminium corrosion reaction on the density, porosity, and thermal insulation capability of porous fire bricks. The reaction between aluminium and alkaline solution produces hydrogen and other sediment products. The test specimens of fire bricks were made from the mixture of castable cement, aluminium powder of 325 mesh in size (0, 0.1, 1, and 2 wt% with respect to castable cement), and 0.185 M KOH solution. The structural examination of the specimens shows the increase of porosity to 22.7 - 30.6% and the decrease of density in the range of 1.135-1.503 g/mL. In addition, the samples possess average pore size of 0.001-0.003 cm3 with the thermal insulation in the range of 47-78%.
NASA Astrophysics Data System (ADS)
Hadizadeh, Jafar; Foit, Franklin F.
2000-04-01
Cement phases such as calcite or quartz often incorporate trace elements from the parent fluids as they crystallize. Experimental sedimentary diagenesis indicates that trace element partition coefficients reflect rates of cementation. The applicability of these findings to fault zone cementation is examined as we make a preliminary attempt to estimate calcite cementation rate in a brittle fault zone directly from the fault-rock composition data. Samples for this study were collected from the Knoxville outcrop of the Saltville fault in Tennessee. The cementation rates for the fault rock samples range from 1×10 -12 to 3×10 -13 m3/ h per m, in agreement with some experimental rates and the rates reported for samples from the DSDP sites. When applied to a non-responsive pore-system model, these rates result in rapid precipitation sealing indicating the influence exerted by the surface-area/volume ratio of the pore network. We find it feasible to obtain a reasonable range of values for the cementation rate using the trace element partition method. However, the study also indicates the need for relatively accurate values for the trace/carrier element ratio in the fault zone syntectonic pore fluid, and exhumed cement.
1H NMR Cryoporometry Study of the Melting Behavior of Water in White Cement
NASA Astrophysics Data System (ADS)
Boguszyńska, Joanna; Tritt-Goc, Jadwiga
2004-09-01
The pore size of white cement samples is studied by the melting behaviour of water confined in it, using 1H NMR cryopormetry. The influence of the preparing method and antifreeze admixture on the pore size and distribution in cement samples is investigated at 283 K. The addition of an antifreeze admixture [containing 1% Sika Rapid 2 by weight of the dry cement] influences the porosity. In wet prepared samples we observed a significant increase in the quantity of mesopores between 0.8 and 5 nm and a smaller increase of mesopores between 5 and 10 nm, when compared to cement without admixture. The compressive strength is related to the porosity of the cement. Therefore the cement with Sika Rapid 2, wet prepared at 278 K shows a higher strength than all other measured samples.
Impact of Casing Expansion on the Mechanical and Petro-Physical Properties of Wellbore Cements
NASA Astrophysics Data System (ADS)
Oyibo, A. E.
2014-12-01
The main objective of this research is to investigate the applicability of expandable casing technology as a remediation technique for leaky wells resulting in gas migration problems. Micro annulus is usually created at the cement-formation/cement-casing interface or within the cement matrix either due to poor primary cementing or as a result of activities such as temperature and pressure variation or fracturing operations. Recent reports on gas migration in hydraulically fractured wellbores, has raised concerns on the contamination of fresh water aquifers resulting from fluid migration though this flow path. A unique bench-scale physical model which utilizes expandable tubulars in the remediation of micro annular gas flow has been used to simulate expansion of a previously-cemented casing under field-like conditions. Three different designs of cement slurry: regular 16.4 lb. /gal, 16.4 lb. /gal base slurry foamed to 13 lb. /gal and 16.4 lb. /gal cement slurry with 10% salt concentration. Gas flow path (microannulus) was artificially created at the pipe-cement interface by rotating the inner pipe in a pipe inside pipe assembly with cement in the annulus within the first few hours of hydration to create debonding at the cement-casing interface. Nitrogen gas flow-through experiments were performed before and after the expansion to confirm the sealing of the microannulus. The results obtained confirmed the effectiveness of this technique in the complete closure of gas leakage path, providing seal-tight cement-formation interface free of microannulus. The manipulation of the cement sheath during the casing expansion resulted in improved porosity, permeability and the strength of the cement sheath. SEM micrographs revealed decrease in pore size and fracturing of unhydrated cement grains within the cement matrix. This technology has great potential to become one of the leading cement remediation techniques for leaks behind the casing if implemented. Keywords: Wellbore Integrity, Casing Expansion, Well Gas Leaks, CSH, Pore Collapse, Cement Pore Water.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Schroefl, Christof, E-mail: christof.schroefl@tu-dresden.de; Mechtcherine, Viktor; Vontobel, Peter
2015-09-15
Water sorption of two superabsorbent polymers in cement-based pastes has been characterized by neutron radiography. Cement pastes with W/C of 0.25 and 0.50 and one additionally containing silica fume (W/C = 0.42) were investigated. The SAPs differed in their inherent sorption kinetics in extracted cement pore solution (SAP 1: self-releasing; SAP 2: retentive). Desorption from SAP 1 started very early after paste preparation. Hence, its individual non-retentiveness governs its behavior only. SAP 2 released water into all matrices, but its kinetics were different. In the paste with the highest W/C, some moderate water release was recorded from the beginning. Inmore » the other two pastes, SAP 2 retained its stored liquid during the dormant period, i.e., up to the percolation threshold. Intense desorption then set in and continued throughout the acceleration period. These findings explain the pronouncedly higher efficiency of SAP 2 as internal curing admixture as compared to SAP 1.« less
SCM Paste Samples Exposed To Aggressive Solutions. Cementitious Barriers Partnership
DOE Office of Scientific and Technical Information (OSTI.GOV)
Foster, T.
This report summarizes experimental work performed by SIMCO Technologies Inc. (SIMCO) as part of the Cementitious Barriers Partnership (CBP) project. The test series followed an experimental program dedicated to the study of ordinary Portland cement (OPC) hydrated cement pastes exposed to aggressive solutions. In the present study, the scope is extended to hydrated cement pastes incorporating supplementary cementitious materials (SCM) such as fly ash and ground granulated blast furnace slag (GGBFS). Also, the range of aggressive contact solutions was expanded. The experimental program aimed at testing aggressive contact solutions that more closely mimic the chemical composition of saltstone pore solution.more » Five different solutions, some of which incorporated high levels of carbonate and nitrate, were placed in contact with four different hydrated cement paste mixes. In all solutions, 150 mmol/L of SO 4 2– (14 400 ppm) were present. The solutions included different pH conditions and different sodium content. Two paste mixes were equivalent to Vault 1/4 and Vault 2 concrete mixes used at SRS in storage structures. Two additional paste mixes, cast at the same water-to-cement ratio and using the same cements but without SCMs, were also tested. The damage evolution in samples was monitored using ultrasonic pulse velocity (UPV) and mass measurements. After three and twelve months of exposure conditions, samples were taken out of solution containers and analyzed to perform migration tests and porosity measurements. Globally, results were in line with the previous study and confirmed that high pH may limit the formation of some deleterious phases like gypsum. In this case, ettringite may form but is not necessarily associated with damage. However, the high concentration of sodium may be associated with the formation of an AFm-like mineral called U-phase. The most significant evidences of damage were all associated with the Vault 2 paste analog. This material proved very sensitive to high pH. All measurement techniques used to monitor and evaluate damage to samples indicated significant alterations to this mix when immersed in contact solutions containing sodium hydroxide. It was hypothesized that the low cement content, combined with high silica content coming from silica fume, fly ash and GGBFS led to the presence unreacted silica. It is possible that the pozzolanic reaction of these SCMs could not be activated due to the low alkali content, a direct consequence of low cement content. In this scenario, the material end up having a lot of silica available to react upon contact with sodium hydroxide, possibly forming a gel that may be similar to the gel formed in alkali-silica reactions. This scenario needs further experimental confirmation, but it may well explain the poor behavior of mix PV2 in presence of NaOH.« less
Acoustic response of cemented granular sedimentary rocks: molecular dynamics modeling.
García, Xavier; Medina, Ernesto
2007-06-01
The effect of cementation processes on the acoustical properties of sands is studied via molecular dynamics simulation methods. We propose numerical methods where the initial uncemented sand is built by simulating the settling process of sediments. Uncemented samples of different porosity are considered by emulating natural mechanical compaction of sediments due to overburden. Cementation is considered through a particle-based model that captures the underlying physics behind the process. In our simulations, we consider samples with different degrees of compaction and cementing materials with distinct elastic properties. The microstructure of cemented sands is taken into account while adding cement at specific locations within the pores, such as grain-to-grain contacts. Results show that the acoustical properties of cemented sands are strongly dependent on the amount of cement, its stiffness relative to the hosting medium, and its location within the pores. Simulation results are in good correspondence with available experimental data and compare favorably with some theoretical predictions for the sound velocity within a range of cement saturation, porosity, and confining pressure.
NEUTRON RADIOGRAPHY MEASUREMENT OF SALT SOLUTION ABSORPTION IN MORTAR
Lucero, Catherine L.; Spragg, Robert P.; Bentz, Dale P.; Hussey, Daniel S.; Jacobson, David L.; Weiss, W. Jason
2017-01-01
Some concrete pavements in the US have recently exhibited premature joint deterioration. It is hypothesized that one component of this damage can be attributed to a reaction that occurs when salt-laden water is absorbed in the concrete and reacts with the matrix. This study examines the absorption of CaCl2 solution in mortar via neutron imaging. Mortar specimens were prepared with water to cement ratios, (w/c), of 0.36, 0.42 and 0.50 by mass and exposed to chloride solutions with concentrations ranging from 0 % to 29.8 % by mass. Depth of fluid penetration and moisture content along the specimen length were determined for 96 h after exposure. At high salt concentration (29.8 %), the sorption rate decreased by over 80 % in all samples. Along with changes in surface tension and viscosity, CaCl2 reacts with the cement paste to produce products (Friedel’s salt, Kuzel’s salt, or calcium oxychloride) that block pores and reduce absorption. PMID:28626299
NEUTRON RADIOGRAPHY MEASUREMENT OF SALT SOLUTION ABSORPTION IN MORTAR.
Lucero, Catherine L; Spragg, Robert P; Bentz, Dale P; Hussey, Daniel S; Jacobson, David L; Weiss, W Jason
2017-01-01
Some concrete pavements in the US have recently exhibited premature joint deterioration. It is hypothesized that one component of this damage can be attributed to a reaction that occurs when salt-laden water is absorbed in the concrete and reacts with the matrix. This study examines the absorption of CaCl 2 solution in mortar via neutron imaging. Mortar specimens were prepared with water to cement ratios, ( w/c ), of 0.36, 0.42 and 0.50 by mass and exposed to chloride solutions with concentrations ranging from 0 % to 29.8 % by mass. Depth of fluid penetration and moisture content along the specimen length were determined for 96 h after exposure. At high salt concentration (29.8 %), the sorption rate decreased by over 80 % in all samples. Along with changes in surface tension and viscosity, CaCl 2 reacts with the cement paste to produce products (Friedel's salt, Kuzel's salt, or calcium oxychloride) that block pores and reduce absorption.
How mobile are protons in the structure of dental glass ionomer cements?
Benetti, Ana R.; Jacobsen, Johan; Lehnhoff, Benedict; Momsen, Niels C. R.; Okhrimenko, Denis V.; Telling, Mark T. F.; Kardjilov, Nikolay; Strobl, Markus; Seydel, Tilo; Manke, Ingo; Bordallo, Heloisa N.
2015-01-01
The development of dental materials with improved properties and increased longevity can save costs and minimize discomfort for patients. Due to their good biocompatibility, glass ionomer cements are an interesting restorative option. However, these cements have limited mechanical strength to survive in the challenging oral environment. Therefore, a better understanding of the structure and hydration process of these cements can bring the necessary understanding to further developments. Neutrons and X-rays have been used to investigate the highly complex pore structure, as well as to assess the hydrogen mobility within these cements. Our findings suggest that the lower mechanical strength in glass ionomer cements results not only from the presence of pores, but also from the increased hydrogen mobility within the material. The relationship between microstructure, hydrogen mobility and strength brings insights into the material's durability, also demonstrating the need and opening the possibility for further research in these dental cements. PMID:25754555
How mobile are protons in the structure of dental glass ionomer cements?
NASA Astrophysics Data System (ADS)
Benetti, Ana R.; Jacobsen, Johan; Lehnhoff, Benedict; Momsen, Niels C. R.; Okhrimenko, Denis V.; Telling, Mark T. F.; Kardjilov, Nikolay; Strobl, Markus; Seydel, Tilo; Manke, Ingo; Bordallo, Heloisa N.
2015-03-01
The development of dental materials with improved properties and increased longevity can save costs and minimize discomfort for patients. Due to their good biocompatibility, glass ionomer cements are an interesting restorative option. However, these cements have limited mechanical strength to survive in the challenging oral environment. Therefore, a better understanding of the structure and hydration process of these cements can bring the necessary understanding to further developments. Neutrons and X-rays have been used to investigate the highly complex pore structure, as well as to assess the hydrogen mobility within these cements. Our findings suggest that the lower mechanical strength in glass ionomer cements results not only from the presence of pores, but also from the increased hydrogen mobility within the material. The relationship between microstructure, hydrogen mobility and strength brings insights into the material's durability, also demonstrating the need and opening the possibility for further research in these dental cements.
Durability of Cement Composites Reinforced with Sisal Fiber
NASA Astrophysics Data System (ADS)
Wei, Jianqiang
This dissertation focuses mainly on investigating the aging mechanisms and degradation kinetics of sisal fiber, as well as the approaches to mitigate its degradation in the matrix of cement composites. In contrast to previous works reported in the literature, a novel approach is proposed in this study to directly determine the fiber's degradation rate by separately studying the composition changes, mechanical and physical properties of the embedded sisal fibers. Cement hydration is presented to be a crucial factor in understanding fiber degradation behavior. The degradation mechanisms of natural fiber consist of mineralization of cell walls, alkali hydrolysis of lignin and hemicellulose, as well as the cellulose decomposition which includes stripping of cellulose microfibrils and alkaline hydrolysis of amorphous regions in cellulose chains. Two mineralization mechanisms, CH-mineralization and self-mineralization, are proposed. The degradation kinetics of sisal fiber in the cement matrix are also analyzed and a model to predict the degradation rate of cellulose for natural fiber embedded in cement is outlined. The results indicate that the time needed to completely degrade the cellulose in the matrix with cement replacement by 30wt.% metakaolin is 13 times longer than that in pure cement. A novel and scientific method is presented to determine accelerated aging conditions, and to evaluating sisal fiber's degradation rate and durability of natural fiber-reinforced cement composites. Among the static aggressive environments, the most effective approach for accelerating the degradation of natural fiber in cement composites is to soak the samples or change the humidity at 70 °C and higher temperature. However, the dynamic wetting and drying cycling treatment has a more accelerating effect on the alkali hydrolysis of fiber's amorphous components evidenced by the highest crystallinity indices, minimum content of holocellulose, and lowest tensile strength. Based on the understanding of degradation mechanisms, two approaches are proposed to mitigate the degradation of sisal fiber in the cement matrix. In order to relieve the aggressive environment of hydrated cement, cement substitution by a combination of metakaolin and nanoclay, and a combination of rice husk ash and limestone are studied. Both metakaolin and nanoclay significantly optimize the cement hydration, while the combination of these two supplementary cementitious materials validates their complementary and synergistic effect at different stages of aging. The presented approaches effectively reduce the calcium hydroxide content and the alkalinity of the pore solution, thereby mitigating the fiber degradation and improving both the initial mechanical properties and durability of the fiber-cement composites. The role of rice husk ash in cement modification is mainly as the active cementitious supplementary material. In order to improve the degradation resistance of sisal fiber itself, two novel, simple, and economical pretreatments of the fibers (thermal and sodium carbonate treatment) are investigated. Both thermal treatment and Na 2CO3 treatment effectively improve the durability of sisal fiber-reinforced concrete. The thermal treatment achieves improvement of cellulose's crystallization, which ensures the initial strength and improved durability of sisal fiber. A layer consisting of calcium carbonate sediments, which protects the internals of a fiber from the strong alkali pore solution, is formed and filled in pits and cavities on the Na2CO3 treated sisal fiber's surface.
Methane hydrate formation in partially water-saturated Ottawa sand
Waite, W.F.; Winters, W.J.; Mason, D.H.
2004-01-01
Bulk properties of gas hydrate-bearing sediment strongly depend on whether hydrate forms primarily in the pore fluid, becomes a load-bearing member of the sediment matrix, or cements sediment grains. Our compressional wave speed measurements through partially water-saturated, methane hydrate-bearing Ottawa sands suggest hydrate surrounds and cements sediment grains. The three Ottawa sand packs tested in the Gas Hydrate And Sediment Test Laboratory Instrument (GHASTLI) contain 38(1)% porosity, initially with distilled water saturating 58, 31, and 16% of that pore space, respectively. From the volume of methane gas produced during hydrate dissociation, we calculated the hydrate concentration in the pore space to be 70, 37, and 20% respectively. Based on these hydrate concentrations and our measured compressional wave speeds, we used a rock physics model to differentiate between potential pore-space hydrate distributions. Model results suggest methane hydrate cements unconsolidated sediment when forming in systems containing an abundant gas phase.
NASA Astrophysics Data System (ADS)
Dussenova, D.; Bilheux, H.; Radonjic, M.
2012-12-01
Wellbore Cement studies have been ongoing for decades. The studies vary from efforts to reduce permeability and resistance to corrosive environment to issues with gas migration also known as Sustained Casing Pressure (SCP). These practical issues often lead to health and safety problems as well as huge economic loss in oil and gas industry. Several techniques have been employed to reduce the impact of gas leakage. In this study we purely focus on expandable liners, which are introduced as part of oil well reconstruction and work-overs and as well abandonment procedures that help in prevention of SCP. Expandable liner is a tube that after application of a certain tool can increase its diameter. The increase in diameter creates extra force on hydrated cement that results in reducing width of interface fractures and cement-tube de-bonding. Moreover, this also causes cement to change its microstructure and other porous medium properties, primarily hydraulic conductivity. In order to examine changes before and after operations, cement pore structure must be well characterized and correlated to cement slurry design as well as chemical and physical environmental conditions. As modern oil well pipes and tubes contain iron, it is difficult to perform X-ray tomography of a bulk measurement of the cement in its wellbore conditions, which are tube wall-cement-tube wall. Neutron imaging is a complementary technique to x-ray imaging and is well suited for detection of light elements imbedded in metallic containers. Thus, Neutron Imaging (NI) is investigated as a tool for the detection of pore structure of hydrated wellbore cement. Recent measurements were conducted at the Oak Ridge National Laboratory (ORNL) High Flux Isotope Reactor (HFIR) neutron imaging facility. NI is is highly sensitive to light elements such as Hydrogen (H). Oil well cements that have undergone a full hydration contain on average 30%-40% of free water in its pore structure. The unreacted water is the main storage of the hydrogen atom. In such case, neutron tomography does not give information of the pore structure as neutrons will strongly scatter of H and the data have low count and low statistics or low neutron transmission. Hence, as the comparison and the possible tuning technique, neutron tomography measurements are performed on a Deuterium Oxide (D2O) or heavy water samples the same dimensions, cement composition, cement/liquid content and hydration time as the H2O samples. The advantage of using heavy water is that the total neutron cross-section for Deuterium is approximately four times smaller than Hydrogen's and, thus, permits better neutron transmission, i.e. better statistics. D2O does not alter cement properties or its chemical composition; therefore, the samples are almost identical. Comparison of the measurements using water and heavy water samples and the preparation of the measurement cement samples are discussed in this
Diagenetic history of the Surma Group sandstones (Miocene) in the Surma Basin, Bangladesh
NASA Astrophysics Data System (ADS)
Rahman, M. Julleh Jalalur; McCann, Tom
2012-02-01
This study examines the various diagenetic controls of the Miocene Surma Group sandstones encountered in petroleum exploration wells from the Surma Basin, which is situated in the northeastern part of the Bengal Basin, Bangladesh. The principal diagenetic minerals/cements in the Surma Group sandstones are Fe-carbonates (with Fe-calcite dominating), quartz overgrowths and authigenic clays (predominantly chlorite, illite-smectite and minor kaolin). The isotopic composition of the carbonate cement revealed a narrow range of δ 18O values (-10.3‰ to -12.4‰) and a wide range of δ 13C value (+1.4‰ to -23.1‰). The δ 13C VPDB and δ 18O VPDB values of the carbonate cements reveal that carbon was most likely derived from the thermal maturation of organic matter during burial, as well as from the dissolution of isolated carbonate clasts and precipitated from mixed marine-meteoric pore waters. The relationship between the intergranular volume (IGV) versus cement volume indicates that compaction played a more significant role than cementation in destroying the primary porosity. However, cementation also played a major role in drastically reducing porosity and permeability in sandstones with poikilotopic, pore-filling blocky cements formed in early to intermediate and deep burial areas. In addition to Fe-carbonate cements, various clay minerals including illite-smectite and chlorite occur as pore-filling and pore-lining authigenic phases. Significant secondary porosity has been generated at depths from 2500 m to 4728 m. The best reservoir rocks found at depths of 2500-3300 m are well sorted, relatively coarse grained; more loosely packed and better rounded sandstones having good porosities (20-30%) and high permeabilities (12-6000 mD). These good quality reservoir rocks are, however, not uniformly distributed and can be considered to be compartmentalized as a result of interbedding with sandstone layers of low to moderate porosities, low permeabilities owing to poor sorting and extensive compaction and cementation.
QUANTIFYING THE MICROMECHANICAL EFFECTS OF VARIABLE CEMENT IN GRANULAR POROUS MEDIA
DOE Office of Scientific and Technical Information (OSTI.GOV)
Boutt, David F; Goodwin, Laurel B
2010-03-01
The mechanical and hydrologic behavior of clastic rocks and sediments is fundamentally controlled by variables such as grain size and shape, sorting, grain and cement mineralogy, porosity, and %cement - parameters that are not used directly in field-scale models of coupled flow and deformation. To improve our understanding of the relationship between these micromechanical properties and bulk behavior we focused on (1) relating detailed, quantitative characterization of the grain-pore systems to both hydrologic and mechanical properties of a suite of variably quartz-cemented quartz arenite samples and (2) the use of a combination of discrete element method (DEM) and poroelastic modelsmore » parameterized by data from the natural samples to isolate and compare the influence of changes in the mechanical and hydrologic properties of granular porous media due to changes in degree of cementation. Quartz overgrowths, the most common form of authigenic cements in sandstones, are responsible for significant porosity and permeability reduction. The distribution of quartz overgrowths is controlled by available pore space and the crystallographic orientations of individual quartz grains. Study of the St. Peter Sandstone allowed evaluation of the relative effects of quartz cementation and compaction on final grain and pore morphology, showing that progressive quartz cementation modifies the grain framework in consistent, predictable ways. Detailed microstructural characterization and multiple regression analyses show that with progressive diagenesis, the number and length of grain contacts increases as the number of pores increases, the number of large, well-connected pores decreases, and pores become rounder. These changes cause a decrease in pore size variability that leads to a decrease in bulk permeability and both stiffening and strengthening of the grain framework. The consistent nature of these changes allows us to predict variations in hydrologic and mechanical properties with progressive diagenesis, and explore the impact of these changes on aquifer behavior. Several examples of this predictive capability are offered. In one application, data from natural sandstones are used to calibrate the proportionality constant of the Kozeny- Carman relationship, improving the ability to predict permeability in quartz-cemented quartz arenites. In another, the bond-to-grain ratio (BGR) is used to parameterize a discrete element model with data acquired from sandstone samples. The DEM results provide input to poroelastic models used to explore the hydrologic, mechanical, and coupled hydrologic and mechanical response of the sandstone to pumping stresses. This modeling exercise shows that at the macroscale, changes in mechanical and hydrologic properties directly influence the magnitude and area of aquifer deformation. The significant difference in sensitivity of the system to the mechanical properties alone versus its sensitivity to coupled mechanical and hydrologic properties demonstrates the importance of including hydrologic properties that are adjusted for changes in cementation in fluid storage and deformation studies. The large magnitude of radial deformation compared to vertical deformation in these models emphasizes the importance of considering three dimensional deformation in fluid flow and deformation studies.« less
NASA Astrophysics Data System (ADS)
Niu, Q.; Zhang, C.
2017-12-01
Archie's law is an important empirical relationship linking the electrical resistivity of geological materials to their porosity. It has been found experimentally that the porosity exponent m in Archie's law in sedimentary rocks might be related to the degree of cementation, and therefore m is termed as "cementation factor" in most literatures. Despite it has been known for many years, there is lack of well-accepted physical interpretations of the porosity exponent. Some theoretical and experimental evidences have also shown that m may be controlled by the particle and/or pore shape. In this study, we conduct a pore-scale modeling of the porosity exponent that incorporates different geological processes. The evolution of m of eight synthetic samples with different particle sizes and shapes are calculated during two geological processes, i.e., compaction and cementation. The numerical results show that in dilute conditions, m is controlled by the particle shape. As the samples deviate from dilute conditions, m increases gradually due to the strong interaction between particles. When the samples are at static equilibrium, m is noticeably larger than its values at dilution condition. The numerical simulation results also show that both geological compaction and cementation induce a significant increase in m. In addition, the geometric characteristics of these samples (e.g., pore space/throat size, and their distributions) during compaction and cementation are also calculated. Preliminary analysis shows a unique correlation between the pore size broadness and porosity exponent for all eight samples. However, such a correlation is not found between m and other geometric characteristics.
Geomechanical Behaviors of Laboratory-Formed Non-Cementing Hydrate-Bearing Sediments
NASA Astrophysics Data System (ADS)
Seol, Y.
2015-12-01
Natural hydrate-bearing sediments (HBS) have been known to exist with non-cementing pore habits, i.e., pore-filling, load-bearing, or patchy type. However, few laboratory studies have been conducted to characterize geomechanical behaviors of non-cementing CH4-HBS, which are of great importance in engineering the process of drilling and gas production in natural hydrate reservoir. In this study, we conducted multi-stage drained triaxial tests on laboratory synthesized CH4-HBS samples, which were formed in sand-clay mixtures (5%wt kaolinite) to have non-cementing habits. Three different effective confining stresses, σ3' = 0.69, 1.38, and 2.76 MPa, were applied on the HBS with the hydrate saturation, Sh, in the range of 0 to ~ 40%. The result confirms that the strength and stiffness of HBS increases with effective confining stress and hydrate saturation. It is also demonstrated that when compared to the cementing HBS, the non-cementing HBS has lower strength and cohesion, owing to less inter-particle adhesion effects from non-cementing hydrate.
Castable cements to prevent corrosion of metals in molten salts
Gomez-Vidal, Judith C.; Morton, E.
2016-04-22
Castable cements on metals form a protective barrier that is able to prevent permeation of molten salts towards metallic surfaces. Silica-based castable cements are capable of protecting containment metallic alloys from the corrosive attack of molten chlorides at temperatures as high as 650 °C. Boron nitride (BN) blocking the pores in the cured cement prevents permeation of the molten chloride towards the metal surface. The cements tested are not chemically stable in molten carbonates, because the bonding components dissolved into molten carbonates salt. The corrosion rate is 7.72±0.32 mm/year for bare stainless steel 347 in molten eutectic NaCl – 65.58more » wt% LiCl at 650 °C, which is the baseline used for determining how well the cement protects the metallic surfaces from corrosion. In particular the metal fully encapsulated with Aremco 645-N with pores filled with boron nitride immersed in molten eutectic NaCl – 65.58 wt% LiCl at 650 °C shows a corrosion rate of 9E-04 mm/year. Here, the present study gives initial corrosion rates. Long-term tests are required to determine if Aremco 645-N with BN coating on metal has long term chemical stability for blocking salt permeation through coating pores.« less
NASA Astrophysics Data System (ADS)
Lucero, Catherine L.; Bentz, Dale P.; Hussey, Daniel S.; Jacobson, David L.; Weiss, W. Jason
Air entrainment is commonly added to concrete to help in reducing the potential for freeze thaw damage. It is hypothesized that the entrained air voids remain unsaturated or partially saturated long after the smaller pores fill with water. Small gel and capillary pores in the cement matrix fill quickly on exposure to water, but larger pores (entrapped and entrained air voids) require longer times or other methods to achieve saturation. As such, it is important to quantitatively determine the water content and degree of saturation in air entrained cementitious materials. In order to further investigate properties of cement-based mortar, a model based on Beer's Law has been developed to interpret neutron radiographs. This model is a powerful tool for analyzing images acquired from neutron radiography. A mortar with a known volume of aggregate, water to cement ratio and degree of hydration can be imaged and the degree of saturation can be estimated.
NASA Astrophysics Data System (ADS)
Norbisrath, Jan Henrik
Carbonate rocks are known to have complex and heterogeneous pore structures, which result from their biogenic origin and strong affinity for diagenetic processes that change their pore structure after burial. The combination of sheer endless variations of precursor biogenic material, depositional environments, and diagenetic effects results in rocks that are interesting to study but intricate to understand. Many schemes to categorize the diversity of carbonate rocks are in use today; most are based on the macropore structure and qualitative thin-section analysis. Many studies, however, acknowledge that micropores have a significant influence on the macroscopic petrophysical rock properties, which are essential to determine reservoir quality. Micropores are, by definition, smaller than the thickness of a thin-section (< 30 microm) and hence cannot be quantified with conventional methods. For their analysis, scanning electron microscopy (SEM) is the logical next step. The challenge is that mechanical polishing methods produce excessive surface roughness at micron scale; the resulting surfaces are not suited for quantification of micropores. Advances in broad-ion-beam (BIB) milling enable preparation of nanometer-precision 2D sections that are suited for quantitative analysis with the SEM. To accomplish the objective of accurate quantification of carbonate micropores, part one of this dissertation employs the BIB-SEM technique on a variety of carbonate rock samples and finds four major carbonate microporosity types: (1) small intercrystalline, (2) large inter-crystalline, (3) intercement, and (4) micromoldic. Each microporosity type shows a distinct capacity to conduct electrical charge, which largely controls the magnitude and range of cementation factors (m) in rocks with such microporosity type. The BIB-SEM method is also used on a dataset of mixed carbonate-siliciclastic (mudrock) samples with high kerogen and pyrite content. Results show that the nanopore geometry here has little influence on cementation factors, and instead porosity is the main control on m in mudrocks. Cementation factors are crucial for estimates of oil-in-place and water saturation in a wireline application, and a slight change of (assumed) cementation factor can change the interpreter's evaluation from dry hole to discovery. Therefore, accurate determination of cementation factors is a critical task in formation evaluation, similar to accurate estimates of permeability. To achieve this goal, this dissertation utilizes a new approach of using complex resistivity spectra (CRS) to assess the pore geometry and its resulting electrical and fluid flow properties. Specifically, frequency dispersion of complex resistivity in the kHz range is used as input for a new model to predict cementation factor and permeability in a wide variety of core plug samples. The underlying concept that relates CRS to flow properties is that both are related to pore geometry. CRS are linked to pore geometry by interfacial polarization effects at the fluid-rock boundary that control the phase and amplitude shift of an applied alternating current. Larger interfacial area results in higher phase shifts, but also indicates a more intricate pore structure that often results in lower permeability and higher cementation factors. The findings from this dissertation imply that (1) the CRS prediction method greatly improves estimates of cementation factors and permeability in carbonate, dolomite, and mixed siliciclastic rocks, (2) there are at least four distinct microporosity types in carbonate rocks, which have great impact on cementation factors and permeability, (3) nanopore geometry has a small impact on electrical flow properties in mudrocks where the main control on cementation factors is porosity, and (4) all sedimentary limestone and mixed carbonate-siliciclastic rocks have power law pore size distributions.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pyatina, Tatiana; Sugama, Toshifumi; Moon, Juhyuk
An alkali-activated blend of aluminum cement and class F fly ash is an attractive solution for geothermal wells where cement is exposed to significant thermal shocks and aggressive environments. Set-control additives enable the safe cement placement in a well but may compromise its mechanical properties. Here, this work evaluates the effect of a tartaric-acid set retarder on phase composition, microstructure, and strength development of a sodium-metasilicate-activated calcium aluminate/fly ash class F blend after curing at 85 °C, 200 °C or 300 °C. The hardened materials were characterized with X-ray diffraction, thermogravimetric analysis, X-ray computed tomography, and combined scanning electron microscopy/energy-dispersivemore » X-ray spectroscopy and tested for mechanical strength. With increasing temperature, a higher number of phase transitions in non-retarded specimens was found as a result of fast cement hydration. The differences in the phase compositions were also attributed to tartaric acid interactions with metal ions released by the blend in retarded samples. The retarded samples showed higher total porosity but reduced percentage of large pores (above 500 µm) and greater compressive strength after 300 °C curing. Lastly, mechanical properties of the set cements were not compromised by the retarder.« less
Pyatina, Tatiana; Sugama, Toshifumi; Moon, Juhyuk; James, Simon
2016-01-01
An alkali-activated blend of aluminum cement and class F fly ash is an attractive solution for geothermal wells where cement is exposed to significant thermal shocks and aggressive environments. Set-control additives enable the safe cement placement in a well but may compromise its mechanical properties. This work evaluates the effect of a tartaric-acid set retarder on phase composition, microstructure, and strength development of a sodium-metasilicate-activated calcium aluminate/fly ash class F blend after curing at 85 °C, 200 °C or 300 °C. The hardened materials were characterized with X-ray diffraction, thermogravimetric analysis, X-ray computed tomography, and combined scanning electron microscopy/energy-dispersive X-ray spectroscopy and tested for mechanical strength. With increasing temperature, a higher number of phase transitions in non-retarded specimens was found as a result of fast cement hydration. The differences in the phase compositions were also attributed to tartaric acid interactions with metal ions released by the blend in retarded samples. The retarded samples showed higher total porosity but reduced percentage of large pores (above 500 µm) and greater compressive strength after 300 °C curing. Mechanical properties of the set cements were not compromised by the retarder. PMID:28773543
Pyatina, Tatiana; Sugama, Toshifumi; Moon, Juhyuk; ...
2016-05-27
An alkali-activated blend of aluminum cement and class F fly ash is an attractive solution for geothermal wells where cement is exposed to significant thermal shocks and aggressive environments. Set-control additives enable the safe cement placement in a well but may compromise its mechanical properties. Here, this work evaluates the effect of a tartaric-acid set retarder on phase composition, microstructure, and strength development of a sodium-metasilicate-activated calcium aluminate/fly ash class F blend after curing at 85 °C, 200 °C or 300 °C. The hardened materials were characterized with X-ray diffraction, thermogravimetric analysis, X-ray computed tomography, and combined scanning electron microscopy/energy-dispersivemore » X-ray spectroscopy and tested for mechanical strength. With increasing temperature, a higher number of phase transitions in non-retarded specimens was found as a result of fast cement hydration. The differences in the phase compositions were also attributed to tartaric acid interactions with metal ions released by the blend in retarded samples. The retarded samples showed higher total porosity but reduced percentage of large pores (above 500 µm) and greater compressive strength after 300 °C curing. Lastly, mechanical properties of the set cements were not compromised by the retarder.« less
Pyatina, Tatiana; Sugama, Toshifumi; Moon, Juhyuk; James, Simon
2016-05-27
An alkali-activated blend of aluminum cement and class F fly ash is an attractive solution for geothermal wells where cement is exposed to significant thermal shocks and aggressive environments. Set-control additives enable the safe cement placement in a well but may compromise its mechanical properties. This work evaluates the effect of a tartaric-acid set retarder on phase composition, microstructure, and strength development of a sodium-metasilicate-activated calcium aluminate/fly ash class F blend after curing at 85 °C, 200 °C or 300 °C. The hardened materials were characterized with X-ray diffraction, thermogravimetric analysis, X-ray computed tomography, and combined scanning electron microscopy/energy-dispersive X-ray spectroscopy and tested for mechanical strength. With increasing temperature, a higher number of phase transitions in non-retarded specimens was found as a result of fast cement hydration. The differences in the phase compositions were also attributed to tartaric acid interactions with metal ions released by the blend in retarded samples. The retarded samples showed higher total porosity but reduced percentage of large pores (above 500 µm) and greater compressive strength after 300 °C curing. Mechanical properties of the set cements were not compromised by the retarder.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kruger, A.A.; Olson, R.A.; Tennis, P.D.
1995-04-01
Portland cement blended with fly ash and attapulgite clay was mixed with high-alkaline solution simulating low-level radioactive waste stream at a one-to-one weight ratio. Mixtures were adiabatically and isothermally cured at various temperatures and analyzed for phase composition, total alkalinity, pore solution chemistry, and transport properties as measured by impedance spectroscopy. Total alkalinity is characterized by two main drops. The early one corresponds to a rapid removal of phosphorous, aluminum, sodium, and to a lesser extent potassium solution. The second drop from about 10 h to 3 days is mainly associated with the removal of aluminum, silicon, and sodium. Thereafter,more » the total alkalinity continues descending, but at a lower rate. All pastes display a rapid flow loss that is attributed to an early precipitation of hydrated products. Hemicarbonate appears as early as one hour after mixing and is probably followed by apatite precipitation. However, the former is unstable and decomposes at a rate that is inversely related to the curing temperature. At high temperatures, zeolite appears at about 10 h after mixing. At 30 days, the stabilized crystalline composition Includes zeolite, apatite and other minor amounts of CaCO{sub 3}, quartz, and monosulfate Impedance spectra conform with the chemical and mineralogical data. The normalized conductivity of the pastes shows an early drop, which is followed by a main decrease from about 12 h to three days. At three days, the permeability of the cement-based waste as calculated by Katz-Thompson equation is over three orders of magnitude lower than that of ordinary portland cement paste. However, a further decrease in the calculated permeability is questionable. Chemical stabilization is favorable through incorporation of waste species into apatite and zeolite.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Cwirzen, Andrzej; Penttala, Vesa
2005-04-01
The influence of the cement paste-aggregate interfacial transition zone (ITZ) on the frost durability of high-performance silica fume concrete (HPSFC) has been studied. Investigation was carried out on eight non-air-entrained concretes having water-to-binder (W/B) ratios of 0.3, 0.35 and 0.42 and different additions of condensed silica fume. Studies on the microstructure and composition of the cement paste have been made by means of environmental scanning electron microscope (ESEM)-BSE, ESEM-EDX and mercury intrusion porosimetry (MIP) analysis. The results showed that the transition zone initiates and accelerates damaging mechanisms by enhancing movement of the pore solution within the concrete during freezing andmore » thawing cycles. Cracks filled with ettringite were primarily formed in the ITZ. The test concretes having good frost-deicing salt durability featured a narrow transition zone and a decreased Ca/Si atomic ratio in the transition zone compared to the bulk cement paste. Moderate additions of silica fume seemed to densify the microstructure of the ITZ.« less
Microstructural and Microanalytical Study on Concrete Exposed to the Sulfate Environment
NASA Astrophysics Data System (ADS)
Qing, Fang; Beixing, Li; Jiangang, Yin; Xiaolu, Yuan
2017-11-01
Microstructural properties have been examined to investigate the effect of mineral admixtures on the sulfate resistance of concrete. Concrete and cement paste specimens made with ordinary Portland cement (OPC) or ordinary Portland cement incorporating 20% fly ash (FA) or 30% ground blast furnace slag (GBFS), were made and exposed to 250 cycles of the cyclic sulfate environment. Microstructural and Microanalytical study was conducted by means of x-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectroscopy (EDS) and mercury intrusion porosimetry (MIP). Results indicate that the pore structure of concrete after sulfate exposure possesses the fractal feature. The OPC concrete presents more complex pore internal surface, higher porosity and less micro-pores than the concrete incorporating fly ash and GBFS. Portlandite in OPC concrete and OPC-FA concrete is mainly converted to gypsum; while for OPC-GBFS concrete, both gypsum and ettringite are formed. In the cyclic sulfate environment, repeated hydration and dehydration of sulfates produce the expansive stress in pores, aggravating the demolishment of concrete structure.
NASA Astrophysics Data System (ADS)
Pierre, Catherine; Blanc-Valleron, Marie-Madeleine; Boudouma, Omar; Lofi, Johanna
2017-12-01
The New Jersey continental shelf extends 150 km off the shoreline. During IODP Expedition 313, siliciclastic deposits of late Eocene to late Pleistocene age were drilled down to 631, 669 and 755 m below seafloor at sites 27A, 28A and 29A respectively in very shallow waters (33.5 to 36 m depth). Pore water salinities display multilayered brackish-salty-brine units 10 to 170 m thick, where low-salinity water is preferentially stored in fine-grained sediments. The sharp boundaries of these buried aquifers are often marked by cemented layers a few centimetres thick. The mineralogy and scanning electron microscope observations of these layers show two phases of cementation by authigenic minerals: (1) the early carbonate cement is frequently associated with pyrite, and (2) the late silicate cement infills the residual porosity. The isotopic compositions of the carbonate cements vary widely: -2.4 < δ18O ‰ VPDB < +2.8; -15.1 < δ13C ‰ VPDB < +15.6. The δ18O values indicate that the carbonate cements precipitated with pore waters comprising variable mixtures of seawater and 18O-depleted fresh water originating from submarine groundwater discharge. The δ13C values of the carbonate cements are related to organic matter diagenesis, providing 13C-depleted dissolved inorganic carbon during bacterial sulphate reduction and anaerobic oxidation of methane, and 13C-rich dissolved inorganic carbon during methanogenesis. The diagenetic cementation processes included chemical weathering of reactive silicate minerals by the CO2-rich pore waters issued from organic matter diagenesis that released bicarbonate, cations and dissolved silica, which were further precipitated as carbonate and silicate cements. The estimated range of temperature (18±4 °C) during carbonate precipitation is consistent with carbonate cementation at moderate burial depths; however, silicate cementation occurred later during diagenesis at deeper burial depths.
NASA Astrophysics Data System (ADS)
Radonjic, M.; Du, H.
2015-12-01
Shale caprocks and wellbore cements are two of the most common subsurface impermeable barriers in the oil and gas industry. More than 60% of effective seals for geologic hydrocarbon bearing formations as natural hydraulic barriers constitute of shale rocks. Wellbore cements provide zonal isolation as an engineered hydraulic barrier to ensure controlled fluid flow from the reservoir to the production facilities. Shale caprocks were deposited and formed by squeezing excess formation water and mineralogical transformations at different temperatures and pressures. In a similar process, wellbore cements are subjected to compression during expandable tubular operations, which lead to a rapid pore water propagation and secondary mineral precipitation within the cement. The focus of this research was to investigate the effect of wellbore cement compression on its microstructure and mechanical properties, as well as a preliminary comparison of shale caprocks and hydrated cement. The purpose of comparative evaluation of engineered vs natural hydraulic barrier materials is to further improve wellbore cement durability when in contact with geofluids. The micro-indentation was utilized to evaluate the change in cement mechanical properties caused by compression. Indentation experiments showed an overall increase in hardness and Young's modulus of compressed cement. Furthermore, SEM imaging and Electron Probe Microanalysis showed mineralogical alterations and decrease in porosity. These can be correlated with the cement rehydration caused by microstructure changes as a result of compression. The mechanical properties were also quantitatively compared to shale caprock samples in order to investigate the similarities of hydraulic barrier features that could help to improve the subsurface application of cement in zonal isolation. The comparison results showed that the poro-mechanical characteristics of wellbore cement appear to be improved when inherent pore sizes are shifted to predominantly nano-scale range as characteristic of pore-size distribution typical for shale rocks. The effect of compression on cement appears to petrophysically alter cement towards the properties of shale caprocks, although the process is achieved much faster than in the case of shale diagenesis over geological times.
Viani, Alberto; Sotiriadis, Konstantinos; Kumpová, Ivana; Mancini, Lucia; Appavou, Marie-Sousai
2017-04-01
To characterize the microstructure of two zinc phosphate cement formulations in order to investigate the role of liquid/solid ratio and composition of powder component, on the developed porosity and, consequently, on compressive strength. X-ray powder diffraction with the Rietveld method was used to study the phase composition of zinc oxide powder and cements. Powder component and cement microstructure were investigated with scanning electron microscopy. Small angle neutron scattering (SANS) and microfocus X-ray computed tomography (XmCT) were together employed to characterize porosity and microstructure of dental cements. Compressive strength tests were performed to evaluate their mechanical performance. The beneficial effects obtained by the addition of Al, Mg and B to modulate powder reactivity were mitigated by the crystallization of a Zn aluminate phase not involved in the cement setting reaction. Both cements showed spherical pores with a bimodal distribution at the micro/nano-scale. Pores, containing a low density gel-like phase, developed through segregation of liquid during setting. Increasing liquid/solid ratio from 0.378 to 0.571, increased both SANS and XmCT-derived specific surface area (by 56% and 22%, respectively), porosity (XmCT-derived porosity increased from 3.8% to 5.2%), the relative fraction of large pores ≥50μm, decreased compressive strength from 50±3MPa to 39±3MPa, and favored microstructural and compositional inhomogeneities. Explain aspects of powder design affecting the setting reaction and, in turn, cement performance, to help in optimizing cement formulation. The mechanism behind development of porosity and specific surface area explains mechanical performance, and processes such as erosion and fluoride release/uptake. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.
Pore size distribution of OPC and SRPC mortars in presence of chlorides
DOE Office of Scientific and Technical Information (OSTI.GOV)
Suryavanshi, A.K.; Scantlebury, J.D.; Lyon, S.B.
1995-07-01
The pore structure of chloride-free ordinary portland cement (OPC) and sulphate resistant portland cement (SRPC) mortars are compared with the corresponding mortars with NaCl and CaCl{sub 2} added during mixing. In both OPC and SRPC mortars the addition of chlorides reduced the total accessible pore volumes compared to the corresponding chloride-free mortars. Also, in the presence of chlorides, the number of coarse pores were increased. These changes in the pore structure are believed to be due to dense calcium silicate hydrate (C-S-H) gel morphology formed in the presence of chlorides. The SRPC showed greater changes in pore structures than themore » OPC with equivalent amounts of chlorides added. This may be due to the lower chloride binding capacity of the SRPC and hence the higher availability of free chlorides to modify the gel morphology.« less
Effects of nano-SiO(2) and different ash particle sizes on sludge ash-cement mortar.
Lin, K L; Chang, W C; Lin, D F; Luo, H L; Tsai, M C
2008-09-01
The effects of nano-SiO(2) on three ash particle sizes in mortar were studied by replacing a portion of the cement with incinerated sewage sludge ash. Results indicate that the amount of water needed at standard consistency increased as more nano-SiO(2) was added. Moreover, a reduction in setting time became noticeable for smaller ash particle sizes. The compressive strength of the ash-cement mortar increased as more nano-SiO(2) was added. Additionally, with 2% nano-SiO(2) added and a cure length of 7 days, the compressive strength of the ash-cement mortar with 1 microm ash particle size was about 1.5 times better that of 75microm particle size. Further, nano-SiO(2) functioned to fill pores for ash-cement mortar with different ash particle sizes. However, the effects of this pore-filling varied with ash particle size. Higher amounts of nano-SiO(2) better influenced the ash-cement mortar with larger ash particle sizes.
NASA Astrophysics Data System (ADS)
Hosa, Aleksandra; Wood, Rachel
2017-06-01
The reservoir properties of carbonate rocks are controlled by both deposition and diagenesis. The latter includes the early precipitation of calcite cements, which can exert a strong control on the evolution of subsequent diagenetic pathways. We quantify the impact of early marine cement growth in grainstones on evolving pore space by examining trends in the relationship between cementation and permeability using a 3D process-based model (Calcite3D). The model assumes varying proportions of polycrystalline and monocrystalline grain types, upon which we grow isopachous and syntaxial calcite cement types, respectively. We model two syntaxial cement shapes, compact and elongated, that approximate the geometries of typical rhombohedral calcite forms. Results demonstrate the effect of cement competition: an increasing proportion of monocrystalline grains creates stronger competition and a reduction in the impact of individual grains on final calcite cement volume and porosity. Isopachous cement is effective in closing pore throats and limiting permeability. We also show that the impact of syntaxial cement on porosity occlusion and therefore flow is highly dependent on monocrystalline grain location and the orientation of crystal axes. This demonstrates the importance of diagenetic overprint in controlling the evolution of rock properties, but also that this process can be essentially random. We also show that diagenesis alone can create notable heterogeneity in the permeability of carbonates. While Calcite3D is successful in modelling realistic changes in cement volumes and pore space morphology, modelled permeabilities (0.01 -30D) are above the range reported in reservoir grainstones due to the very high permeability of the initial synthetic sediment deposit (58.9D). Poroperm data generated by Calcite3D, however, exhibits a linear relationship between the logarithms of porosity and permeability with a high coefficient of determination, as observed in natural media.
Direct observation of void evolution during cement hydration
Moradian, Masoud; Hu, Qinang; Aboustait, Mohammed; ...
2017-09-28
This study follows the hydration of both portland cement and tricalcium silicate pastes between 30 min and 16 h of hydration. In-situ fast X-ray Computed Tomography (fCT) was used to make direct observations of the air-filled void formation in w/s of 0.40 to 0.70 with a micron resolution. The results show that over the first hour of the acceleration period the volume of air-filled voids reaches a maximum value and then decreases during the acceleration period and stays constant. The void distribution changes from a few coarse voids to a large number of smaller and more uniformly distributed voids. Thismore » behavior is suggested to be controlled by changes in the ionic strength that cause exsolution of dissolved air from the pore solution.« less
Direct observation of void evolution during cement hydration
DOE Office of Scientific and Technical Information (OSTI.GOV)
Moradian, Masoud; Hu, Qinang; Aboustait, Mohammed
This study follows the hydration of both portland cement and tricalcium silicate pastes between 30 min and 16 h of hydration. In-situ fast X-ray Computed Tomography (fCT) was used to make direct observations of the air-filled void formation in w/s of 0.40 to 0.70 with a micron resolution. The results show that over the first hour of the acceleration period the volume of air-filled voids reaches a maximum value and then decreases during the acceleration period and stays constant. The void distribution changes from a few coarse voids to a large number of smaller and more uniformly distributed voids. Thismore » behavior is suggested to be controlled by changes in the ionic strength that cause exsolution of dissolved air from the pore solution.« less
Tian, Zhenghong; Bu, Jingwu
2014-01-01
The uniaxial compression response of manufactured sand mortars proportioned using different water-cement ratio and sand-cement ratio is examined. Pore structure parameters such as porosity, threshold diameter, mean diameter, and total amounts of macropores, as well as shape and size of micropores are quantified by using mercury intrusion porosimetry (MIP) technique. Test results indicate that strains at peak stress and compressive strength decreased with the increasing sand-cement ratio due to insufficient binders to wrap up entire sand. A compression stress-strain model of normal concrete extending to predict the stress-strain relationships of manufactured sand mortar is verified and agreed well with experimental data. Furthermore, the stress-strain model constant is found to be influenced by threshold diameter, mean diameter, shape, and size of micropores. A mathematical model relating stress-strain model constants to the relevant pore structure parameters of manufactured sand mortar is developed. PMID:25133257
Tian, Zhenghong; Bu, Jingwu
2014-01-01
The uniaxial compression response of manufactured sand mortars proportioned using different water-cement ratio and sand-cement ratio is examined. Pore structure parameters such as porosity, threshold diameter, mean diameter, and total amounts of macropores, as well as shape and size of micropores are quantified by using mercury intrusion porosimetry (MIP) technique. Test results indicate that strains at peak stress and compressive strength decreased with the increasing sand-cement ratio due to insufficient binders to wrap up entire sand. A compression stress-strain model of normal concrete extending to predict the stress-strain relationships of manufactured sand mortar is verified and agreed well with experimental data. Furthermore, the stress-strain model constant is found to be influenced by threshold diameter, mean diameter, shape, and size of micropores. A mathematical model relating stress-strain model constants to the relevant pore structure parameters of manufactured sand mortar is developed.
On the Interaction between Superabsorbent Hydrogels and Cementitious Materials
NASA Astrophysics Data System (ADS)
Farzanian, Khashayar
Autogenous shrinkage induced cracking is a major concern in high performance concretes (HPC), which are produced with low water to cement ratios. Internal curing to maintain high relative humidity in HPC with the use of an internal water reservoir has proven effective in mitigating autogenous shrinkage in HPC. Superabsorbent polymers (SAP) or hydrogels have received increasing attention as an internal curing agent in recent years. A key advantage of SAP is its versatility in size distribution and absorption/desorption characteristics, which allow it to be adapted to specific mix designs. Understanding the behavior of superabsorbent hydrogels in cementitious materials is critical for accurate design of internal curing. The primary goal of this study is to fundamentally understand the interaction between superabsorbent hydrogels and cementitious materials. In the first step, the effect of chemical and mechanical conditions on the absorption of hydrogels is investigated. In the second step, the desorption of hydrogels in contact with porous cementitious materials is examined to aid in understanding the mechanisms of water release from superabsorbent hydrogels (SAP) into cementitious materials. The dependence of hydrogel desorption on the microstructure of cementitious materials and relative humidity is studied. It is shown that the capillary forces developed at the interface between the hydrogel and cementitious materials increased the desorption of the hydrogels. The size of hydrogels is shown to influence desorption, beyond the known size dependence of bulk diffusion, through debonding from the cementitious matrix, thereby decreasing the effect of the Laplace pressure on desorption. In the third step, the desorption of hydrogels synthesized with varied chemical compositions in cementitious materials are investigated. The absorption, chemical structure and mechanical response of hydrogels swollen in a cement mixture are studied. The effect of the capillary forces on the desorption of hydrogels is investigated in relation to the chemical composition of the hydrogels. In the second set of experiments of this part, the behavior of the hydrogels in a hydrating cement paste is monitored by tracking the size and morphology evolution of hydrogels interacting with the cement paste matrix. It is shown that the changes on the surface characteristics of hydrogels as a result of interactions with the pore solution and cement particles can affect the desorption rate of hydrogels in contact with a porous cementitious material. Scanning electron microscopic (SEM) examination demonstrates two different desorption modes with distinct morphologies of hydrogels depending on the chemical composition of hydrogels. The effect of the interfacial bonding between the hydrogels and the cementitious matrix and its relation to the desorption is illustrated. The desorption of hydrogels with different chemical compositions in blended cement mixture containing different supplementary cementitious materials (SCMs) such as slag, fly ash, silica fume and two types of glass powders, are examined. The absorption/desorption kinetics of hydrogels in different hydrating blended cement mixtures are monitored by freeze drying the samples at different times. The surface characteristics of different hydrogels after interaction with pore solution, cement particles and SCMs particles are examined and their relation to interfacial bonding is illustrated. It is shown that different SCMs can cause distinct changes on interfacial bonding. The understanding of hydrogel behavior in cementitious materials helps with accurate mixture design for internal curing. The kinetics of desorption is crucial for the purpose of internal curing. The understanding of release mechanisms and the change in the hydrogel morphology is important for the self-healing and self-sealing applications. Two major contributions of this research are (1) to show the effect of capillary forces developed at the interface between cementitious matrix and hydrogel which can increase the rate of desorption dramatically and (2) to illustrate the chemo-physical interaction between cement pore solution and hydrating particles with hydrogels which can affect the interfacial bonding between hydrogel and cement. These two main contributions will be useful to understand the absorption and desorption behavior of hydrogel in cementitious materials. Two main strengths of experimental procedures of this research are (1) use of in-house synthesis of hydrogels that permits establishing a link between the chemical composition of hydrogels and their behavior in cementitious materials and (2) use of freeze drying for the first time to monitor the behavior of hydrogels interacting with a hydrating cementitious matrix.
Shock Wave Propagation in Cementitious Materials at Micro/Meso Scales
2015-08-31
ABSTRACT 16. SECURITY CLASSIFICATION OF: Shock wave response of heterogeneous materials like cement and concrete is greatly influenced by the...constituents and their statistical distributions. The microstructure of cement is complex due to the presence of unhydrated water, nano /micro pores, and other...heterogeneous materials like cement and concrete is greatly influenced by the constituents and their statistical distributions. The microstructure of cement
Probing the Dynamics of Biomineralization at the Pore Scale Using X-ray Computed Tomography
NASA Astrophysics Data System (ADS)
Armstrong, R. T.; Ajo Franklin, J. B.
2009-12-01
Biomineralization is a natural subsurface process that upon stimulation can dramatically affect soil mechanics and hydraulics. This work presents the results of a study where synchrotron based X-Ray Computed Microtomography (CMT) is used to investigate temporal cementation dynamics and the spatial distribution of biogenic CaCO3 at the pore-scale, thus, shedding light on pore clogging and contact cementation. To facilitate these studies we have developed a family of flow-through bioreactors (ID 8 mm) which can be scanned continuously during precipitation experiments. The reactor is also equipped with differential pressure transducers to allow measurement of sample permeability. Porosity permeability correlations, cementation morphology, CaCO3 spatial distribution, and bulk cementation are addressed herein. Sporosarcina pasteurii (formally Bacillus pasteurii), our model organism, is a prevalent aerobic, motile, soil microbe with a very active urease enzyme. Hydrolysis of urea by the urease enzyme generates carbonate ions, ammonium and an increase in pH which favors carbonate precipitation if appropriate metal cations (e.g. Ca2+) are available. Brightfield microscope results show that precipitation occurs within close proximity of the cell membrane reducing microbial motility and forming a CaCO3 precipitate with a "fluffy" appearance. Besides providing an aqueous environment favorable for mineralization S. pasteurii also provides nucleation sites on its cell membrane. Since this microbe is very effective at inducing carbonate precipitation over a relativity short time span (2-3 days), it was used exclusively in our experiments. Prior to CMT imaging the feasibility of temporal imaging was investigated. Viable cell counts taken before and after imaging showed that a considerable amount of bacteria survived the monochromatic (30 KeV) X-ray exposure. Cementation experiments initiated with inoculation of the CMT column with microbes and urea media, cells were allowed to attach to particle surfaces, then subjected to sequential cementation treatments of urea media and calcium chloride. Current results indicate a morphological difference in formed CaCO3 depending on microbial acclimation to the system (i.e. surface attached or free floating microbes) and CaCO3 spatial arrangements within the porous matrix (i.e. pore necks or pore bodies). Our initial studies indicate that synchrotron CMT will be a powerful tool for pore-scale monitoring of biomineralization, a process relevant to geological carbon sequestration, bioremediation, enhanced oil recovery, slope stability and etc.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Majid, Z.A.; Mahmud, H.; Shaaban, M.G.
Stabilization/solidification of hazardous wastes is used to convert hazardous metal hydroxide waste sludge into a solid mass with better handling properties. This study investigated the pore size development of ordinary portland cement pastes containing metal hydroxide waste sludge and rice husk ash using mercury intrusion porosimetry. The effects of acre and the addition of rice husk ash on pore size development and strength were studied. It was found that the pore structures of mixes changed significantly with curing acre. The pore size shifted from 1,204 to 324 {angstrom} for 3-day old cement paste, and from 956 to 263 {angstrom} formore » a 7-day old sample. A reduction in pore size distribution for different curing ages was also observed in the other mixtures. From this limited study, no conclusion could be made as to any correlation between strength development and porosity. 10 refs., 6 figs., 3 tabs.« less
Long, Wu-Jian; Li, Hao-Dao; Fang, Chang-Le; Xing, Feng
2018-01-09
The properties of graphene oxide (GO)-based cement paste can be significantly affected by the state of GO dispersion. In this study, the effects of uniformly dispersed and re-agglomerated GO on the rheological, mechanical properties and microstructure of cement paste were systematically investigated. Two distinct dispersion states can be achieved by altering the mixing sequence: Polycarboxylate-ether (PCE) mixed with GO-cement or cement mixed with GO-PCE. The experimental results showed that the yield stress and plastic viscosity increased with the uniformly dispersed GO when compared to those of re-agglomerated GO cement paste. Moreover, the 3-day compressive and flexural strengths of uniformly dispersed GO paste were 8% and 27%, respectively, higher than those of re-agglomerated GO pastes. The results of X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy analyses demonstrated that uniformly dispersed GO more effectively promotes the formation of hydration products in hardened cement paste. Furthermore, a porosity analysis using mercury intrusion porosimetry revealed that the homogeneous dispersion of GO can better inhibit the formation of large-size pores and optimize the pore size distribution at 3 and 7 days than the re-agglomerated GO.
NASA Astrophysics Data System (ADS)
Barnes, H.; Spinelli, G. A.; Mozley, P.
2015-12-01
Fault-zones are an important control on fluid flow, affecting groundwater supply, hydrocarbon/contaminant migration, and waste/carbon storage. However, current models of fault seal are inadequate, primarily focusing on juxtaposition and entrainment effects, despite the recognition that fault-zone cementation is common and can dramatically reduce permeability. We map the 3D cementation patterns of the variably cemented Loma Blanca fault from the land surface to ~40 m depth, using electrical resistivity and induced polarization (IP). The carbonate-cemented fault zone is a region of anomalously low normalized chargeability, relative to the surrounding host material. Zones of low-normalized chargeability immediately under the exposed cement provide the first ground-truth that a cemented fault yields an observable IP anomaly. Low-normalized chargeability extends down from the surface exposure, surrounded by zones of high-normalized chargeability, at an orientation consistent with normal faults in the region; this likely indicates cementation of the fault zone at depth, which could be confirmed by drilling and coring. Our observations are consistent with: 1) the expectation that carbonate cement in a sandstone should lower normalized chargeability by reducing pore-surface area and bridging gaps in the pore space, and 2) laboratory experiments confirming that calcite precipitation within a column of glass beads decreases polarization magnitude. The ability to characterize spatial variations in the degree of fault-zone cementation with resistivity and IP has exciting implications for improving predictive models of the hydrogeologic impacts of cementation within faults.
NASA Astrophysics Data System (ADS)
Zhang, Zuhua; Wang, Hao
2016-08-01
The pore characteristics of GFCs manufactured in the laboratory with 0-16% foam additions were examined using image analysis (IA) and vacuum water saturation techniques. The pore size distribution, pore shape and porosity were obtained. The IA method provides a suitable approach to obtain the information of large pores, which are more important in affecting the compressive strength of GFC. By examining the applicability of the existing models of predicting compressive strength of foam concrete, a modified Ryshkevitch’s model is proposed for GFC, in which only the porosity that is contributed by the pores over a critical diameter (>100 μm) is considered. This “critical void model” is shown to have very satisfying prediction capability in the studied range of porosity. A compression-modulus model for Portland cement concrete is recommended for predicting the compression modulus elasticity of GFC. This study confirms that GFC have similar pore structures and mechanical behavior as those Portland cement foam concrete and can be used alternatively in the industry for the construction and insulation purposes.
Shrinkage deformation of cement foam concrete
NASA Astrophysics Data System (ADS)
Kudyakov, A. I.; Steshenko, A. B.
2015-01-01
The article presents the results of research of dispersion-reinforced cement foam concrete with chrysotile asbestos fibers. The goal was to study the patterns of influence of chrysotile asbestos fibers on drying shrinkage deformation of cement foam concrete of natural hardening. The chrysotile asbestos fiber contains cylindrical fiber shaped particles with a diameter of 0.55 micron to 8 microns, which are composed of nanostructures of the same form with diameters up to 55 nm and length up to 22 microns. Taking into account the wall thickness, effective reinforcement can be achieved only by microtube foam materials, the so- called carbon nanotubes, the dimensions of which are of power less that the wall pore diameter. The presence of not reinforced foam concrete pores with perforated walls causes a decrease in its strength, decreases the mechanical properties of the investigated material and increases its shrinkage. The microstructure investigation results have shown that introduction of chrysotile asbestos fibers in an amount of 2 % by weight of cement provides the finely porous foam concrete structure with more uniform size closed pores, which are uniformly distributed over the volume. This reduces the shrinkage deformation of foam concrete by 50%.
2018-01-01
This study compares the differences and similarities of two types of superplasticizers—NSF (Naphthalene Sulfonate Formaldehyde) and PCE (PolyCarboxylate Ester)—in fresh cement paste systems, in terms of adsorption, dynamic yield stress, and thixotropic index. Results show that with either NSF or PCE addition, the more superplasticizer is added, the more it is adsorbed and the more it remains in the interstitial pore solution. The dynamic yield stress and thixotropic index also decrease with increasing addition the amount of either superplasticizer. However, NSF is less efficient in decreasing the dynamic yield stress than PCE. More importantly, the decreasing patterns of dynamic yield stress and thixotropic index are different with NSF and PCE additions; this is tied to the adsorption and dispersing mechanisms of these two types of superplasticizers. PMID:29710782
DOE Office of Scientific and Technical Information (OSTI.GOV)
Maliva, R.G.; Dickson, J.A.D.; Smalley, P.C.
1995-01-02
The Chalk Group (Cretaceous/Tertiary) in the Machar Field (British North Sea) contains both fracture-filling and microcrystalline calcite cements. Modeling of fluid-rock interaction using data on light stable isotopes obtained by whole rock analyses and laser ablation analyses of calcite cements reveal that the fracture and matrix diagenetic systems were largely decoupled. The calcium and carbonate of the fracture-filling calcite cements were derived largely from the adjacent chalk matrix. The fracture diagenetic system had a high water-rock ratio, which maintained a relatively stable water {delta}{sup 18}O ratio during calcite dissolution and precipitation. The chalk matrix, on the contrary, had a lowmore » molar water-rock ratio during recrystallization, which resulted in increases in the pore-water {delta}{sup 18}O value during recrystallization at elevated temperatures. This evolution of the pore-water {delta}{sup 18}O value is manifested by highly variable cement {delta}{sup 18}O values. The present-day formation waters of the Machar Field have {sup 87}Sr/{sup 86}Sr ratios significantly higher than the whole rock and fracture-filling cement calcite values, evidence that the chemical composition of the formation waters is not representative of that of the pore waters during chalk recrystallization. Little diagenesis is therefore now occurring in the Machar Field. The diagenetic systems of the chalk matrix and fractures both had a high degree of openness with respect to carbon, because of the introduction of organically derived bicarbonate rather than advection of water through the chalk. The bulk of calcite cementation in fractures and the recrystallization and cementation of the chalk matrix occurred at temperatures in the 80--100 C range, at or just below the present-day reservoir temperature of 97 C.« less
Hydration-dependent dynamics of water in calcium-silicate-hydrate: A QENS study by global model.
Le, Peisi; Fratini, Emiliano; Chen, Sow-Hsin
2018-02-02
In a saturated cement paste, there are three different types of water: the structural water chemically reacted with cement, the constrained water absorbed to the surface of the pores, and the free water in the center of the pores. Each type has different physicochemical state and unique relation to cement porosity. The different water types have different dynamics which can be detected using quasi-elastic neutron scattering (QENS). Since the porosity of a hardened cement paste is impacted strongly by the water to cement ratio (w/c), it should be possible to extract the hydration dependence of the pores by exploiting the dynamical parameters of the confined water. Three C-S-H samples with different water levels, 8%, 17% and 30% were measured using QENS. The measurements were carried out in the scattering vector, Q, range from 0.5 Å -1 to 1.3 Å -1 , and in the temperature interval from 230 K to 280 K. The data were analyzed using a novel global model developed for cement QENS spectra. The results show that while increasing the water content, the structural water index (SWI) decreases and the confining radius, a, increases. Both SWI and a have a linear relationship with the water content. The Arrhenius plot of the translational relaxation time shows that the constrained water dominates the non-structural water at water contents lower than 17%. The rotational activation energy is smaller for lower water content. The analysis demonstrated that our newly proposed global model is practical and useful for analyzing cement QENS data. Copyright © 2018 Elsevier B.V. All rights reserved.
Zhao, Yi-Nan; Fan, Jun-Jun; Li, Zhi-Quan; Liu, Yan-Wu; Wu, Yao-Ping; Liu, Jian
2017-02-01
Calcium phosphate cement (CPC) porous scaffold is widely used as a suitable bone substitute to repair bone defect, but the optimal pore size is unclear yet. The current study aimed to evaluate the effect of different pore sizes on the processing of bone formation in repairing segmental bone defect of rabbits using CPC porous scaffolds. Three kinds of CPC porous scaffolds with 5 mm diameters and 12 mm length were prepared with the same porosity but different pore sizes (Group A: 200-300 µm, Group B: 300-450 µm, Group C: 450-600 µm, respectively). Twelve millimeter segmental bone defects were created in the middle of the radius bone and filled with different kinds of CPC cylindrical scaffolds. After 4, 12, and 24 weeks, alkaline phosphatase (ALP), histological assessment, and mechanical properties evaluation were performed in all three groups. After 4 weeks, ALP activity increased in all groups but was highest in Group A with smallest pore size. The new bone formation within the scaffolds was not obvious in all groups. After 12 weeks, the new bone formation within the scaffolds was obvious in each group and highest in Group A. At 24 weeks, no significant difference in new bone formation was observed among different groups. Besides the osteoconductive effect, Group A with smallest pore size also had the best mechanical properties in vivo at 12 weeks. We demonstrate that pore size has a significant effect on the osteoconductivity and mechanical properties of calcium phosphate cement porous scaffold in vivo. Small pore size favors the bone formation in the early stage and may be more suitable for repairing segmental bone defect in vivo. © 2016 International Center for Artificial Organs and Transplantation and Wiley Periodicals, Inc.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ye, G.; Liu, X.; De Schutter, G.
2007-06-15
Self-compacting concrete, as a new smart building material with various advanced properties, has been used for a wide range of structures and infrastructures. However little investigation have been reported on the properties of Self-compacting when it is exposed to elevated temperatures. Previous experiments on fire test have shown the differences between high performance concrete and traditional concrete at elevated temperature. This difference is largely depending on the microstructural properties of concrete matrix, i.e. the cement paste, especially on the porosity, pore size distribution and the connectivity of pores in cement pastes. In this contribution, the investigations are focused on themore » cement paste. The phase distribution and microstructural changes of self-compacting cement paste at elevated temperatures are examined by mercury intrusion porosimetry and scanning electron microscopy. The chemical decomposition of self-compacting cement paste at different temperatures is determined by thermogravimetric analysis. The experimental results of self-compacting cement paste are compared with those of high performance cement paste and traditional cement paste. It was found that self-compacting cement paste shows a higher change of the total porosity in comparison with high performance cement paste. When the temperature is higher than 700 deg. C, a dramatic loss of mass was observed in the self-compacting cement paste samples with addition of limestone filler. This implies that the SCC made by this type of self-compacting cement paste will probably show larger damage once exposed to fire. Investigation has shown that 0.5 kg/m{sup 3} of Polypropylene fibers in the self-compacting cement paste can avoid the damage efficiently.« less
NASA Astrophysics Data System (ADS)
Mozley, P.; Yoon, H.; Williams, R. T.; Goodwin, L. B.
2015-12-01
The spatial distribution of pore-filling authigenic minerals (cements) is highly variable and controlled in large part by the mineralogy of the cements and host sediment grains. Two end-member distributions of cements that commonly occur in sedimentary material are: (1) concretionary, in which precipitation occurred in specific zones throughout the sediment, with intervening areas largely uncemented; and (2) grain-rimming, in which precipitation occurred on grain-surfaces relatively uniformly throughout the rock. Concretions form in rocks in which sediment grains have a different composition from the cement, whereas rim cements form in those that have the same composition. Both the mechanical attributes and permeability of a given volume of rock are affected to a much greater extent by grain rimming cements, which have a significant impact on properties at even low abundances. Concretionary cements have little impact on bulk properties until relatively large volumes have precipitated (~80% cemented) and concretions begin to link up. Precipitation of cement in fault zones also impacts both mechanical and hydrologic properties. Cementation will stiffen and strengthen unlithified sediment, thereby controlling the locus of fracturing in protolith or damage zones. Where fracture networks form in fault damage zones, they are initially high permeability elements. However, progressive cementation greatly diminishes fracture permeability, resulting in cyclical permeability variation linked to fault slip. To quantitatively describe the interactions of groundwater flow, permeability, and patterns and abundance of cements, we use pore-scale modeling of coupled fluid flow, reactive transport, and heterogeneous mineral-surface reactions. By exploring the effects of varying distributions of porosity and mineralogy, which impact patterns of cementation, we provide mechanistic explanations of the interactions of coupled processes under various flow and chemistry conditions.
Estimating pore and cement volumes in thin section
Halley, R.B.
1978-01-01
Point count estimates of pore, grain and cement volumes from thin sections are inaccurate, often by more than 100 percent, even though they may be surprisingly precise (reproducibility + or - 3 percent). Errors are produced by: 1) inclusion of submicroscopic pore space within solid volume and 2) edge effects caused by grain curvature within a 30-micron thick thin section. Submicroscopic porosity may be measured by various physical tests or may be visually estimated from scanning electron micrographs. Edge error takes the form of an envelope around grains and increases with decreasing grain size and sorting, increasing grain irregularity and tighter grain packing. Cements are greatly involved in edge error because of their position at grain peripheries and their generally small grain size. Edge error is minimized by methods which reduce the thickness of the sample viewed during point counting. Methods which effectively reduce thickness include use of ultra-thin thin sections or acetate peels, point counting in reflected light, or carefully focusing and counting on the upper surface of the thin section.
Impact of drying on pore structures in ettringite-rich cements
DOE Office of Scientific and Technical Information (OSTI.GOV)
Galan, I., E-mail: isabelgalan@abdn.ac.uk; Beltagui, H.; García-Maté, M.
Drying techniques affect the properties of cement pastes to varying extents. The effect of different drying techniques on calcium sulfoaluminate-based (C$A) cements and their constituent phases is reported for a range of simulated and commercial C$A pastes which are benchmarked against an OPC paste. The recommended methodologies used to dry samples were identified from the literature and include D-drying and solvent exchange. These methods were used in conjunction with mercury intrusion porosimetry (MIP) and X-ray powder diffraction (XRPD) measurements to assess the changes in pore structure and the damage to crystalline phases, respectively. D-drying and isopropanol exchange are the mostmore » satisfactory and least damaging methods for drying C$A based pastes.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Liu, X.; Magnel Laboratory for Concrete Research, Department of Structural Engineering, Ghent University, Technologiepark-Zwijnaarde 904 B-9052, Ghent; Ye, G.
2008-04-15
With the increasing application of self-compacting concrete (SCC) in construction and infrastructure, the fire spalling behavior of SCC has been attracting due attention. In high performance concrete (HPC), addition of polypropylene fibers (PP fibers) is widely used as an effective method to prevent explosive spalling. Hence, it would be useful to investigate whether the PP fibers are also efficient in SCC to avoid explosive spalling. However, no universal agreement exists concerning the fundamental mechanism of reducing the spalling risk by adding PP fiber. For SCC, the reduction of flowability should be considered when adding a significant amount of fibres. Inmore » this investigation, both the micro-level and macro-level properties of pastes with different fiber contents were studied in order to investigate the role of PP fiber at elevated temperature in self-compacting cement paste samples. The micro properties were studied by backscattering electron microscopy (BSE) and mercury intrusion porosimetry (MIP) tests. The modification of the pore structure at elevated temperature was investigated as well as the morphology of the PP fibers. Some macro properties were measured, such as the gas permeability of self-compacting cement paste after heating at different temperatures. The factors influencing gas permeability were analyzed. It is shown that with the melting of PP fiber, no significant increase in total pore volume is obtained. However, the connectivity of isolated pores increases, leading to an increase of gas permeability. With the increase of temperature, the addition of PP fibers reduces the damage of cement pastes, as seen from the total pore volume and the threshold pore diameter changes. From this investigation, it is concluded that the connectivity of pores as well as the creation of micro cracks are the major factors which determine the gas permeability after exposure to high temperatures. Furthermore, the connectivity of the pores acts as a dominant factor for temperatures below 300 deg. C. For higher temperatures micro cracks are becoming the major factor which influences the gas permeability.« less
Bordallo, Heloisa N; Aldridge, Laurence P; Desmedt, Arnaud
2006-09-14
Portland cement reacts with water to form an amorphous paste through a chemical reaction called hydration. In concrete the formation of pastes causes the mix to harden and gain strength to form a rock-like mass. Within this process lies the key to a remarkable peculiarity of concrete: it is plastic and soft when newly mixed, strong and durable when hardened. These qualities explain why one material, concrete, can build skyscrapers, bridges, sidewalks and superhighways, houses, and dams. The character of the concrete is determined by the quality of the paste. Creep and shrinkage of concrete specimens occur during the loss and gain of water from cement paste. To better understand the role of water in mature concrete, a series of quasielastic neutron scattering (QENS) experiments were carried out on cement pastes with water/cement ratio varying between 0.32 and 0.6. The samples were cured for about 28 days in sealed containers so that the initial water content would not change. These experiments were carried out with an actual sample of Portland cement rather than with the components of cement studied by other workers. The QENS spectra differentiated between three different water interactions: water that was chemically bound into the cement paste, the physically bound or "glassy water" that interacted with the surface of the gel pores in the paste, and unbound water molecules that are confined within the larger capillary pores of cement paste. The dynamics of the "glassy" and "unboud" water in an extended time scale, from a hundred picoseconds to a few nanoseconds, could be clearly differentiated from the data. While the observed motions on the picosecond time scale are mainly stochastic reorientations of the water molecules, the dynamics observed on the nanosecond range can be attributed to long-range diffusion. Diffusive motion was characterized by diffusion constants in the range of (0.6-2) 10(-9) m(2)/s, with significant reduction compared to the rate of diffusion for bulk water. This reduction of the water diffusion is discussed in terms of the interaction of the water with the calcium silicate gel and the ions present in the pore water.
NASA Astrophysics Data System (ADS)
Pierre, C.; Blanc-Valleron, M. M.; Lofi, J.
2016-12-01
The New Jersey continental shelf extends up to 150 km away from the shoreline. During IODP Expedition 313 the siliciclastic deposits of late Eocene to late Pleistocene age were drilled down to 631 mbsf, 669 mbsf and 700 mbsf at the three sites 27A, 28A, 29A respectively, in very shallow water depth (33.5 to 36 m). Pore water salinities display multilayered fresh-salty-brine units 10 to 170 m thick, where freshwater is preferentially stored in fine-grained sediments (van Geldern et al 2013 ; Lofi et al 2013). The sharp boundaries of these buried aquifers are often marked by hardly cemented layers a few centimeters thick. The mineralogy and SEM observations of these layers show two phases of cementation by authigenic minerals : (1) the early carbonate cement is made of Fe-dolomite, ankerite and occasionally calcite, frequently associated with pyrite (2) the late silicate cement (silica, K-Fe-rich clay minerals, zeolites) fills in the residual porosity. The isotopic compositions of the carbonate cements vary in wide ranges : -2.4 < δ18O‰ VPDB < +2.8 ; -15.1< δ13C ‰ VPDB <+15.6. The δ18O values indicate carbonate precipitation with pore waters more or less depleted in 18O of the buried aquifers. The δ13C values of carbonate are related to organic matter diagenesis providing 13C-depleted DIC during bacterial sulphate reduction (with pyrite as a by-product of the reaction) and 13C-rich DIC during methanogenesis. The diagenetic cementation processes included chemical weathering of reactive silicate minerals by the CO2-rich pore waters issued from organic matter diagenesis that released bicarbonate, cations and dissolved silica, which were further precipitated as carbonate and silicate cements. The temperature estimated (18 ± 4°C) for the precipitation of carbonate indicates that cementation occurred at moderate burial depths, i.e. probably very soon after deposition. Lofi J et al 2013. Geosphere, 9, 4, 1009-1024 Van Geldern R et al 2013. Geosphere, 9, 1, 96-112
Beyea, S D; Balcom, B J; Bremner, T W; Prado, P J; Cross, A R; Armstrong, R L; Grattan-Bellew, P E
1998-11-01
The removal of water from pores in hardened cement paste smaller than 50 nm results in cracking of the cement matrix due to the tensile stresses induced by drying shrinkage. Cracks in the matrix fundamentally alter the permeability of the material, and therefore directly affect the drying behaviour. Using Single-Point Imaging (SPI), we obtain one-dimensional moisture profiles of hydrated White Portland cement cylinders as a function of drying time. The drying behaviour of White Portland cement, is distinctly different from the drying behaviour of related concrete materials containing aggregates.
NASA Astrophysics Data System (ADS)
Nam, Jingak
Effects of (1) cement alkalinity (low, normal and high), (2) exposure conditions (RH and temperature), (3) rebar surface condition (as-received versus cleaned) and (4) density and distribution of air voids at the steel-concrete interface on the chloride threshold and time-to-corrosion for reinforcing steel in concrete have been studied. Also, experiments were performed to evaluate effects of RH and temperature on the diffusion of chloride in concrete and develop a method for ex-situ pH measurement of concrete pore water. Once specimens were fabricated and exposed to a corrosive chloride solution, various experimental techniques were employed to determine time-to-corrosion, chloride threshold, diffusion coefficient and void density along the rebar trace as well as pore water pH. Based upon the resultant data, several findings related to the above parameters have been obtained as summarized below. First, time for the corrosion initiation was longest for G109 concrete specimens with high alkalinity cement (HA). Also, chloride threshold increased with increasing time-to-corrosion and cement alkalinity. Consequently, the HA specimens exhibited the highest chloride threshold compared to low and normal alkalinity ones. Second, high temperature and temperature variations reduced time-to-corrosion of reinforcing steel in concrete since chloride diffusion was accelerated at higher temperature and possibly by temperature variations. The lowest chloride threshold values were found for outdoor exposed specimens suggesting that variation of RH or temperature (or both) facilitated rapid chloride diffusion. Third, an elevated time-to-corrosion and chloride threshold values were found for the wire brushed steel specimens compared to as-received ones. The higher ratio of [OH-]/[Fe n+] on the wire brushed steel surface compared to that of as-received case can be the possible cause because the higher ratio of this parameter enables the formation of a more protective passive film on the rebar. Fourth, voids at the steel-concrete interface facilitated passive film breakdown and onset of localized corrosion. This tendency for corrosion initiation increased in proportion to void size irrespective of specimen type. Also, [Cl -]th decreased with increasing void diameter. In addition, new ex-situ leaching method for determining concrete pore water alkalinity was developed.
NASA Astrophysics Data System (ADS)
Vincent, Benoit; Brigaud, Benjamin; Emmanuel, Laurent; Loreau, Jean-Paul
2017-04-01
The scope of this work is to investigate, at a high resolution, the oxygen isotope composition (δ18Ocarb) of diagenetic products (synsedimentary and burial calcite cements) in shallow-marine carbonates. SIMS (Secondary Ion Mass Spectrometry) microprobe analyses were performed on thin sections from Oxfordian and Kimmeridgian Formations of the eastern Paris Basin and compared to data obtained on the same diagenetic products by conventional mass spectrometry (acid digestion). Hereby obtained, δ18O are similar, but the SIMS dataset displays a larger range of values. The isotopic zonation obtained by SIMS transects through sequences of cements filling pores, reveals an (expected) isotopic depletion from older stage synsedimentary calcites to younger stage blocky calcites and that follows the CL (cathodoluminescence) zonation. SIMS analyses however show that synsedimentary cements precipitated in intra-skeletal pores, have heavier δ18O than their inter-particle counterparts, with an offset of + 4‰V-PDB, despite similar petrographical characteristics. This difference is maintained in the δ18O of the first stages of blocky calcite cements, intra-skeletal blocky calcites showing heavier δ18O than the time equivalent and petrographically identical inter-particle calcites, with an offset of + 5‰V-PDB. These offsets are tentatively explained by the precipitation of cements under non-equilibrium conditions in intra-skeletal pores, where organic matter decay may have played a key role, acting notably on the pH. The occurrence of isolated micro-diagenetic environments, co-existing at the thin section scale, is tentatively proposed as an explanation to these small scale and high amplitude δ18O heterogeneities. These results may question the sampling strategy for future works. Microdrilling may miss the observed range of variation, but averaging the values may not necessarily lead to real misinterpretations if a critical selection of samples is performed, targeting potentially similar micro-diagenetic environments and avoiding potentially specific ones, i.e. closed intra-skeletal pores. These results also definitely underscore the need for additional experiments to improve the reliability of SIMS, in order to develop the use of this very high resolution technique for carbonate diagenesis studies.
Cement hydration from hours to centuries controlled by diffusion through barrier shells of C-S-H
NASA Astrophysics Data System (ADS)
Rahimi-Aghdam, Saeed; Bažant, Zdeněk P.; Abdolhosseini Qomi, M. J.
2017-02-01
Although a few good models for cement hydration exist, they have some limitations. Some do not take into account the complete range of variation of pore relative humidity and temperature, and apply over durations limited from up a few months to up to about a year. The ones that are applicable for long durations are either computationally too intensive for use in finite element programs or predict the hydration to terminate after few months. However, recent tests of autogenous shrinkage and swelling in water imply that the hydration may continue, at decaying rate, for decades, provided that a not too low relative pore humidity (above 0.7) persists for a long time, as expected for the cores of thick concrete structural members. Therefore, and because design lifetimes of over hundred years are required for large concrete structures, a new hydration model for a hundred year lifespan and beyond is developed. The new model considers that, after the first day of hydration, the remnants of anhydrous cement grains, gradually consumed by hydration, are enveloped by contiguous, gradually thickening, spherical barrier shells of calcium-silicate hydrate (C-S-H). The hydration progress is controlled by transport of water from capillary pores through the barrier shells toward the interface with anhydrous cement. The transport is driven by a difference of humidity, defined by equivalence with the difference in chemical potential of water. Although, during the period of 4-24 h, the C-S-H forms discontinuous nano-globules around the cement grain, an equivalent barrier shell control was formulated for this period, too, for ease and effectiveness of calculation. The entire model is calibrated and validated by published test data on the evolution of hydration degree for various cement types, particle size distributions, water-cement ratios and temperatures. Computationally, this model is sufficiently effective for calculating the evolution of hydration degree (or aging) at every integration point of every finite element in a large structure.
NASA Astrophysics Data System (ADS)
Panchmatia, Parth
Numerous laboratory and field studies have demonstrated that concrete incorporating air cooled blast furnace slag (ACBFS) aggregate showed a higher degree of infilling of voids with ettringite as opposed to concrete prepared using naturally mined carbonate aggregates when exposed to similar environmental conditions. This observation prompted some to link the deterioration observed in the ACBFS aggregate concrete structures to the compromised freeze-thaw resistance due to infilling of air voids. Concerns about the release of sulfur from ACBFS aggregate into the pore solution of concrete had been presented as the reason for the observed ettringite deposits in the air voids. However, literature quantifying the influence of ACBFS aggregate on the chemistry of the pore solution of concrete is absent. Therefore, the main purpose of this research was to quantify the effects of ACBFS aggregate on the chemistry of the pore solution of mortars incorporating them. Coarse and crushed ACBFS aggregates were submerged in artificial pore solutions (APSs) representing pore solutions of 3-day, 7-day, and 28-day hydrated plain, binary, and ternary paste systems. The change in the chemistry of these artificial pore solutions was recorded to quantify the chemical contribution of ACBFS aggregate to the pore solution of concrete. It was observed that the sulfate concentration of all APSs increased once they were in contact with either coarse or crushed ACBFS aggregate. After 28 days of contact, the increase in sulfate concentration of the APSs ranged from 4.85 - 12.23 mmol/L and 14.21 - 16.87 mmol/L for contact with coarse and crushed ACBFS aggregate, respectively. More than 40% of the total sulfate that was released by the ACBFS aggregate occurred during the first 72 hours (3 days) of its contact with the APSs. There was little or no difference in the amount of sulfate released from ACBFS aggregate in the different types of APSs. In other words, the type of binder solution from which pore solution was extracted had no effect on the amount of sulfate that was released when it was in contact with ACBFS aggregate. The relatively quick release of sulfur from ACBFS aggregate into the APSs prompted investigation of the chemical composition of the pore solution of mortar (at early stages of hydration) incorporating ACBFS aggregate. The chemical composition of the pore solutions obtained from mortars prepared using ACBFS aggregate and plain and binary paste matrices was compared those of mortars prepared using Ottawa sand and plain and binary paste matrices. After 7 days of hydration, the sulfur (S) concentration of the pore solution extracted from mortars prepared using ACBFS aggregate was 3.4 - 5.6 times greater than that obtained from corresponding mortars (i.e. mortars with the same paste matrix) prepared using Ottawa sand. Binary mortars containing fly ash (FA) showed the lowest S content after 7 days of hydration amongst all mortars prepared using ACBFS aggregate. On the other hand, binary mortars prepared using slag cement (SC) and ACBFS aggregate had the highest S concentration after 7 days of hydration. These effects on the S concentration in the pore solutions can be explained by the difference in the chemical makeup of the binders, and not because of different rate of release of S from ACBFS into the pore solution. In addition, TGA analysis of 7-day hydrated mortars revealed that the ettringite, monosulfate, and calcium hydroxide content was lower in mortars prepared using ACBFS aggregate as opposed to those prepared using Ottawa sand. This could be because of the low degree of hydration in mortars with ACBFS aggregate because of the high sulfate concentration in its pore solution. The properties of the interfacial transition zone (ITZ), i.e. the zone in the vicinity of the aggregate surface, depends on the property of the aggregate such as its porosity and texture. Therefore, it is expected that the properties of ITZ around the ACBFS particle, which is porous and proven to contribute sulfate, be different from the ITZ around the naturally mined siliceous aggregate. Image analysis conducted on backscattered images obtained using scanning electron microscope revealed that the ITZ of naturally mined siliceous aggregate was more porous compared to the ITZ of ACBFS aggregate. In addition, calcium hydroxide deposits were more frequent and larger in size in the ITZ around siliceous sand than in the case of the ITZ around the ACBFS aggregate.
NASA Astrophysics Data System (ADS)
Hamilton, T. S.; Enkin, R. J.; Esteban, L.
2007-05-01
Bulk magnetic properties provide a sensitive measure of sedimentary diagenesis related to the stability and growth of gas hydrates. The deposit at Mallik (Mackenzie Delta, Canadian Arctic) occurs in unconsolidated Tertiary sands, but is absent in interstratified silt layers. A detailed sampling of the JAPEX/JNOC/GSC Mallik 5L-38 core tested the use of magnetic properties for detecting diagenetic changes related to the hydrate. Petrographic studies reveal that the sands are well sorted and clean, with quartz > chert >> muscovite and little fines content. Excepting a few rare bands of indurated dolomite in the midst of the gas hydrate zone, there is little or no cementation in the sands. Detrital magnetite is the dominant magnetic mineral, comprising up to a few percent of the sand grain population. In contrast, the muddier layers have a somewhat different detrital grain composition, richer in lithic (sedimentary and metamorphic) grains, feldspar, and clays. They are extensively diagenetically altered (to as much as 30- 40%) and cemented with carbonates, clays, chlorite and the iron sulphide greigite (the dominant magnetic mineral). The greigite is recognized by its isotropic creamy-white reflectance, cubic to prismatic habit, and characteristic tarnish to faintly bluish bireflectant mackinawite. Habits range from disseminated cubes and colliform masses to inflationary massive sulphide veins and clots. Rare detrital grains of magnetite were observed among the silt grains, but never in a reaction relationship or overgrown. Instead the greigite has nucleated separately, in tensional fractures and granular masses up to 4 mm across. In this particular sediment sequence, being so quartz and chert rich, there is insufficient local source for the introduced cements (calcite, dolomite, greigite, clays, jarosite), so ions must have been introduced by fluid flow. Magnetic studies reveal a bi-modal character related to the lithology (sands versus silts) and their magnetic mineralogy. Silt samples are significantly stronger than sand samples in saturation magnetization and magnetic susceptibility. The silt samples have single-domain to pseudo-single domain coercivity ratios whereas the gas hydrate bearing sands have a more multi-domain nature. Sands with current gas hydrate concentrations > 80% have less magnetic material and single domain characteristics. The source of the greigite, carbonates, and other diagenetic minerals was apparently concentrated solutes excluded from formation waters by the freezing and formation of the water dominated gas hydrate. The hydrates served as a cementing agent for the unconsolidated sediments, allowing them to fracture. Some layers have been so inflated by the introduction carbonate and sulfide cements that they resemble hydrothermal tufa and skarns with floating sand grains. In the silts, the magnetic properties reflect the mixture of primary detrital magnetite and diagenetic greigite in various grain sizes and concentrations. At Mallik, the magnetic properties are sensitive to the diagenetic mineralogy and redox state associated with the transport of methane and pore fluids and the creation of gas hydrates. Hypersaline brines, produced by solute exclusion from pore waters, fractured and inflated less permeable sediments and forced rapid disequilibrium growth of greigite without dissolving primary detrital magnetite grains.
NASA Astrophysics Data System (ADS)
Mehmani, Ayaz; Mehmani, Yashar; Prodanović, Maša.; Balhoff, Matthew
2015-06-01
We explore tracer breakthrough profiles (TBP) as a macroscopic property to infer the pore-space topology of tight gas sandstone and carbonate rocks at the core scale. The following features were modeled via three-dimensional multiscale networks: microporosity within dissolved grains and pore-filling clay, cementation in the absence and presence of microporosity (each classified into uniform, pore-preferred, and throat-preferred modes), layering, vug, and microcrack inclusion. A priori knowledge of the extent and location of each process was assumed to be known. With the exception of an equal importance of macropores and pore-filling micropores, TBPs show little sensitivity to the fraction of micropores present. In general, significant sensitivity of the TBPs was observed for uniform and throat-preferred cementation. Layering parallel to the fluid flow direction had a considerable impact on TBPs whereas layering perpendicular to flow did not. Microcrack orientations seemed of minor importance in affecting TBPs. This article was corrected on 9 Nov 2015. See the end of the full text for details.
NASA Astrophysics Data System (ADS)
Wu, Z.; Luhmann, A. J.; Rinehart, A. J.; Mozley, P.; Dewers, T. A.
2017-12-01
Carbon Capture, Utilization and Storage (CCUS) in transmissive reservoirs is a proposed mechanism in reducing CO2 emissions. Injection of CO2 perturbs reservoir chemistry, and can modify porosity and permeability and alter mineralogy. However, little work has been done on the coupling of rock alteration by CO2 injection and the mechanical integrity of the reservoir. In this study, we perform flow-through experiments on calcite- and dolomite-cemented Pennsylvanian Morrow B Sandstone (West Texas, USA) cores. We hypothesize that poikilotopic calcite cement has a larger impact on chemo-mechanical alteration than disseminated dolomite cement given similar CO2 exposure. With one control brine flow-through experiment and two CO2-plus-brine flow-through experiments for each cement composition, flow rates of 0.1 and 0.01 ml/min were applied under 4200 psi pore fluid pressure and 5000 psi confining pressure at 71 °C. Fluid chemistry and permeability data enable monitoring of mineral dissolution. Ultrasonic velocities were measured pre-test using 1.2 MHz source-receiver pairs at 0.5 MPa axial load and show calcite-cemented samples with higher dynamic elastic moduli than dolomite-cemented samples. Velocities measured post-experiment will identify changes from fluid-rock interaction. We plan to conduct cylinder-splitting destructive mechanical test (Brazil test) to measure the pristine and altered tensile strength of different cemented sandstones. The experiments will identify extents to which cement composition and texture control chemo-mechanical degradation of CCUS reservoirs. Funding for this project is provided by the U.S. Department of Energy's (DOE) National Energy Technology Laboratory (NETL) through the Southwest Regional Partnership on Carbon Sequestration (SWP) under Award No. DE-FC26-05NT42591. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia LLC, a wholly owned subsidiary of Honeywell International Inc. for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525.
Pore morphology effect in microlog for porosity prediction in a mature field
Teh, W.J.; Willhite, G.P.; Doveton, J.H.; Tsau, J.S.
2011-01-01
In an matured field, developed during the 1950s, no porosity logs were available from sources other than invaded zone resistivity Rxo . The microresistivity porosity is calibrated with the core porosity to yield an accurate estimate of the porosity. However, the procedure of calibrating the porosity with Rxo for a linear regression model may not be predictive without an understanding of the pore types in the reservoir interval. A thorough investigation of the pore types, based on the lithofacies description obtained from the core analysis, and its role in obtaining a good estimate of porosity is demonstrated in the Ogallah field. Therefore, the objective of this paper is to separate the porosity-microlog data into pore-type based zones with characteristic cementation exponents (m) in this multi-petrotype reservoir with a complex mixture of Arbuckle dolomite and sandstone rock. The value of m is critical in making estimates of water saturation. "Rule of thumb" values of cementation might lead to errors in water saturation on either the optimistic or the pessimistic side. The rock types in the Ogallah contain interparticle/intercrystalline, vugs and fractures distributed through the rock-facies, which influence the values of cementation factor. We use the modern typed well to shed light on the Archie's equation parameter values. Rock fabric numbers and flow zone indices have been identified for classification of dolomite and sandstone, respectively. The analysis brings out characteristic cementation factors for distinct pore types in the Arbuckle rock. The porosity predictions The analysis results also compliment the petrofacies delineation using LDA in this complicated rock layout as a quality control of the statistical application. The comparison between the predicted and core porosities shows a significant improvement over using a single m value for carbonates and sandstones which will lead to improved description of a matured field. Copyright 2011, Society of Petroleum Engineers.
Unusual calcite cementing of quartz grains on Chandeleur Island Beach, offshore Louisiana
DOE Office of Scientific and Technical Information (OSTI.GOV)
Mitchell-Tapping, H.J.
1983-09-01
A very unusual calcite cement was found in some beachchips from an unconsolidated beach surface of Chandeleur Island offshore approximately 35 nmi (65 km) south of Mississippi in the Gulf of Mexico. The beachchips are irregularly shaped and are well cemented by this unusual calcite. This calcite crystal structure has not been reported previously as existing in a marine environment. A similar cement has been found in freshwater lake beachrock and in some travertine samples. The calcite crystals are elongate parallel to the c-optic axis, and are composed of bunches of crystallite blades. The crystallite blades of each crystal bunchmore » are pointed and are more bladed than freshwater cement crystals. The intercrystallite pore space contains no fine calcite silt as was observed in the lake samples. Fresh water provided by rainfall may be held in the pore spaces and bounded to the quartz-grain surfaces by ionic attraction. Marine spray above and saline water concentrated underneath from a sandwich effect at the micropore level, allowing rapid growth and precipitation of these very unusual calcite crystals in a single-phase low-salinity fluid.« less
NASA Astrophysics Data System (ADS)
Leroy, P. G.; Gaboreau, S.; Zimmermann, E.; Hoerdt, A.; Claret, F.; Huisman, J. A.; Tournassat, C.
2017-12-01
Low-pH concretes are foreseen to be used in nuclear waste disposal. Understanding their reactivity upon the considered host-rock is a key point. Evolution of mineralogy, porosity, pore size distribution and connectivity can be monitored in situ using geophysical methods such as induced polarization (IP). This electrical method consists of injecting an alternating current and measuring the resulting voltage in the porous medium. Spectral IP (SIP) measurements in the 10 mHz to 10 kHz frequency range were carried out on low-pH concrete and cement paste first in equilibrium and then in contact with a CO2 enriched and diluted water. We observed a very high resistivity of the materials (> 10 kOhm m) and a strong phase shift between injected current and measured voltage (superior to 40 mrad and above 100 mrad for frequencies > 100 Hz). These observations were modelled by considering membrane polarization with ion exclusion in nanopores whose surface electrical properties were computed using a basic Stern model of the cement/water interface. Pore size distribution was deduced from SIP and was compared to the measured ones. In addition, we observed a decrease of the material resistivity due to the dissolution of cement in contact with external water. Our results show that SIP may be a valuable method to monitor the mineralogy and the petrophysical and transport properties of cements.
NASA Astrophysics Data System (ADS)
Ghabezloo, S.; Sulem, J.; Saint-Marc, J.
2009-04-01
It is well-known that there is no unique permeability-porosity relationship that can be applied to all porous materials. For a given evolution process that changes both permeability and porosity of a porous material, for example elastic or plastic compaction, microcracking or chemical alteration, it is usually assumed that there is an empirical relationship in the form of a power-law or exponential relationship between these parameters. The coefficients of these empirical relationships depend strongly on the properties of the material and of the evolution process. For the case of the power-law permeability-porosity relationship, a review of the literature shows that the exponent of this relation may be integer or non-integer, constant or variable, and the reported values of exponent vary between 1.1 and 25.4 for different materials and evolution processes, but no clear correlation between the exponenet and the petrophysical properties could be found. This wide variability of the permeability-porosity relationship highlights the necessity of experimental evaluation of this relationship for each material and evolution process. An experimental method is presented for the evaluation of a permeability-porosity relationship in a low-permeability porous material using the results of a single transient test. This method accounts for both elastic and non-elastic deformations of the sample during the test and is applied to a hardened class G oil well cement paste. An initial hydrostatic undrained loading is applied to the sample which generates an excess pore pressure, related to the applied hydrostatic stress by the Skempton coefficient of the material. The generated excess pore pressure is then released at one end of the sample while monitoring the pore pressure at the other end and the radial strain in the middle of the sample during the dissipation of the pore pressure. These measurements are back analysed using a finite-difference numerical scheme to evaluate the permeability and its evolution with porosity change. The stress-dependent character of the poroelastic parameters of the hardened cement paste (Ghabezloo et al., 2008) and also the creep of the material during the test add some particular aspects to the back-analysis, which makes this problem different from the classical solutions of transient permeability evaluation tests. The effect of creep of the sample during the test on the measured pore pressure and volume change is taken into account in the analysis. This approach permits to calibrate a power law permeability-porosity relationship for the tested hardened cement paste and also two parameters of a viscoelastic model for the creep of the material. The porosity sensitivity exponent of the power-law is evaluated equal to 11 and is shown to be mostly independent of the stress level and of the creep strains. The proposed method can be applied to different low permeability porous materials and for the case of non-creeping materials, the same type of analysis can be used to calibrate either a permeability-porosity or a permeability-effective stress relationship for the compaction of the tested material using a single transient test. References: 1.Ghabezloo S., Sulem J., Saint-Marc, J. (2008) Evaluation of a permeability-porosity relationship in a low permeability creeping material using a single transient test. Int J Rock Mech Min Sci, in press, DOI 10.1016/j.ijrmms.2008.10.003. 2.Ghabezloo, S., Sulem, J., Guédon, S., Martineau, F., Saint-Marc, J. (2008) Poromechanical behaviour of hardened cement paste under isotropic loading. Cement and Concrete Research, 38(12), 1424-1437.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Langton, C. A.
The objective of this study was to identify potential chemical degradation mechanisms for the Saltstone Disposal Unit (SDU) concretes, which over the performance life of the structures may be exposed to highly alkaline sodium salt solutions containing sulfate, hydroxide, and other potentially corrosive chemicals in salt solution and saltstone flush water, drain water, leachate and / or pore solution. The samples analyzed in this study were cement pastes prepared in the SIMCO Technologies, Inc. concrete laboratory. They were based on the paste fractions of the concretes used to construct the Saltstone Disposal Units (SDUs). SDU 1 and 4 concrete pastesmore » were represented by the PV1 test specimens. The paste in the SDU 2, 3, 5, and 6 concrete was represented by the PV2 test specimens. SIMCO Technologies, Inc. selected the chemicals and proportions in the aggressive solutions to approximate proportions in the saltstone pore solution [2, 3, 5, and 6]. These test specimens were cured for 56 days in curing chamber before being immersed in aggressive solutions. After exposure, the samples were frozen to prevent additional chemical transport and reaction. Selected archived (retrieved from the freezer) samples were sent to the Savannah River National Laboratory (SRNL) for additional characterization using x-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive x-ray (EDX) spectroscopy. Characterization results are summarized in this report. In addition, a correlation between the oxide composition of the pastes and their chemical durability in the alkaline salt solutions is provided.« less
Smith, Brandon T; Santoro, Marco; Grosfeld, Eline C; Shah, Sarita R; van den Beucken, Jeroen J J P; Jansen, John A; Mikos, Antonios G
2017-03-01
Calcium phosphate cements (CPCs) have been extensively investigated as scaffolds in bone tissue engineering in light of their chemical composition closely resembling the mineral component of bone extracellular matrix. Yet, the degradation kinetics of many CPCs is slow compared to de novo bone formation. In order to overcome this shortcoming, the use of porogens within CPCs has been suggested as a potential strategy to increase scaffold porosity and promote surface degradation. This study explored the usage of glucose microparticles (GMPs) as porogens for the introduction of macroporosity within CPCs, and characterized the handling properties and physicochemical characteristics of CPCs containing GMPs. Samples were fabricated with four different weight fractions of GMPs (10, 20, 30, and 40%) and two different size ranges (100-150μm and 150-300μm), and were assayed for porosity, pore size distribution, morphology, and compressive mechanical properties. Samples were further tested for their handling properties - specifically, setting time and cohesiveness. Additionally, these same analyses were conducted on samples exposed to a physiological solution in order to estimate the dissolution kinetics of GMPs and its effect on the properties of the composite. GMPs were efficiently encapsulated and homogeneously dispersed in the resulting composite. Although setting times increased for GMP/CPC formulations compared to control CPC material, increasing the Na 2 HPO 4 concentration in the liquid phase decreased the initial setting time to clinically acceptable values (i.e. <15min). Incorporation of GMPs led to the formation of instant macroporosity upon cement setting, and encapsulated GMPs completely dissolved in three days, resulting in a further increase in scaffold porosity. However, the dissolution of GMPs decreased scaffold compressive strength. Overall, the introduction of GMPs into CPC resulted in macroporous scaffolds with good handling properties, as well as designer porosity and pore size distribution via selection of the appropriate size/weight fraction of GMPs. The data demonstrate that GMPs are promising porogens for the production of highly tunable porous CPC scaffolds. Calcium phosphate cements have shown great promise for the regeneration of bone. However, macropores (>100μm) are required for promoting bone ingrowth. Several studies have investigated methods to generate macroporosity within calcium phosphate cements but many of these methods either affect the cement setting or take weeks or months to generate the maximum porosity. This work offers a new method for generating macroporosity within calcium phosphate cements by utilizing glucose microparticles. The microparticles dissolve in less then 72h, thereby generating scaffolds with maximum porosity in short period of time. The results will offer a new method for generating macroporosity within calcium phosphate cements. Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Study on the hydration and microstructure of Portland cement containing diethanol-isopropanolamine
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ma, Suhua, E-mail: yc982@163.com; Li, Weifeng; Zhang, Shenbiao
2015-01-15
Diethanol-isopropanolamine (DEIPA) is a tertiary alkanolamine used in the formulation of cement grinding-aid additives and concrete early-strength agents. In this research, isothermal calorimetry was used to study the hydration kinetics of Portland cement with DEIPA. A combination of X-ray powder diffraction (XRPD), scanning electron microscopy (SEM), differential scanning calorimetry (DSC)–thermogravimetric (TG) analysis and micro-Raman spectroscopy was used to investigate the phase development in the process of hydration. Mercury intrusion porosimetry was used to study the pore size distribution and porosity. The results indicate that DEIPA promotes the formation of ettringite (AFt) and enhances the second hydration rate of the aluminatemore » and ferrite phases, the transformation of AFt into monosulfoaluminate (AFm) and the formation of microcrystalline portlandite (CH) at early stages. At later stages, DEIPA accelerates the hydration of alite and reduces the pore size and porosity.« less
Porous polymethylmethacrylate as bone substitute in the craniofacial area.
Bruens, Marco L; Pieterman, Herman; de Wijn, Joost R; Vaandrager, J Michael
2003-01-01
In craniofacial surgery, alloplastic materials are used for correcting bony defects. Porous polymethylmethacrylate (PMMA) is a biocompatible and nondegradable bone cement. Porous PMMA is formed by the classic bone cement formulation of methylmethacrylate liquid and PMMA powder in which an aqueous biodegradable carboxymethylcellulose gel is dispersed to create pores in the cement when cured. Pores give bone the opportunity to grow in, resulting in a better fixation of the prostheses. We evaluated the long-term results (n = 14), up to 20 years, of augmentations and defect fillings in the craniofacial area, with special interest in possible side effects and bone ingrowth. The evaluation consisted of a questionnaire, a physical examination, and a computed tomography (CT) scan. There were no side effects that could be ascribed to the porous PMMA. Twelve CT scans showed bone ingrowth into the prostheses, proving the validity behind the concept of porous PMMA.
NASA Astrophysics Data System (ADS)
Estokova, A.; Smolakova, M.; Luptakova, A.; Strigac, J.
2017-10-01
Water absorptivity is heavily influenced by the volume and connectivity of pores in the pore network of cement composites and has been used as an important parameter for quantifying their durability. To improve the durability and permeability of mortars, various mineral admixtures such as furnace slag, silica fume or fly ash are added into the mortar and concrete mixtures. These admixtures provide numerous important advantages such as corrosion control, improvement of mechanical and physical properties and better workability. This study investigated the changes in absorptivity of cement mortars with different amounts of mineral admixture, represented by granulated blast furnace slag, under aggressive bacterial influence. The water absorptivity of mortars specimens exposed to sulphur-oxidising bacteria A. thiooxidans for the period of 3 and 6 months has changed due to bio-corrosion-based degradation process. The differences in water absorptivity in dependence on the mortars composition have been observed.
Development of low-pH cementitious materials for HLRW repositories
DOE Office of Scientific and Technical Information (OSTI.GOV)
Garcia Calvo, J.L., E-mail: jolgac@ietcc.csic.e; Hidalgo, A.; Alonso, C.
One of the most accepted engineering construction concepts of underground repositories for high radioactive waste considers the use of low-pH cementitious materials. This paper deals with the design of those based on Ordinary Portland Cements with high contents of silica fume and/or fly ashes that modify most of the concrete 'standard' properties, the pore fluid composition and the microstructure of the hydrated products. Their resistance to long-term groundwater aggression is also evaluated. The results show that the use of OPC cement binders with high silica content produces low-pH pore waters and the microstructure of these cement pastes is different frommore » the conventional OPC ones, generating C-S-H gels with lower CaO/SiO{sub 2} ratios that possibly bind alkali ions. Leaching tests show a good resistance of low-pH concretes against groundwater aggression although an altered front can be observed.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Verba, Circe; Montross, Scott; Spaulding, Richard
Geologic carbon storage (GCS) is a potentially viable strategy to reduce greenhouse emissions. Understanding the risks to engineered and geologic structures associated with GCS is an important first step towards developing practices for safe and effective storage. The widespread utilization of foamed cement in wells may mean that carbon dioxide (CO 2)/brine/foamed cement reactions may occur within these GCS sites. Characterizing the difference in alteration rates as well as the physical and mechanical impact of CO 2/brine/foamed cement is an important preliminary step to ensuring offshore and onshore GCS is a prudent anthropogenic CO 2 mitigation choice. In a typicalmore » oil and gas well, cement is placed in the annulus between the steel casing and formation rock for both zonal isolation and casing support. The cement must have sufficient strength to secure the casing in the hole and withstand the stress of drilling, perforating, and fracturing (e.g. API, 1997, 2010 Worldwide Cementing Practices). As such, measuring the mechanical and properties of cement is an important step in predicting cement behavior under applied downhole stresses (Nelson, 2006). Zonal isolation is the prevention of fluids migrating to different zones outside of the casing and is strongly impacted by the permeability of the wellbore cement (Nelson, 2006). Zonal isolation depends on both the mechanical behavior and permeability (a physical property) of the cement (Mueller and Eid, 2006; Nelson, 2006). Long-term integrity of cement depends on the mechanical properties of the cement sheath, such as Young’s Modulus (Griffith et al., 2004). The cement sheath’s ability to withstand the stresses from changes in pressure and temperature is predominantly determined by the mechanical properties, including Young’s modulus, Poisson’s ratio, and tensile strength. Any geochemical alteration may impact both the mechanical and physical properties of the cement, thus ultimately impacting the structural integrity of the wellbore. In this study, atmospheric foamed cements were generated using a neat cement and three foam qualities (volume of entrained gas in the cement) - 10%, 20%, and 30 % gas volume. The samples were immersed in a 0.25 M NaCl brine followed by the injection of supercritical CO 2 at 28.9 MPa and 50°C. Petrophysical properties were examined for representative samples using computed tomography (CT) and scanning electron microscopy (SEM). CT scanning of representative samples across the range of reacted cements revealed macroscopic changes in structure due to brine/CO 2/cement interactions. The high foam quality samples resulted in more CO 2-saturated brine infiltrating radially deeper into the cement and thus were more susceptible to alteration. After 56 days of exposure, the 30% foam quality sample had the most reaction resulting in an alteration depth of 8.35 ± 0.13 mm with a calculated 34.6 ± 0.2% reacted area and 5.76 ± 0.2% reacted pore space area. The neat sample on the other hand, had a reaction depth of 0.31 ± 0.13 mm with a calculated 0.15 ± 0.08% reacted area and 0.57 ± 0.05% reacted pore area. Physical measurements of the exposed samples were consistent with this degree of alteration having 47.02% porosity and the highest permeability of 0.041 mD. These results indicate that the greater surface area provided by the increase of pore space in the higher quality foam coupled with carbonate diffusion reactions enabled greater alteration.« less
NASA Astrophysics Data System (ADS)
Xi, Kelai; Cao, Yingchang; Jahren, Jens; Zhu, Rukai; Bjørlykke, Knut; Haile, Beyene Girma; Zheng, Lijing; Hellevang, Helge
2015-12-01
The Lower Cretaceous Quantou Formation in the southern Songliao Basin is the typical tight oil sandstone in China. For effective exploration, appraisal and production from such a tight oil sandstone, the diagenesis and reservoir quality must be thoroughly studied first. The tight oil sandstone has been examined by a variety of methods, including core and thin section observation, XRD, SEM, CL, fluorescence, electron probing analysis, fluid inclusion and isotope testing and quantitative determination of reservoir properties. The sandstones are mostly lithic arkoses and feldspathic litharenites with fine to medium grain size and moderate to good sorting. The sandstones are dominated by feldspar, quartz, and volcanic rock fragments showing various stages of disintegration. The reservoir properties are quite poor, with low porosity (average 8.54%) and permeability (average 0.493 mD), small pore-throat radius (average 0.206 μm) and high displacement pressure (mostly higher than 1 MPa). The tight sandstone reservoirs have undergone significant diagenetic alterations such as compaction, feldspar dissolution, quartz cementation, carbonate cementation (mainly ferrocalcite and ankerite) and clay mineral alteration. As to the onset time, the oil emplacement was prior to the carbonate cementation but posterior to the quartz cementation and feldspar dissolution. The smectite to illite reaction and pressure solution at stylolites provide a most important silica sources for quartz cementation. Carbonate cements increase towards interbedded mudstones. Mechanical compaction has played a more important role than cementation in destroying the reservoir quality of the K1q4 sandstone reservoirs. Mixed-layer illite/smectite and illite reduced the porosity and permeability significantly, while chlorite preserved the porosity and permeability since it tends to be oil wet so that later carbonate cementation can be inhibited to some extent. It is likely that the oil emplacement occurred later than the tight rock formation (with the porosity close to 10%). However, thicker sandstone bodies (more than 2 m) constitute potential hydrocarbon reservoirs.
Mechano-Chemical Interactions at Cement-Geomaterial Interfaces in Repository and Borehole Scenarios
NASA Astrophysics Data System (ADS)
Mohagheghi, J. R.; Dewers, T. A.; Matteo, E. N.; Heath, J. E.; Jove Colon, C. F.; Fuller, T.
2017-12-01
A number of factors negatively affect wellbore integrity including interactions at boundaries between cement and surrounding geomaterial. These include mechanical and chemical mechanisms that can lead to wellbore failure. To examine these interactions, potential coupling, and pathways to failure, we discuss progress on an experimental and modeling study involving cement-clay and cement-salt interfaces. A sample shotcrete-bentonite interface from the FEBEX heater test at the Grimsel Test Site in Switzerland is examined using multi-beam scanning electron microscopy (mSEM) at 4 nm resolution over an area 10's of square millimeters. We examine changes in alteration as manifested by pore structural changes as a function of distance from the interface. A parallel effort examines time-dependent changes in interface structure in cement cores in a triaxial coreholder. Cores are exposed to conditions of 70oC, 14 MPa pressure, and small differential loads, with degradation being monitored by effluent pH, pulse-echo ultrasonics, and piston displacement (measuring sample shortening). We will measure the mechanical consequences of interface alteration using nano-indentation. Experimental results are being incorporated as a validation effort in a coupled reactive-transport mechanics model linking the Sandia ALBANY finite element code, the KAYENTA elasto-plastic constitutive model, with the reactive transport code PFLOTRAN. Plans call to apply the model to understanding the evolution of the FEBEX sample, as well as a cement-salt sample from the Waste Isolation Pilot Plant in Carlsbad, New Mexico. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia LLC, a wholly owned subsidiary of Honeywell International Inc. for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525. SAND 2017-8277 A
Zhong, Xinyan; Shang, Ruishu; Huang, Lihong
2016-01-01
Carbonate cements, such as calcite, dolomite, ferrocalcite and ankerite, play important roles in the formation of pores in sandstones: precipitation of carbonate cements modifies pores and inhibits compaction, while dissolution creates secondary pores. This work proposed a precipitation-dissolution model for carbonate cements-CO2-H2O system by means of ion equilibrium concentration ([M2+], M = Ca, Mg, Fe or Mn) with different factors, such as temperature, depth, pH, PCO2, variable rock composition and overpressure. Precipitation-dissolution reaction routes were also analyzed by minimization of the total Gibbs free energy (ΔG). Δ[M2+], the variation of [Ca2+], [Fe2+], [Mg2+] or [Mn2+] for every 100 m of burial depths, is used to predict precipitation or dissolution. The calculation results indicate that the increasing temperature results in decrease of equilibrium constant of reactions, while the increasing pressure results in a relatively smaller increase of equilibrium constant; As a result, with increasing burial depth, which brings about increase of both temperature and pressure, carbonate cements dissolve firstly and produces the maximal dissolved amounts, and then precipitation happens with further increasing depth; For example, calcite is dissolving from 0.0 km to 3.0 km with a maximal value of [Ca2+] at depth of 0.8 km, and then precipitates with depth deeper than 3.0 km. Meanwhile, with an increasing CO2 mole fraction in the gaseous phase from 0.1% to 10.0% in carbonate systems, the aqueous concentration of metal ions increases, e.g., dissolved amount of CaFe0.7Mg0.3(CO3)2 increases and reaches maximum of 1.78 mmol·L-1 and 8.26 mmol·L-1 at burial depth of 0.7 km with CO2 mole fraction of 0.1% and 10.0%, respectively. For the influence of overpressure in the calcite system, with overpressure ranging from 36 MPa to 83 MPa, pH reaches a minimum of 6.8 at overpressure of 51 MPa; meanwhile, Δ[Ca2+] increases slightly from -2.24 mmol·L-1 to -2.17 mmol·L-1 and remains negative, indicating it is also a precipitation process at burial depth of 3.9 km where overpressure generated. The method used in this study can be applied in assessing burial precipitation-dissolution processes and predicting possible pores in reservoirs with carbonate cement-water-carbon dioxide. PMID:27907043
Duan, Yiping; Feng, Mingshi; Zhong, Xinyan; Shang, Ruishu; Huang, Lihong
2016-01-01
Carbonate cements, such as calcite, dolomite, ferrocalcite and ankerite, play important roles in the formation of pores in sandstones: precipitation of carbonate cements modifies pores and inhibits compaction, while dissolution creates secondary pores. This work proposed a precipitation-dissolution model for carbonate cements-CO2-H2O system by means of ion equilibrium concentration ([M2+], M = Ca, Mg, Fe or Mn) with different factors, such as temperature, depth, pH, [Formula: see text], variable rock composition and overpressure. Precipitation-dissolution reaction routes were also analyzed by minimization of the total Gibbs free energy (ΔG). Δ[M2+], the variation of [Ca2+], [Fe2+], [Mg2+] or [Mn2+] for every 100 m of burial depths, is used to predict precipitation or dissolution. The calculation results indicate that the increasing temperature results in decrease of equilibrium constant of reactions, while the increasing pressure results in a relatively smaller increase of equilibrium constant; As a result, with increasing burial depth, which brings about increase of both temperature and pressure, carbonate cements dissolve firstly and produces the maximal dissolved amounts, and then precipitation happens with further increasing depth; For example, calcite is dissolving from 0.0 km to 3.0 km with a maximal value of [Ca2+] at depth of 0.8 km, and then precipitates with depth deeper than 3.0 km. Meanwhile, with an increasing CO2 mole fraction in the gaseous phase from 0.1% to 10.0% in carbonate systems, the aqueous concentration of metal ions increases, e.g., dissolved amount of CaFe0.7Mg0.3(CO3)2 increases and reaches maximum of 1.78 mmol·L-1 and 8.26 mmol·L-1 at burial depth of 0.7 km with CO2 mole fraction of 0.1% and 10.0%, respectively. For the influence of overpressure in the calcite system, with overpressure ranging from 36 MPa to 83 MPa, pH reaches a minimum of 6.8 at overpressure of 51 MPa; meanwhile, Δ[Ca2+] increases slightly from -2.24 mmol·L-1 to -2.17 mmol·L-1 and remains negative, indicating it is also a precipitation process at burial depth of 3.9 km where overpressure generated. The method used in this study can be applied in assessing burial precipitation-dissolution processes and predicting possible pores in reservoirs with carbonate cement-water-carbon dioxide.
Sorption of radionuclides by cement-based barrier materials
DOE Office of Scientific and Technical Information (OSTI.GOV)
Li, Kefei, E-mail: likefei@tsinghua.edu.cn; Pang, Xiaoyun
2014-11-15
This paper investigates the sorption of radionuclide ions, {sup 137}Cs{sup +} and {sup 90}Sr{sup 2+}, by cement-based barrier materials for radioactive waste disposal. A mortar with ternary binder is prepared and powder samples are ground from the hardened material following a predetermined granulometry. After pre-equilibrium with an artificial pore solution, the sorption behaviors of powder samples are investigated through single sorption and blended sorption. The results show that: (1) no systematic difference is observed for single and blended sorptions thus the interaction between {sup 137}Cs{sup +} and {sup 90}Sr{sup 2+} sorptions must be weak; (2) the sorption kinetics is rapidmore » and all characteristic times are less than 1d; (3) the sorption capacity is enhanced by C–A–S–H hydrates and the measured K{sub d} values can be predicted from C–S–H sorption data with Ca/Si ratio equal to Ca/(Si + Al) ratio.« less
Early cements versus pore-water chemical composition in the subsurface of the sabkha of Abu Dhabi
NASA Astrophysics Data System (ADS)
Paul, Andreas; Yuan, Peng; Court, Wesley M.; Lokier, Stephen W.; Dutton, Kirsten E.; Van der Land, Cees; Lessa Andrade, Luiza; Sherry, Angela; Head, Ian M.
2017-04-01
The coastal sabkha of Abu Dhabi is a complex depositional system in an extremely arid climate. This depositional system is marked by the formation of primary carbonate and microbial deposits, and by the development of secondary evaporite and cement phases. A number of earlier studies have assessed the formation of these secondary phases, yet no research has established a relationship between lateral and vertical variations in the chemical composition of pore water and the nature of, in particular, the precipitating pore-filling cements, re-crystallisation features and dissolution. This study aims to establish an understanding of the environmental and sedimentary factors that control early post-depositional changes to sediment composition as a result of sediment - pore water interactions. A particular focus is to characterise changes in the chemistry of the pore water throughout a tidal cycle, aiming at understanding how the influx of 'fresh' lagoonal sea water influences the chemistry of the pore water, and which elements are replenished on a daily basis. The initial data presented here is based upon the relationship between the petrographic analysis of sediment samples and lateral and vertical variations in the chemistry of in-situ sampled pore water. The pore water is characterised with respect to pH, salinity, alkalinity, dissolved organic carbon, and the concentrations of a variety of common metallic and non-metallic elements, including (but not limited to) Ca, Fe, Mg, P, S and Sr. Initial results show that concentrations of Mg, P, and V, and the ratios Mg/Ca and Sr/Ca are highest at the seaward sampling locations. Contrastingly, individual concentrations for Ca, Sr, Fe, Si, and Cu are highest at the most landward locality. In particular the higher concentrations for Ca and Sr might indicate diagenetic processes and are thus enriched as a result of e.g. aragonite dissolution. A striking pattern in Mg concentrations show the highest values for this element within a buried microbial mat. This might point to an enrichment process within this organo-sedimentary layer, that might ultimately contribute to bacterially controlled and/or mediated dolomite formation.
NASA Astrophysics Data System (ADS)
Korolev, E.; Eskin, A.; Kolchugin, A.; Morozov, V.; Khramchenkov, M.; Gabdelvalieva, R.
2018-05-01
Ashalchinskoye bitumen deposit is an experimental platform for testing technology of high-viscosity oil extraction from reservoir rocks. Last time for enhanced of oil recovery in reservoir used pressurization a water vapor with a temperature of ∼ 180 ° C (SAGD technology). However, what happens in sandstone reservoir is little known. We did a study of the effects of water vapor on the structural components of bitumen saturated sandstone. In paper were studied the rock samples at base condition and after one week exposure by water vapour. The thermal analysis showed that steaming helps to removes light and middle oil fractions with a boiling point up to 360 ° C from oil saturated sandstones. Content of heavy oil fractions virtually unchanged. Studying the composition of water extractions of samples showed that the process of aquathermolysis of oil is accompanied by a lowering of the pH of the pore solution from 7.4 to 6.5 and rise content in several times of mobile cations Ca2+, Mg2+ and HCO3 -, SO4 2- anions. Follows from this that the thermal steam effect by bitumen saturated sandstones leads to partial oxidation of hydrocarbons with to form a carbon dioxide. The source of sulfate ions were oxidized pyrite aggregates. Due to the increasing acidity of condensed water, which fills the pore space of samples, pore fluid becomes aggressive to calcite and dolomite cement of bitumen saturated sandstones. As a result of the dissolution of carbonate cement the pore fluid enriched by calcium and magnesium cations. Clearly, that the process is accompanied by reduction of contact strength between fragments of minerals and rocks. Resulting part of compounds is separated from the outer side of samples and falls to bottom of water vapor container. Decreasing the amount of calcite and dolomite anions in samples in a steam-treated influence is confirmed by X-Ray analysis. X-Ray analysis data of study adscititious component of rocks showed that when influenced of water vapor to bitumen saturated sandstones there are the processes of transformation of clay minerals. Mixed-illite-montmorillonite phase is primarily exposed to changes. In this case we fix initial stage of the destruction of polycrystalline particles mixed-mineral. Reducing the size of clay minerals particles along the normal to the layers (L001) is the result from lower energy costs of delamination and disintegration the crystallites along this direction, in comparison with others. Thus, using of SAGD technology at exploitation of Ashalchinskoye bitumen saturated reservoir will be followed by acidification of the pore fluid, activation processes of dissolution calcite cement and transformation of mixed-layers clays minerals.
Methane gas hydrate effect on sediment acoustic and strength properties
Winters, W.J.; Waite, W.F.; Mason, D.H.; Gilbert, L.Y.; Pecher, I.A.
2007-01-01
To improve our understanding of the interaction of methane gas hydrate with host sediment, we studied: (1) the effects of gas hydrate and ice on acoustic velocity in different sediment types, (2) effect of different hydrate formation mechanisms on measured acoustic properties (3) dependence of shear strength on pore space contents, and (4) pore pressure effects during undrained shear.A wide range in acoustic p-wave velocities (Vp) were measured in coarse-grained sediment for different pore space occupants. Vp ranged from less than 1 km/s for gas-charged sediment to 1.77–1.94 km/s for water-saturated sediment, 2.91–4.00 km/s for sediment with varying degrees of hydrate saturation, and 3.88–4.33 km/s for frozen sediment. Vp measured in fine-grained sediment containing gas hydrate was substantially lower (1.97 km/s). Acoustic models based on measured Vp indicate that hydrate which formed in high gas flux environments can cement coarse-grained sediment, whereas hydrate formed from methane dissolved in the pore fluid may not.The presence of gas hydrate and other solid pore-filling material, such as ice, increased the sediment shear strength. The magnitude of that increase is related to the amount of hydrate in the pore space and cementation characteristics between the hydrate and sediment grains. We have found, that for consolidation stresses associated with the upper several hundred meters of sub-bottom depth, pore pressures decreased during shear in coarse-grained sediment containing gas hydrate, whereas pore pressure in fine-grained sediment typically increased during shear. The presence of free gas in pore spaces damped pore pressure response during shear and reduced the strengthening effect of gas hydrate in sands.
The formation and potential importance of cemented layers in inactive sulfide mine tailings
DOE Office of Scientific and Technical Information (OSTI.GOV)
Blowes, D.W.; Reardon, E.J.; Cherry, J.A.
Investigations of inactive sulfide-rich tailings impoundments at the Heath Steele (New Brunswick) and Waite Amulet (Quebec) minesites have revealed two distinct types of cemented layers or hardpans. That at Heath Steele is 10-15 cm thick, occurs 20-30 cm below the depth of active oxidation, is continuous throughout the tailings impoundment, and is characterized by cementation of tailings by gypsum and Fe(II) solid phases, principally melanterite. Hardpan at the Waite Amulet site is only 1-5 cm thick, is laterally discontinuous (10-100 cm), occurs at the depth of active oxidation, and is characterized by cementation of tailings by Fe(III) minerals, principally goethite,more » lepidocrocite, ferrihydrite, and jarosite. At Heath Steele, an accumulation of gas-phase CO{sub 2}, of up to 60{percent} of the pore gas, occurs below the hardpan. The calculated diffusivity of the hardpan layer is only about 1/100 that of the overlying, uncemented tailings. The pore-water chemistry at Heath Steele has changed little over a 10-year period, suggesting that the cemented layer restricts the movement of dissolved metals through the tailings and also acts as a zone of metal accumulation. Generation of a cemented layer therefore has significant environmental and economic implications. It is likely that, in sulfide-rich tailings impoundments, the addition of carbonate-rich buffering material during the late stages of tailings deposition would enhance the formation of hardpan layers.« less
Constraining the Texture and Composition of Pore-Filling Cements at Gale Crater, Mars
NASA Technical Reports Server (NTRS)
Siebach, K. L.; Grotzinger, J. P.; McLennan, S. M.; Hurowitz, J. A.; Ming, D. W.; Vaniman, D. T.; Rampe, E. B.; Blaney, D. L.; Kah, L. C.
2015-01-01
The Mars Science Laboratory (MSL) rover Curiosity has encountered a wide variety of sedimentary rocks deposited in fluvio-lacuestrine sequences at the base of Gale Crater. The presence of sedimentary rocks requires that initial sediments underwent diagenesis and were lithified. Lithification involves sediment compaction, cementation, and re-crystallization (or authigenic) processes. Analysis of the texture and composition of the cement can reveal the environmental conditions when the cements were deposited, enabling better understanding of early environments present within Gale Crater. The first step in lithification is sediment compaction. The Gale crater sediments do not show evidence for extensive compaction prior to cementation; the Sheepbed mudstone in Yellowknife Bay (YKB) has preserved void spaces ("hollow nodules"), indicating that sediments were cemented around the hollow prior to compaction, and conglomerates show imbrication, indicating minimal grain reorganization prior to lithification. Furthermore, assuming the maximum burial depth of these sediments is equivalent to the depth of Gale Crater, the sediments were never under more than 1 kb of pressure, and assuming a 15 C/km thermal gradient in the late Noachian, the maximum temperature of diagenesis would have been approximately 75 C. This is comparable to shallow burial diagenetic conditions on Earth. The cementation and recrystallization components of lithification are closely intertwined. Cementation describes the precipitation of minerals between grains from pore fluids, and recrystallization (or authigenesis) is when the original sedimentary mineral grains are altered into secondary minerals. The presence of authigenic smectites and magnetite in the YKB formation suggests that some recrystallization has taken place. The relatively high percentage of XRD-amorphous material (25-40%) detected by CheMin suggests that this recrystallization may be limited in scope, and therefore may not contribute significantly to the cementing material. However, relatively persistent amorphous components could exist in the Martian environment (e.g. amorphous MgSO4), so recrystallization, including loss of crystallinity, cannot yet be excluded as a method of cementation. In order to describe the rock cementation, both the rock textures and their composition must be considered. Here, we attempt to summarize the current understanding of the textural and compositional aspects of the cement across the rocks analyzed by Curiosity to this point.
Effect of some biotic factors on microbially-induced calcite precipitation in cement mortar.
Al-Salloum, Yousef; Abbas, H; Sheikh, Q I; Hadi, S; Alsayed, Saleh; Almusallam, Tarek
2017-02-01
Sporosarcina pasteurii , a common soil bacterium has been tested for microbial treatment of cement mortar. The present study also seeks to investigate the effects of growth medium, bacterial concentration and different buffers concerning the preparation of bacterial suspensions on the compressive strength of cement mortar. Two growth media, six different suspensions and two bacterial concentrations were used in the study. The influence of growth medium on calcification efficiency of S. pasteurii was insignificant. Significant improvement in the compressive as well as the tensile strength of cement mortar was observed. Microbial mineral precipitation visualized by Scanning Electron Microscopy (SEM) shows fibrous material that increased the strength of cement mortar. Formation of thin strands of fillers observed through SEM micrographs improves the pore structure, impermeability and thus the compressive as well as the tensile strengths of the cement mortar. The type of substrate and its molarity have a significant influence on the strength of cement mortar.
LEACHING BOUNDARY IN CEMENT-BASED WASTE FORMS
Cement-based fixation systems are among the most commonly employed stabilization/solidification techniques. These cement haste mixtures, however, are vulnerable to ardic leaching solutions. Leaching of cement-based waste forms in acetic acid solutions with different acidic streng...
Durability of pulp fiber-cement composites
NASA Astrophysics Data System (ADS)
Mohr, Benjamin J.
Wood pulp fibers are a unique reinforcing material as they are non-hazardous, renewable, and readily available at relatively low cost compared to other commercially available fibers. Today, pulp fiber-cement composites can be found in products such as extruded non-pressure pipes and non-structural building materials, mainly thin-sheet products. Although natural fibers have been used historically to reinforce various building materials, little scientific effort has been devoted to the examination of natural fibers to reinforce engineering materials until recently. The need for this type of fundamental research has been emphasized by widespread awareness of moisture-related failures of some engineered materials; these failures have led to the filing of national- and state-level class action lawsuits against several manufacturers. Thus, if pulp fiber-cement composites are to be used for exterior structural applications, the effects of cyclical wet/dry (rain/heat) exposure on performance must be known. Pulp fiber-cement composites have been tested in flexure to examine the progression of strength and toughness degradation. Based on scanning electron microscopy (SEM), environmental scanning electron microscopy (ESEM), energy dispersive spectroscopy (EDS), a three-part model describing the mechanisms of progressive degradation has been proposed: (1) initial fiber-cement/fiber interlayer debonding, (2) reprecipitation of crystalline and amorphous ettringite within the void space at the former fiber-cement interface, and (3) fiber embrittlement due to reprecipitation of calcium hydroxide filling the spaces within the fiber cell wall structure. Finally, as a means to mitigate kraft pulp fiber-cement composite degradation, the effects of partial portland cement replacement with various supplementary cementitious materials (SCMs) has been investigated for their effect on mitigating kraft pulp fiber-cement composite mechanical property degradation (i.e., strength and toughness losses) during wet/dry cycling. SCMs have been found to be effective in mitigating composite degradation through several processes, including a reduction in the calcium hydroxide content, stabilization of monosulfate by maintaining pore solution pH, and a decrease in ettringite reprecipitation accomplished by increased binding of aluminum in calcium aluminate phases and calcium in the calcium silicate hydrate (C-S-H) phase.
Diagenesis in coastal carbonates related to Pleistocene sea level, Bermuda Platform
DOE Office of Scientific and Technical Information (OSTI.GOV)
Vollbrecht, R.; Meischner, D.
1996-01-01
Pleistocene glacioeustatic sea-level oscillation on the stable Bermuda Platform is expressed in a succession of shallow-water carbonates interrupted by lowstand unconformities. In Bermuda, the maximum highstands of the last 400,000 yr ranged within 10 m around the present level. Coastal carbonates of various highstands are exposed along the present shoreline. These carbonates were penetrated by meteoric and marine pore waters during lowstands and highstands following on deposition. Two representative Pleistocene shoreline sections were studied to see whether early diagenesis has recorded these pore-water changes. The sediments of both sections show multiple generations of cement. Optical and scanning electron microscopy, cathodoluminescencemore » microscopy, X-ray diffraction, microprobe studies and stable-isotope analyses were used to determine the diagenetic environments involved. Regardless of the degree of substrate cementation, freshwater alteration was mainly vadose whereas marine cementation was either phreatic or vadose or both. Early diagenetic oscillation is easier recorded in coastal successions than in lagoonal sediments, mainly because marine cementation is more active nearshore.Because the coastal environment is prone to wave destruction, the potential for preserving these diagenetic features is usually low. Data published on tectonically unstable areas suggest that early diagenetic oscillation may characterize stable coastlines.« less
NASA Astrophysics Data System (ADS)
Yang, Z.; Juanes, R.
2015-12-01
The geomechanical processes associated with subsurface fluid injection/extraction is of central importance for many industrial operations related to energy and water resources. However, the mechanisms controlling the stability and slip motion of a preexisting geologic fault remain poorly understood and are critical for the assessment of seismic risk. In this work, we develop a coupled hydro-geomechanical model to investigate the effect of fluid injection induced pressure perturbation on the slip behavior of a sealing fault. The model couples single-phase flow in the pores and mechanics of the solid phase. Granular packs (see example in Fig. 1a) are numerically generated where the grains can be either bonded or not, depending on the degree of cementation. A pore network is extracted for each granular pack with pore body volumes and pore throat conductivities calculated rigorously based on geometry of the local pore space. The pore fluid pressure is solved via an explicit scheme, taking into account the effect of deformation of the solid matrix. The mechanics part of the model is solved using the discrete element method (DEM). We first test the validity of the model with regard to the classical one-dimensional consolidation problem where an analytical solution exists. We then demonstrate the ability of the coupled model to reproduce rock deformation behavior measured in triaxial laboratory tests under the influence of pore pressure. We proceed to study the fault stability in presence of a pressure discontinuity across the impermeable fault which is implemented as a plane with its intersected pore throats being deactivated and thus obstructing fluid flow (Fig. 1b, c). We focus on the onset of shear failure along preexisting faults. We discuss the fault stability criterion in light of the numerical results obtained from the DEM simulations coupled with pore fluid flow. The implication on how should faults be treated in a large-scale continuum model is also presented.
NASA Astrophysics Data System (ADS)
Weiss, David K.; Head, James W.
2017-05-01
The present-day martian mean annual surface temperature is well below freezing at all latitudes; this produces a near-surface portion of the crust that is below the freezing point of water for > 2 consecutive years (defined as permafrost). This permafrost layer (i.e., the cryosphere) is a few to tens of km thick depending on latitude. Below the base of the permafrost (i.e., the cryosphere), groundwater is stable if it exists, and can increase and decrease in abundance as the freezing isotherm rises and falls. Where water is available, ice fills the pore space within the cryosphere; this region is known as the ice-cemented cryosphere (ICC). The potential for a large reservoir of pore ice beneath the surface has been the subject of much discussion: previous studies have demonstrated that the theoretical thickness of the martian cryosphere in the Amazonian period ranges from up to ∼9 km at the equator to ∼10-22 km at the poles. The total thickness of ice that might fill the pore space within the cryosphere (the ICC), however, remains unknown. A class of martian crater, the Hesperian-Amazonian-aged single-layered ejecta crater, is widely accepted as having formed by impact into an ice-cemented target. Although the target structure related to the larger multiple-layered ejecta craters remains uncertain, they have recently been interpreted to be formed by impact crater excavation below the ice-cemented target, and here we tentatively adopt this interpretation in order to infer the thickness of the ice-cemented cryosphere. Our global examination of the excavation depths of these crater populations points to a Hesperian-Amazonian-aged ice-cemented cryosphere that is ∼1.3 km thick at the equator, and ∼2.3 km thick at the poles (corresponding to a global equivalent water layer of ∼200 m assuming ∼20% pore ice at the surface). To explore the implications of this result on the martian climatic and hydrologic evolution, we then assess the surface temperature, atmospheric pressure, obliquity, and surface heat flux conditions under which the downward-propagating cryosphere freezing front matches the inferred ice-cemented cryosphere. The thermal models which can best reproduce the inferred ice-cemented cryosphere occur for obliquities between 25° and 45° and CO2 atmospheric pressures ≤600 mbar, but require increased heat fluxes and surface temperatures/pressures relative to the Amazonian period. Because the inferred ice-cemented cryosphere is much thinner compared with Amazonian-aged cryosphere thermal models, we suggest that the ice-cemented cryosphere ceased growing when it exhausted the underlying groundwater supply (i.e., ICC stabilization) in a more ancient period in Mars geologic history. Our thermal analysis suggests that this ICC stabilization likely occurred sometime before or at ∼3.0-3.3 Ga (during or before the Late Hesperian or Early Amazonian period). If groundwater remained below the ICC during the earlier Late Noachian period, our models predict that mean annual surface temperatures during this time were ≥212-227 K. If the Late Noachian had a pure CO2 atmosphere, this places a minimum bound on the Late Noachian atmospheric pressure of ≥390-850 mbar. These models suggest that deep groundwater is not abundant or does not persist in the subsurface of Mars today, and that diffusive loss of ice from the subsurface has been minimal.
Experimental Study on Modification of Concrete with Asphalt Admixture
NASA Astrophysics Data System (ADS)
Bołtryk, Michał; Małaszkiewicz, Dorota; Pawluczuk, Edyta
2017-10-01
Durability of engineering structures made of cement concrete with high compressive strength is a very vital issue, especially when they are exposed to different aggressive environments and dynamic loads. Concrete resistance to weathering actions and chemical attack can be improved by combined chemical and mechanical modification of concrete microstructure. Asphalt admixture in the form of asphalt paste (AP) was used for chemical modification of cement composite microstructure. Concrete structure was formed using special technology of compaction. A stand for vibro-vibropressing with regulated vibrator force and pressing force was developed. The following properties of the modified concrete were tested: compressive strength, water absorption, freeze-thaw resistance, scaling resistance in the presence of de-icing agents, chloride migration, resistance to CO2 and corrosion in aggressive solutions. Corrosion resistance was tested alternately in 1.8% solutions of NH4Cl, MgSO4, (NH2)2CO and CaCl2, which were altered every 7 days; the experiment lasted 9.5 months. Optimum compaction parameters in semi-industrial conditions were determined: ratio between piston stress (Qp ) and external top vibrator force (Po ) in the range 0.4÷-0.5 external top vibrator force 4 kN. High strength concretes with compressive strength fcm = 60÷70 MPa, very low water absorption (<1%) and high resistance to aggressive environments were obtained in this study. AP content was reduced from 10% (previous investigations) to 2-4% of cement mass thanks to the special compaction method. Excellent chloride ion penetration resistance and carbonation resistance of concrete containing AP admixture is due to the asphalt barrier formed in pores of cement hydrates against dioxide and chloride ions. Concrete specimens containing AP 4% c.m. and consolidated by vibro-vibropressing method proved to be practically resistant to highly corrosive environment. Vibro-vibropressing compaction technology of concrete modified with AP can be applied in prefabrication plants to produce elements for road, bridge and hydraulic engineering constructions.
NASA Astrophysics Data System (ADS)
Morad, Daniel; Nader, Fadi H.; Gasparrini, Marta; Morad, Sadoon; Rossi, Carlos; Marchionda, Elisabetta; Al Darmaki, Fatima; Martines, Marco; Hellevang, Helge
2018-05-01
This petrographic, stable isotopic and fluid inclusion microthermometric study of the Upper Jurassic limestones of an onshore field, Abu Dhabi, United Arab Emirates (UAE) compares diagenesis in flanks and crest of the anticline. The results revealed that the diagenetic and related reservoir quality evolution occurred during three phases, including: (i) eogenesis to mesogenesis 1, during which reservoir quality across the field was either deteriorated or preserved by calcite cementation presumably derived from marine or evolved marine pore waters. Improvement of reservoir quality was due to the formation of micropores by micritization of allochems and creation of moldic/intragranular pores by dissolution of peloids and skeletal fragments. (ii) Obduction of Oman ophiolites and formation of the anticline of the studied field was accompanied by cementation by saddle dolomite and blocky calcite. High homogenization temperatures (125-175 °C) and high salinity (19-26 wt% NaCl eq) of the fluid inclusions, negative δ18OVPDB values (-7.7 to -2.9‰), saddle shape of dolomite, and the presence of exotic cements (i.e. fluorite and sphalerite) suggest that these carbonates were formed by flux of hot basinal brines, probably related to this tectonic compression event. (iii) Mesogenesis 2 during subsidence subsequent to the obduction event, which resulted in extensive stylolitization and cementation by calcite. This calcite cement occluded most of the remaining moldic and inter-/intragranular pores of the flank limestones (water zone) whereas porosity was preserved in the crest. This study contributes to: (1) our understanding of differences in the impact of diagenesis on reservoir quality evolution in flanks and crests of anticlines, i.e. impact of hydrocarbon emplacement on diagenesis, and (2) relating various diagenetic processes to burial history and tectonic events of foreland basins in the Arabian Gulf area and elsewhere.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jung, Hun Bok; Jansik, Danielle; Um, Wooyong
2013-01-02
ABSTRACT: X-ray microtomography (XMT), a nondestructive three-dimensional imaging technique, was applied to demonstrate its capability to visualize the mineralogical alteration and microstructure changes in hydrated Portland cement exposed to carbon dioxide under geologic sequestration conditions. Steel coupons and basalt fragments were added to the cement paste in order to simulate cement-steel and cement-rock interfaces. XMT image analysis showed the changes of material density and porosity in the degradation front (density: 1.98 g/cm3, porosity: 40%) and the carbonated zone (density: 2.27 g/cm3, porosity: 23%) after reaction with CO2- saturated water for 5 months compared to unaltered cement (density: 2.15 g/cm3, porosity:more » 30%). Three-dimensional XMT imaging was capable of displaying spatially heterogeneous alteration in cement pores, calcium carbonate precipitation in cement cracks, and preferential cement alteration along the cement-steel and cement-rock interfaces. This result also indicates that the interface between cement and host rock or steel casing is likely more vulnerable to a CO2 attack than the cement matrix in a wellbore environment. It is shown here that XMT imaging can potentially provide a new insight into the physical and chemical degradation of wellbore cement by CO2 leakage.« less
NASA Astrophysics Data System (ADS)
Arya, I. W.; Wiraga, I. W.; GAG Suryanegara, I.
2018-01-01
Slope is a part of soil topography formed due to elevation difference from two soil surface. Landslides is frequently occur in natural slope, it is because shear force is greater than shear strength in the soil. There are some factor that influence slope stability such as: rain dissipation, vibration from earthquake, construction and crack in the soil. Slope instability can cause risk in human activity or even threaten human lives. Every years in rainy season, landslides always occur in Indonesia. In 2016, there was some landslide occurred in Bali. One of the most damaging is landslide in Petang district, Badung regency. This landslide caused main road closed entirely. In order to overcome and prevent landslide, a lot of method have been practiced and still looking for more sophisticated method for forecasting slope stability. One of the method to strengthen soil stability is filling the soil pores with some certain material. Cement is one of the material that can be used to fill the soil pores because when it is in liquid form, it can infiltrate into soil pores and fill the gap between soil particles. And after it dry, it can formed a bond with soil particle so that soil become stronger and the slope as well. In this study, it will use experimental method, slope model in laboratory to simulate a real slope behavior in the field. The first model is the slope without any addition of cement. This model will be become a benchmark for the other models. The second model is a slope with improved soil that injects the slope with cement. Injection of cement is done with varying interval distance of injection point is 5 cm and 10 cm. Each slope model will be given a load until the slope collapses. The slope model will also be analyzed with slope stability program. The test results on the improved slope models will be compared with unimproved slope. In the initial test will consist of 3 model. First model is soil without improvement or cement injection, second model is soil with cement injection interval 5 cm and third model is soil with cement injection interval 10 cm. The result is the shear strength (ϕ value) the soil is increase from 32.02° to 47.57°. The increase value of internal friction angle (ϕ) shows that an increase in shear strength of the cement improved soil. While, the value of cohesion (c) is zero indicating there is no cohesion in the soil. This is common for sand soil or sandy soil. The calculation of safety factor with GeoStructural Analysis obtained an increase of safety factor from 0.78 if the soil without cement injection to 1.07 and 1.17 if the soil is injected with cement at a distance of 10 cm and 5 cm.
Lee, Han-Seung; Ryu, Hwa-Sung; Park, Won-Jun; Ismail, Mohamed A.
2015-01-01
In this study, the ability of lithium nitrite and amino alcohol inhibitors to provide corrosion protection to reinforcing steel was investigated. Two types of specimens—reinforcing steel and a reinforced concrete prism that were exposed to chloride ion levels resembling the chloride attack environment—were prepared. An autoclave accelerated corrosion test was then conducted. The variables tested included the chloride-ion concentration and molar ratios of anti-corrosion ingredients in a CaOH2-saturated aqueous solution that simulated a cement-pore solution. A concentration of 25% was used for the lithium nitrite inhibitor LiNO2, and an 80% solution of dimethyl ethanolamine ((CH3)2NCH2CH2OH, hereinafter DMEA) was used for the amino alcohol inhibitor. The test results indicated that the lithium nitrite inhibitor displayed anti-corrosion properties at a molar ratio of inhibitor of ≥0.6; the amino alcohol inhibitor also displayed anti-corrosion properties at molar ratios of inhibitor greater than approximately 0.3. PMID:28787936
Surface roughness of orthodontic band cements with different compositions
van de SANDE, Françoise Hélène; da SILVA, Adriana Fernandes; MICHELON, Douver; PIVA, Evandro; CENCI, Maximiliano Sérgio; DEMARCO, Flávio Fernando
2011-01-01
Objectives The present study evaluated comparatively the surface roughness of four orthodontic band cements after storage in various solutions. Material and Methods eight standardized cylinders were made from 4 materials: zinc phosphate cement (ZP), compomer (C), resin-modified glass ionomer cement (RMGIC) and resin cement (RC). Specimens were stored for 24 h in deionized water and immersed in saline (pH 7.0) or 0.1 M lactic acid solution (pH 4.0) for 15 days. Surface roughness readings were taken with a profilometer (Surfcorder SE1200) before and after the storage period. Data were analyzed by two-way ANOVA and Tukey's test (comparison among cements and storage solutions) or paired t-test (comparison before and after the storage period) at 5% significance level. Results The values for average surface roughness were statistically different (p<0.001) among cements at both baseline and after storage. The roughness values of cements in a decreasing order were ZP>RMGIC>C>R (p<0.001). After 15 days, immersion in lactic acid solution resulted in the highest surface roughness for all cements (p<0.05), except for the RC group (p>0.05). Compared to the current threshold (0.2 µm) related to biofilm accumulation, both RC and C remained below the threshold, even after acidic challenge by immersion in lactic acid solution. Conclusions Storage time and immersion in lactic acid solution increased the surface roughness of the majority of the tested cements. RC presented the smoothest surface and it was not influenced by storage conditions. PMID:21625737
Cox, Sophie C; Jamshidi, Parastoo; Eisenstein, Neil M; Webber, Mark A; Hassanin, Hany; Attallah, Moataz M; Shepherd, Duncan E T; Addison, Owen; Grover, Liam M
2016-07-01
Additive manufacturing technologies have been utilised in healthcare to create patient-specific implants. This study demonstrates the potential to add new implant functionality by further exploiting the design flexibility of these technologies. Selective laser melting was used to manufacture titanium-based (Ti-6Al-4V) implants containing a reservoir. Pore channels, connecting the implant surface to the reservoir, were incorporated to facilitate antibiotic delivery. An injectable brushite, calcium phosphate cement, was formulated as a carrier vehicle for gentamicin. Incorporation of the antibiotic significantly (p=0.01) improved the compressive strength (5.8±0.7MPa) of the cement compared to non-antibiotic samples. The controlled release of gentamicin sulphate from the calcium phosphate cement injected into the implant reservoir was demonstrated in short term elution studies using ultraviolet-visible spectroscopy. Orientation of the implant pore channels were shown, using micro-computed tomography, to impact design reproducibility and the back-pressure generated during cement injection which ultimately altered porosity. The amount of antibiotic released from all implant designs over a 6hour period (<28% of the total amount) were found to exceed the minimum inhibitory concentrations of Staphylococcus aureus (16μg/mL) and Staphylococcus epidermidis (1μg/mL); two bacterial species commonly associated with periprosthetic infections. Antibacterial efficacy was confirmed against both bacterial cultures using an agar diffusion assay. Interestingly, pore channel orientation was shown to influence the directionality of inhibition zones. Promisingly, this work demonstrates the potential to additively manufacture a titanium-based antibiotic eluting implant, which is an attractive alternative to current treatment strategies of periprosthetic infections. Copyright © 2016 Elsevier B.V. All rights reserved.
Mercury removal from aqueous solutions by zinc cementation.
Ku, Young; Wu, Ming-Huan; Shen, Yung-Shen
2002-01-01
The main purpose of this research is to study the addition effect of the surfactant and other operating factors on the treatment of wastewater containing mercury ions in aqueous solution by cementation with sacrificing metal, zinc. The removal of mercury ions from aqueous solutions by cementation of zinc powder was found to be a function of solution pH and temperature, amount of zinc, concentration of mercury ion, contact time and the addition of several organic surfactants. Cementation of mercury was shown to be a feasible process to achieve a very high degree of mercury removal over a broad operational range within a fairly reasonable contact time. The reaction rate is approximately first order with respect to the concentration of mercury ion in aqueous solution. Among the surfactants used in this study, only the presence of SDS, an anionic surfactant, slightly enhanced the cementation rate of mercury. The presence of CTAB and Triton-X100 retarded the cementation of mercury by zinc.
NASA Astrophysics Data System (ADS)
Loudin, L. C.; Yogodzinski, G. M.; Sena, C.; van der Land, C.; Zhang, Z.; Marsaglia, K. M.; Meffre, S.
2014-12-01
Interstitial water (IW) geochemistry provides insight into the diagenetic transformation of sediment to rock by component dissolution/alteration and precipitation of new mineral phases as pore-filling cements, as well as providing insight into ion exchange reactions with secondary minerals. At Site U1438, 67 IW samples were collected within a ~950 m section of volcaniclastic sediments. These were analyzed for pH as well as major and trace elements. The corresponding host sediments were mineralogically characterized by XRD and petrographic observations. Three alteration zones are inferred: 1) the upper alteration zone (~0-300 mbsf) characterized by maximum IW concentrations of Si (790.1 μM), Sr (138.5 μM) and Mn (279.5 μM), consistent with volcanic glass and siliceous microfossil dissolution, enhanced reduction of Mn oxides, and carbonate recrystallization. Maximum concentrations in Li and B coupled with the lowest pH (6.7) imply that Li and B are released into the IW due to silicate dissolution and clay desorption. 2) At intermediate depths (~300 to ~550 mbsf) Mg, K, Sr, Si, Mn, Li, and B are at concentration minima, possibly due to growth of authigenic minerals. B and Li minimum concentrations occur at high pH (~9) suggesting that these elements are preferentially removed from high pH waters during the precipitation of clay mineral and zeolite cements in primary and secondary (dissolution) pores. The mineralogy of these phases is confirmed by XRD data, and their pore-filling nature is seen in thin sections of the coarser lithologies. 3) The deep alteration zone (>~550m) is characterized by an increase in B, Li, Sr and Ca. At ~650 mbsf, Ca becomes the dominant cation in solution consistent with either mineral interaction with the IW, or diffusive input from underlying igneous basement (~1400 mbsf).
Guerrero, A; Goñi, S; Allegro, V R
2009-01-30
The resistance of class C fly ash belite cement (FABC-2-W) to concentrated sodium sulphate salts associated with low level wastes (LLW) and medium level wastes (MLW) is discussed. This study was carried out according to the Koch and Steinegger methodology by testing the flexural strength of mortars immersed in simulated radioactive liquid waste rich in sulphate (48,000 ppm) and demineralised water (used as a reference), at 20 degrees C and 40 degrees C over a period of 180 days. The reaction mechanisms of sulphate ion with the mortar was carried out through a microstructure study, which included the use of Scanning electron microscopy (SEM), porosity and pore-size distribution and X-ray diffraction (XRD). The results showed that the FABC mortar was stable against simulated sulphate radioactive liquid waste (SSRLW) attack at the two chosen temperatures. The enhancement of mechanical properties was a result of the formation of non-expansive ettringite inside the pores and an alkaline activation of the hydraulic activity of cement promoted by the ingress of sulphate. Accordingly, the microstructure was strongly refined.
30 CFR 250.1617 - Application for permit to drill.
Code of Federal Regulations, 2011 CFR
2011-07-01
... well and for well control, including the following: (i) Pore pressure; (ii) Formation fracture..., fracture gradients of the exposed formations, casing setting depths, and cementing intervals, total well...
Elasticity and expansion test performance of geopolymer as oil well cement
NASA Astrophysics Data System (ADS)
Ridha, S.; Hamid, A. I. Abd; Halim, A. H. Abdul; Zamzuri, N. A.
2018-04-01
History has shown that geopolymer cement provides high compressive strength as compared to Class G cement. However, the research had been done at ambient temperature, not at elevated condition which is the common oil well situation. In this research, the physical and mechanical properties performance of the oil well cement were investigated by laboratory work for two types of cement that are geopolymer and Class G cement. The cement samples were produced by mixing the cement according to the API standards. Class C fly ash was used in this study. The alkaline solution was prepared by mixing sodium silicate with NaOH solution. The NaOH solution was prepared by diluting NaOH pellets with distilled water to 8M. The cement samples were cured at a pressure of 3000 psi and a temperature of 130 °C to simulate the downhole condition. After curing, the physical properties of the cement samples were investigated using OYO Sonic Viewer to determine their elastic properties. Autoclave expansion test and compressive strength tests were conducted to determine the expansion value and the strength of the cement samples, respectively. The results showed that the geopolymer cement has a better physical and mechanical properties as compared with Class G cement at elevated condition.
NASA Astrophysics Data System (ADS)
Wang, Y.; Soga, K.; DeJong, J. T.; Kabla, A.
2017-12-01
Microbial-induced carbonate precipitation (MICP), one of the bio-mineralization processes, is an innovative subsurface improvement technique for enhancing the strength and stiffness of soils, and controlling their hydraulic conductivity. These macro-scale engineering properties of MICP treated soils controlled by micro-scale factors of the precipitated carbonate, such as its content, amount and distribution in the soil matrix. The precipitation process itself is affected by bacteria amount, reaction kinetics, porous medium geometry and flow distribution in the soils. Accordingly, to better understand the MICP process at the pore scale a new experimental technique that can observe the entire process of MICP at the pore-scale was developed. In this study, a 2-D transparent microfluidic chip made of Polydimethylsiloxane (PDMS) representing the soil matrix was designed and fabricated. A staged-injection MICP treatment procedure was simulated inside the microfluidic chip while continuously monitored using microscopic techniques. The staged-injection MICP treatment procedure started with the injection of bacteria suspension, followed with the bacteria setting for attachment, and then ended with the multiple injections of cementation liquid. The main MICP processes visualized during this procedure included the bacteria transport and attachment during the bacteria injection, the bacteria attachment and growth during the bacteria settling, the bacteria detachment during the cementation liquid injection, the cementation development during the cementation liquid injection, and the cementation development after the completion of cementation liquid injection. It is suggested that the visualization of the main MICP processes using the microfluidic technique can improve understating of the fundamental mechanisms of MICP and consequently help improve the treatment technique for in situ implementation of MICP.
Yang, Chen; Wang, Xiaoya; Ma, Bing; Zhu, Haibo; Huan, Zhiguang; Ma, Nan; Wu, Chengtie; Chang, Jiang
2017-02-22
Silicate bioactive materials have been widely studied for bone regeneration because of their eminent physicochemical properties and outstanding osteogenic bioactivity, and different methods have been developed to prepare porous silicate bioactive ceramics scaffolds for bone-tissue engineering applications. Among all of these methods, the 3D-printing technique is obviously the most efficient way to control the porous structure. However, 3D-printed bioceramic porous scaffolds need high-temperature sintering, which will cause volume shrinkage and reduce the controllability of the pore structure accuracy. Unlike silicate bioceramic, bioactive silicate cements such as tricalcium silicate (Ca 3 SiO 5 and C 3 S) can be self-set in water to obtain high mechanical strength under mild conditions. Another advantage of using C 3 S to prepare 3D scaffolds is the possibility of simultaneous drug loading. Herein, we, for the first time, demonstrated successful preparation of uniform 3D-printed C 3 S bone cement scaffolds with controllable 3D structure at room temperature. The scaffolds were loaded with two model drugs and showed a loading location controllable drug-release profile. In addition, we developed a surface modification process to create controllable nanotopography on the surface of pore wall of the scaffolds, which showed activity to enhance rat bone-marrow stem cells (rBMSCs) attachment, spreading, and ALP activities. The in vivo experiments revealed that the 3D-printed C 3 S bone cement scaffolds with nanoneedle-structured surfaces significantly improved bone regeneration, as compared to pure C 3 S bone cement scaffolds, suggesting that 3D-printed C 3 S bone cement scaffolds with controllable nanotopography surface are bioactive implantable biomaterials for bone repair.
Mozley, Peter S.; Heath, Jason E.; Dewers, Thomas A.; ...
2016-01-01
The Mount Simon Sandstone and Eau Claire Formation represent a principal reservoir - caprock system for wastewater disposal, geologic CO 2 storage, and compressed air energy storage (CAES) in the Midwestern United States. Of primary concern to site performance is heterogeneity in flow properties that could lead to non-ideal injectivity and distribution of injected fluids (e.g., poor sweep efficiency). Using core samples from the Dallas Center Structure, Iowa, we investigate pore structure that governs flow properties of major lithofacies of these formations. Methods include gas porosimetry and permeametry, mercury intrusion porosimetry, thin section petrography, and X-ray diffraction. The lithofacies exhibitmore » highly variable intra- and inter-informational distributions of pore throat and body sizes. Based on pore-throat size, samples fall into four distinct groups. Micropore-throat dominated samples are from the Eau Claire Formation, whereas the macropore-, mesopore-, and uniform-dominated samples are from the Mount Simon Sandstone. Complex paragenesis governs the high degree of pore and pore-throat size heterogeneity, due to an interplay of precipitation, non-uniform compaction, and later dissolution of cements. Furthermore, the cement dissolution event probably accounts for much of the current porosity in the unit. The unusually heterogeneous nature of the pore networks in the Mount Simon Sandstone indicates that there is a greater-than-normal opportunity for reservoir capillary trapping of non-wetting fluids — as quantified by CO 2 and air column heights — which should be taken into account when assessing the potential of the reservoir-caprock system for CO 2 storage and CAES.« less
The influence of carbon nanotubes on the properties of water solutions and fresh cement pastes
NASA Astrophysics Data System (ADS)
Leonavičius, D.; Pundienė, I.; Girskas, G.; Pranckevičienė, J.; Kligys, M.; Sinica, M.
2017-10-01
It is known, that the properties of cement-based materials can be significantly improved by addition of carbon nanotubes (CNTs). The dispersion of CNTs is an important process due to an extremely high specific surface area. This aspect is very relevant and is one of the main factors for the successful use of CNTs in cement-based materials. The influence of CNTs in different amounts (from 0 to 0.5 percent) on the pH values of water solutions and fresh cement pastes, and also on rheological properties, flow characteristics, setting time and EXO reaction of the fresh cement pastes was analyzed in this work. It was found that the increment of the amount of CNTs leads to decreased pH values of water solutions and fresh cement pastes, and also increases viscosity, setting times and EXO peak times of fresh cement pastes.
Reequilibration of fluid inclusions in low-temperature calcium-carbonate cement
NASA Astrophysics Data System (ADS)
Goldstein, Robert H.
1986-09-01
Calcium-carbonate cements precipitated in low-temperature, near-surface, vadose environments contain fluid inclusions of variable vapor-to-liquid ratios that yield variable homogenization temperatures. Cements precipitated in low-temperature, phreatic environments contain one-phase, all-liquid fluid inclusions. Neomorphism of unstable calcium-carbonate phases may cause reequilibration of fluid inclusions. Stable calcium-carbonate cements of low-temperature origin, which have been deeply buried, contain fluid inclusions of variable homogenization temperature and variable salt composition. Most inclusion fluids are not representative of the fluids present during cement growth and are more indicative of burial pore fluids. Therefore, low-temperature fluid inclusions probably reequilibrate with burial fluids during progressive burial. Reequilibration is likely caused by high internal pressures in inclusions which result in hydrofracturing. The resulting fluid-inclusion population could contain a nearly complete record of burial fluids in which a particular rock has been bathed. *Present address: Department of Geology, University of Kansas, Lawrence, Kansas 66045
Microstructural aspects in steel fiber reinforced acrylic emulsion polymer modified concrete
NASA Astrophysics Data System (ADS)
Hazimmah, Dayang; Ayob, Afizah; Sie Yee, Lau; Chee Cung, Wong
2018-03-01
Scanning electron microscope observations of polymer-free and polymer-modified cements have shown that the polymer particles are partitioned between the inside of hydrates and the surface of anhydrous cement grains. For optimum dosage of acrylic emulsion polymer with 2.5%, the C-S-H gel in this structure is finer and more acicular. Some polymer adheres or deposit on the surface of the C-S-H gel. The presence of acrylic emulsion polymer confines the ionic diffusion so that the Ca(OH)2 crystallized locally to form fine crystals. The void in the structures seems to be smaller but no polymer films appears to be bridging the walls of pores although many polymer bonds or C-S-H spread into the pore spaces. In addition to porosity reduction, acrylic emulsion polymer modified the hydration products in the steel fiber -matrix ITZ. The hydration product C-S-H appeared as a needle like shape. The needle-shaped C-S-H increases and gradually formed the gel, with needles growing into the pore space. The phenomenon is more obvious as curing age increased.
NASA Astrophysics Data System (ADS)
Brown, Megan R. M.; Ge, Shemin; Sheehan, Anne F.; Nakai, Jenny S.
2017-08-01
Mitigation of injection-induced seismicity in Greeley, Colorado, is based largely on proximity of wastewater disposal wells to seismicity and consists of cementation of the bottom of wells to eliminate connection between the disposal interval and crystalline basement. Brief injection rate reductions followed felt events, but injection rates returned to high levels, >250,000 barrels/month, within 6 months. While brief rate reduction reduces seismicity in the short term, overall seismicity is not reduced. We examine contributions to pore pressure change by injection from 22 wells within 30 km of the center of seismicity. The combined injection rate of seven disposal wells within 15 km of the seismicity (Greeley Wells) is correlated with the seismicity rate. We find that injection from NGL-C4A, the well previously suspected as the likely cause of the induced seismicity, is responsible for 28% of pore pressure increase. The other six Greeley Wells contribute 28% of pore pressure increase, and the 15 Far-field Wells between 15 and 30 km from the seismicity contribute 44% of pore pressure increase. Modeling results show that NGL-C4A plays the largest role in increased pore pressure but shows that the six other Greeley Wells have approximately the same influence as NGL-C4A. Furthermore, the 15 Far-field Wells have significant influence on pore pressure near the seismicity. Since the main mitigation action of cementing the bottom of wells has not decreased seismicity, mitigation based on reduced injection rates and spacing wells farther apart would likely have a higher potential for success.
NASA Astrophysics Data System (ADS)
Dubiel, Stanisław; Zubrzycki, Adam; Rybicki, Czesław; Maruta, Michał
2012-11-01
In the south part of the Carpathian Foredeep basement, between Bochnia and Ropczyce, the Upper Jurassic (Oxfordian, Kimmeridian and Tithonian) carbonate complex plays important role as a hydrocarbon bearing formation. It consists of shallow marine carbonates deposited in environments of the outer carbonate ramp as reef limestones (dolomites), microbial - sponge or coral biostromes and marly or micrite limestones as well. The inner pore space system of these rocks was affected by different diagenetic processes as calcite cementation, dissolution, dolomitization and most probably by tectonic fracturing as well. These phenomena have modified pore space systems within limestone / dolomite series forming more or less developed reservoir zones (horizons). According to the interpretation of DST results (analysis of pressure build up curves by log - log method) for 11 intervals (marked out previously by well logging due to porosity increase readings) within the Upper Jurassic formation 3 types of pore/fracture space systems were distinguished: - type I - fracture - vuggy porosity system in which fractures connecting voids and vugs within organogenic carbonates are of great importance for medium flow; - type II - vuggy - fracture porosity system where a pore space consists of weak connected voids and intergranular/intercrystalline pores with minor influence of fractures; - type III - cavern porosity system in which a secondary porosity is developed due to dolomitization and cement/grain dissolution processes.
NASA Astrophysics Data System (ADS)
Torrisi, A.; Torrisi, V.; Tuccitto, N.; Gandolfi, M. G.; Prati, C.; Licciardello, A.
2010-01-01
ToF-SIMS images were obtained from a section of a tooth, obturated by means of a new calcium-silicate based cement (wTCF) after storage for 1 month in a saline solutions (DPBS), in order to simulate the body fluid effects on the obturation. Afterwards, ToF-SIMS spectra were obtained from model samples, prepared by using the same cement paste, after storage for 1 month and 8 months in two different saline solutions (DPBS and HBSS). ToF-SIMS spectra were also obtained from fluorine-free cement (wTC) samples after storage in HBSS for 1 month and 8 months and used for comparison. It was found that the composition of both the saline solution and the cement influenced the composition of the surface of disks and that longer is the storage greater are the differences. Segregation phenomena occur both on the cement obturation of the tooth and on the surface of the disks prepared by using the same cement. Indirect evidences of formation of new crystalline phases are supplied.
Yoon, Hongkyu; Major, Jonathan; Dewers, Thomas; ...
2017-01-05
Dissolved CO 2 in the subsurface resulting from geological CO 2 storage may react with minerals in fractured rocks, confined aquifers, or faults, resulting in mineral precipitation and dissolution. The overall rate of reaction can be affected by coupled processes including hydrodynamics, transport, and reactions at the (sub) pore-scale. In this work pore-scale modeling of coupled fluid flow, reactive transport, and heterogeneous reactions at the mineral surface is applied to account for permeability alterations caused by precipitation-induced pore-blocking. This paper is motivated by observations of CO 2 seeps from a natural CO 2 sequestration analog, Crystal Geyser, Utah. Observations alongmore » the surface exposure of the Little Grand Wash fault indicate the lateral migration of CO 2 seep sites (i.e., alteration zones) of 10–50 m width with spacing on the order of ~100 m over time. Sandstone permeability in alteration zones is reduced by 3–4 orders of magnitude by carbonate cementation compared to unaltered zones. One granular porous medium and one fracture network systems are used to conceptually represent permeable porous media and locations of conduits controlled by fault-segment intersections and/or topography, respectively. Simulation cases accounted for a range of reaction regimes characterized by the Damköhler (Da) and Peclet (Pe) numbers. Pore-scale simulation results demonstrate that combinations of transport (Pe), geochemical conditions (Da), solution chemistry, and pore and fracture configurations contributed to match key patterns observed in the field of how calcite precipitation alters flow paths by pore plugging. This comparison of simulation results with field observations reveals mechanistic explanations of the lateral migration and enhances our understanding of subsurface processes associated with the CO 2 injection. In addition, permeability and porosity relations are constructed from pore-scale simulations which account for a range of reaction regimes characterized by the Da and Pe numbers. Finally, the functional relationships obtained from pore-scale simulations can be used in a continuum scale model that may account for large-scale phenomena mimicking lateral migration of surface CO 2 seeps.« less
Emplacement and dewatering of the world's largest exposed sand injectite complex
NASA Astrophysics Data System (ADS)
Sherry, Timothy J.; Rowe, Christie D.; Kirkpatrick, James D.; Brodsky, Emily E.
2012-08-01
Sandstone injectites form by up or down-section flow of a mobilized sand slurry through fractures in overlying rock. They act as reservoirs and high-permeability conduits through lower permeability rock in hydrocarbon systems. The Yellow Bank Creek Complex, Santa Cruz County, California is the largest known exposure of a sandstone injectite in the world. The complex contains granular textures that record processes of sand slurry flow, multiple pore fluids, and dewatering after emplacement. The injection was initially mobilized from a source containing both water and hydrocarbons. The water-sand slurry reached emplacement depth first, due to lower fluid viscosity. As the sand slurry emplaced, the transition from slurry flow to pore water percolation occurred. This transition resulted in preferred flow channels ˜6 mm wide in which sand grains were weakly aligned (laminae). The hydrocarbon-sand slurry intruded the dewatering sands and locally deformed the laminae. Compaction of the injectite deposit and pore fluid escape caused spaced compaction bands and dewatering pipes which created convolutions of the laminae. The hydrocarbon-rich sand slurry is preserved today as dolomite-cemented sand with oil inclusions. The laminae in this injectite are easily detected due to preferential iron oxide-cementation of the well-aligned sand laminae, and lack of cement in the alternating laminae. Subtle textures like these may develop during sand flow and be present but difficult to detect in other settings. They may explain permeability anisotropy in other sand deposits.
Diagenetic history of late Oligocene-early Miocene carbonates in East Sabah, Malaysia
NASA Astrophysics Data System (ADS)
Zainal Abidin, N. S.; Raymond, R. R.; Bashah, N. S. I.
2017-10-01
Limestones are particularly susceptible to drastic early diagenesis modifications, mainly cementation and dissolution. During the early Miocene, a major tectonic deformation has caused a widespread of uplift in Sabah. This has resulted change in depositional environment from deep to shallow marine, which favours the deposition of Gomantong Limestone. This study aims to investigate the diagenetic history of Gomantong Limestone in East Sabah. Thorough understanding of the diagenetic processes may provide data to unravel the tectonic activities which affected the reservoir quality of the carbonates. Combining the data from comprehensive petrographic analysis, and Scanning Electron Microscopy (SEM) of 30 samples, two main cements type were identified. These are microcrystalline cement and Mg-calcite cement of granular and blocky mosaics which are dominantly seen in all samples. The sequence of diagenesis events are determined as (1) micritization; (2) grain scale compaction; (3) cementation (pore-filling); (4) mechanical compaction and cementation infilling fractures and (5) chemical compaction. These diagenetic events are interpreted as reflection of changes in diagenetic environment from shallow marine to deep burial. The massive cementation in the Gomantong Limestone has resulted into a poor reservoir quality.
Sediment-pore water interactions controlling cementation in the NanTroSEIZE drilling transects
NASA Astrophysics Data System (ADS)
Hong, W.; Spinelli, G. A.; Torres, M. E.
2012-12-01
One goal of the Nankai Trough Seismogenic Zone Experiment (NanTroSEIZE) is to understand how changes in subducting sediment control the transition from aseismic to seismogenic behavior in subduction zones. In the sediment entering the Nankai subduction zone, dramatic changes in physical and chemical properties occur across a diagenetic boundary; they are thought to affect sediment strength and deformation. The dissolution of disseminated volcanic ash and precipitation of silica cement may be responsible for these changes in physical properties, but the mechanism controlling cementation was unclear (Spinelli et al., 2007). In this study, we used CrunchFlow (Steefel, 2009) to simulate chemical reactions and fluid flow through 1-D sediment columns at Integrated Ocean Drilling Program (IODP) sites on the incoming plate in Nankai Trough. The simulations include the thermodynamics and kinetics of sediment-water interactions, advection of pore water and sediment due to compaction, and multi-component diffusion in an accumulating sediment column. Key reactions in the simulations are: ash dissolution, amorphous silica precipitation and dissolution, and zeolite precipitation. The rate of ash decomposition was constrained using Sr isotope data of Joseph et al. (2012). Our model reproduces the distinct diagenetic boundary observed in sediment and pore water chemistry, which defines two zones. Above this boundary (zone 1), dissolved and amorphous silicate contents are high and the potassium concentration remains near seawater values or gradually decreases toward the boundary. Below the boundary, both dissolved and amorphous silicate content drop rapidly, concomitant with a decrease in dissolved potassium. Our model shows that these changes in the system are driven by formation of clinoptilolite in response to changes in pore fluid pH. The low pH values (<7.6) above the diagenetic boundary accelerate ash decomposition and maintain clinoptilolite slightly undersaturated. The dissolved silicate released from ash alteration precipitates as cement, inhibiting consolidation. At or below the boundary, the increase in pH (>8.0), leads to oversaturation (and precipitation) of clinoptilolite. Strong demand of dissolved silicate due to clinoptilolite formation soon depletes the dissolved potassium and silicate; ash and silicate cement are forced to dissolve. The exact set of reactions resulting on the observed pH increase is still unclear, but it likely involves the carbon system. It is noteworthy that the diagenetic boundary at all sites in the incoming plate occurs at the same thermal maturity of the sediments (TTI=0.025), similar to observations on onshore sequences in Japan (Sasaki, 1986).
Influence of Rubber Size on Properties of Crumb Rubber Mortars
Yu, Yong; Zhu, Han
2016-01-01
Studies on the properties and applications of rubber cement-based materials are well documented. The sizes of rubbers used in these materials varied. However, information about the effects of rubber size on the properties of rubber cement-based materials, especially pore structure, mechanical strengths, and drying shrinkage properties, remains limited. Three groups of rubber with major particle sizes of 2–4 mm, 1–3 mm, and 0–2 mm were selected in this study. This paper presents experimental studies on the effects of rubber size on the consistency, fresh density, pore structure, mechanical properties, and drying shrinkage properties of crumb rubber mortars (CRMs). Results demonstrated that the consistency and fresh density of CRMs decreased with the rubber size. As to the pore structure, the total pore volume increased with the decrease of the rubber size. By contrast, the influence of the rubber size on the mesopore (<50 nm) volume is not as significant as that of the rubber content. The mechanical properties of CRMs decreased with the rubber size. Low rubber stiffness and large pore volumes, especially those of small sized rubbers, contribute to the reduction of CRMs strength. The drying shrinkage of CRM increases as the rubber size decreases. The influences of rubber size on capillary tension are not significant. Thus, the shrinkage increases with the decrease of rubber size mainly because of its function in the deformation modulus reduction of CRMs. PMID:28773649
Permeation Properties and Pore Structure of Surface Layer of Fly Ash Concrete
Liu, Jun; Qiu, Qiwen; Xing, Feng; Pan, Dong
2014-01-01
This paper presents an experimental study on the nature of permeation properties and pore structure of concrete surface layers containing fly ash. Concretes containing different dosages of fly ash as a replacement for cement (15% and 30% by weight of total cement materials, respectively) were investigated. Concrete without any fly ash added was also employed as the reference specimen. Laboratory tests were conducted to determine the surface layer properties of concrete including chloride transport, apparent water permeability and pore structure. The results demonstrate that incorporation of fly ash, for the early test period, promotes the chloride ingress at the surface layer of concrete but substituting proportions of fly ash may have little impact on it. With the process of chloride immersion, the chloride concentration at the surface layer of concrete with or without fly ash was found to be nearly the same. In addition, it is suggested that the water permeability at the concrete surface area is closely related to the fly ash contents as well as the chloride exposure time. Pore structure was characterized by means of mercury intrusion porosimetry (MIP) test and the scanning electron microscopy (SEM) images. The modification of pore structure of concrete submersed in distilled water is determined by the pozzolanic reaction of fly ash and the calcium leaching effect. The pozzolanic reaction was more dominant at the immersion time of 180 days while the calcium leaching effect became more evident after 270 days. PMID:28788677
Process for disposal of aqueous solutions containing radioactive isotopes
Colombo, Peter; Neilson, Jr., Robert M.; Becker, Walter W.
1979-01-01
A process for disposing of radioactive aqueous waste solutions whereby the waste solution is utilized as the water of hydration to hydrate densified powdered portland cement in a leakproof container; said waste solution being dispersed without mechanical inter-mixing in situ in said bulk cement, thereafter the hydrated cement body is impregnated with a mixture of a monomer and polymerization catalyst to form polymer throughout the cement body. The entire process being carried out while maintaining the temperature of the components during the process at a temperature below 99.degree. C. The container containing the solid polymer-impregnated body is thereafter stored at a radioactive waste storage dump such as an underground storage dump.
The effect of endodontic materials on the optical density of dyes used in marginal leakage studies.
Kubo, Claudio Hideki; Valera, Marcia Carneiro; Gomes, Ana Paula Martins; Mancini, Maria Nadir Gasparoto; Camargo, Carlos Henrique Ribeiro
2008-01-01
The aim of this study was to determine the effect of the exposure of different endodontic materials to different dye solutions by evaluating the optical density of the dye solutions. Seventy-five plastic tubes were filled with one of the following materials: AH Plus, Sealapex, Portland cement, MTA (Angelus and Pro Root) and fifteen control plastic tubes were not. Each specimen of material and control was immersed in a container with 1 ml of each dye solution. A 0.1 ml-dye solution aliquote was removed before immersion and after 12, 24, 48 and 72 hours of each specimen immersion to record its optical density (OD) in a spectrophotometer. Statistical analysis was performed with ANOVA and Tukey tests (5%). No significant difference was found among any of the solution OD values for AH Plus cement. Portland cement promoted different OD values after 12 hours of immersion. MTA-Angelus cement presented different OD values only for 2% rhodamine B and the MTA-Pro Root cement presented different OD values in all 2% rhodamine B samples. Sealapex cement promoted a reduction in the India Ink OD values. Dye evaluation through OD seems to be an interesting method to select the best dye solution to use in a given marginal leakage study.
NASA Astrophysics Data System (ADS)
Janssen, C.; Wirth, R.; Kienast, M.; Yabe, Y.; Sulem, J.; Dresen, G. H.
2015-12-01
Chemical and mechanical effects of fluids influence the fault mechanical behavior. We analyzed fresh fault rocks from several scientific drilling projects to study the effects of fluids on fault strength. For example, in drill core samples on a rupture plane of an Mw 2.2 earthquake in a deep gold mine in South Africa the main shock occurred on a preexisting plane of weakness that was formed by fluid-rock interaction (magnesiohornblende was intensively altered to chlinochlore). The plane acted as conduit for hydrothermal fluids at some time in the past. The chemical influence of fluids on mineralogical alteration and geomechanical processes in fault core samples from SAFOD (San Andreas Fault Observatory at Depth) is visible in pronounced dissolution-precipitation processes (stylolites, solution seams) as well as in the formation of new phases. Detrital quartz and feldspar grains are partially dissolved and replaced by authigenic illite-smectite (I-S) mixed-layer clay minerals. Transmission Electron Microscopy (TEM) imaging of these grains reveals that the alteration processes and healing were initiated within pores and small intra-grain fissures. Newly formed phyllosilicates growing into open pore spaces likely reduced the fluid permeability. The mechanical influence of fluids is indicated by TEM observations, which document open pores that formed in-situ in the gouge material during or after deformation. Pores were possibly filled with formation water and/or hydrothermal fluids suggesting elevated fluid pressure preventing pore collapse. Fluid-driven healing of fractures in samples from SAFOD and the DGLab Gulf of Corinth project is visible in cementation. Cathodoluminescence microscopy (CL) reveals different generations of calcite veins. Differences in CL-colors suggest repeated infiltration of fluids with different chemical composition from varying sources (formation and meteoric water).
Quantifying Rock Weakening Due to Decreasing Calcite Mineral Content by Numerical Simulations
2018-01-01
The quantification of changes in geomechanical properties due to chemical reactions is of paramount importance for geological subsurface utilisation, since mineral dissolution generally reduces rock stiffness. In the present study, the effective elastic moduli of two digital rock samples, the Fontainebleau and Bentheim sandstones, are numerically determined based on micro-CT images. Reduction in rock stiffness due to the dissolution of 10% calcite cement by volume out of the pore network is quantified for three synthetic spatial calcite distributions (coating, partial filling and random) using representative sub-cubes derived from the digital rock samples. Due to the reduced calcite content, bulk and shear moduli decrease by 34% and 38% in maximum, respectively. Total porosity is clearly the dominant parameter, while spatial calcite distribution has a minor impact, except for a randomly chosen cement distribution within the pore network. Moreover, applying an initial stiffness reduced by 47% for the calcite cement results only in a slightly weaker mechanical behaviour. Using the quantitative approach introduced here substantially improves the accuracy of predictions in elastic rock properties compared to general analytical methods, and further enables quantification of uncertainties related to spatial variations in porosity and mineral distribution. PMID:29614776
Quantifying Rock Weakening Due to Decreasing Calcite Mineral Content by Numerical Simulations.
Wetzel, Maria; Kempka, Thomas; Kühn, Michael
2018-04-01
The quantification of changes in geomechanical properties due to chemical reactions is of paramount importance for geological subsurface utilisation, since mineral dissolution generally reduces rock stiffness. In the present study, the effective elastic moduli of two digital rock samples, the Fontainebleau and Bentheim sandstones, are numerically determined based on micro-CT images. Reduction in rock stiffness due to the dissolution of 10% calcite cement by volume out of the pore network is quantified for three synthetic spatial calcite distributions (coating, partial filling and random) using representative sub-cubes derived from the digital rock samples. Due to the reduced calcite content, bulk and shear moduli decrease by 34% and 38% in maximum, respectively. Total porosity is clearly the dominant parameter, while spatial calcite distribution has a minor impact, except for a randomly chosen cement distribution within the pore network. Moreover, applying an initial stiffness reduced by 47% for the calcite cement results only in a slightly weaker mechanical behaviour. Using the quantitative approach introduced here substantially improves the accuracy of predictions in elastic rock properties compared to general analytical methods, and further enables quantification of uncertainties related to spatial variations in porosity and mineral distribution.
Monteilhet, L; Korb, J-P; Mitchell, J; McDonald, P J
2006-12-01
The first detailed analysis of the two-dimensional (2D) NMR T(2)-T(2) exchange experiment with a period of magnetization storage between the two T(2) relaxation encoding periods (T(2)-store-T(2)) is presented. It is shown that this experiment has certain advantages over the T(1)-T(2) variant for the quantization of chemical exchange. New T(2)-store-T(2) 2D 1H NMR spectra of the pore water within white cement paste are presented. Based on these spectra, the exchange rate of water between the two smallest porosity reservoirs is estimated for the first time. It is found to be of the order of 5 ms{-1}. Further, a careful estimate of the pore sizes of these reservoirs is made. They are found to be of the order of 1.4 nm and 10-30 nm , respectively. A discussion of the results is developed in terms of possible calcium silicate hydrate products. A water diffusion coefficient inferred from the exchange rate and the cement particle size is found to compare favorably with the results of molecular-dynamics simulations to be found in the literature.
Keighin, C.W.; Zech, R.S.; Dunbar, R.W.
1993-01-01
The Point Lookout sandstones are quartz-rich, fine to very-fine grained, and contain moderately variable quantities of potassium feldspar (2 to 20 modal percent) and lithic fragments (9 to 20 modal percent). Locally, sandstone is tightly cemented by carbonate cement; clays are not important as cementing agents, although they significantly reduce permeability of some samples. Pores are small; many are intergranular micropores between crystals of authigenic clay. Depositional environments are highly variable and range from lower shoreface to coastal plain and include minor deltaic environments. The best reservoir characteristics are generally in the upper shoreface sandstones. -from Authors
NASA Astrophysics Data System (ADS)
Zaid, Samir M.
2013-09-01
The Middle Miocene Kareem sandstones are important oil reservoirs in the southwestern part of the Gulf of Suez basin, Egypt. However, their diagenesis and provenance and their impact on reservoir quality, are virtually unknown. Samples from the Zeit Bay Oil Field, and the East Zeit Oil Field represent the Lower Kareem (Rahmi Member) and the Upper Kareem (Shagar Member), were studied using a combination of petrographic, mineralogical and geochemical techniques. The Lower Rahmi sandstones have an average framework composition of Q95F3.4R1.6, and 90% of the quartz grains are monocrystalline. By contrast, the Upper Shagar sandstones are only slightly less quartzose with an average framework composition of Q76F21R3 and 82% of the quartz grains are monocrystalline. The Kareem sandstones are mostly quartzarenite with subordinate subarkose and arkose. Petrographical and geochemical data of sandstones indicate that they were derived from granitic and metamorphic terrains as the main source rock with a subordinate quartzose recycled sedimentary rocks and deposited in a passive continental margin of a syn rift basin. The sandstones of the Kareem Formation show upward decrease in maturity. Petrographic study revealed that dolomite is the dominant cement and generally occurs as fine to medium rhombs pore occluding phase and locally as a grain replacive phase. Authigenic quartz occurs as small euhedral crystals, locally as large pyramidal crystals in the primary pores. Authigenic anhydrites typically occur as poikilotopic rhombs or elongate laths infilling pores but also as vein filling cement. The kaolinite is a by-product of feldspar leaching in the presence of acidic fluid produced during the maturation of organic matter in the adjacent Miocene rocks. Diagenetic features include compaction; dolomite, silica and anhydrite cementation with minor iron-oxide, illite, kaolinite and pyrite cements; dissolution of feldspars, rock fragments. Silica dissolution, grain replacement and carbonate dissolution greatly enhance the petrophysical properties of many sandstone samples.
Giti, Rashin; Vojdani, Mahroo; Abduo, Jaafar; Bagheri, Rafat
2016-06-01
Structural integrity and dimensional stability are the key factors that determine the clinical success and durability of luting cements in the oral cavity. Sorption and solubility of self-adhesive resin luting cements in food-simulating solutions has not been studied sufficiently. This study aimed to compare the sorption and solubility of 2 conventional and 2 self-adhesive resin-based luting cements immersed in four different storage media. A total of 32 disc-shaped specimens were prepared from each of four resin luting cements; seT (SDI), Panavia F (Kuraray), Clearfil SA Cement (Kuraray), and Choice 2 (Bisco). Eight specimens of each material were immersed in all tested solutions including n-heptane 97%, distilled water, apple juice, or Listerine mouth wash. Sorption and solubility were measured by weighing the specimens before and after immersion and desiccation. Data were analyzed by SPSS version 18, using two-way ANOVA and Tukey's HSD test with p≤ 0.05 set as the level of significance. There was a statistically significant interaction between the materials and solutions. The effect of media on the sorption and solubility was material-dependent. While seT showed the highest values of the sorption in almost all solutions, Choice 2 showed the least values of sorption and solubility. Immersion in apple juice caused more sorption than other solutions (p≤ 0.05). The sorption and solubility behavior of the studied cements were significantly affected by their composition and the storage media. The more hydrophobic materials with higher filler content like Choice 2 resin cement showed the least sorption and solubility. Due to their lower sorption and solubility, these types of resin-based luting cements are recommended to be used clinically.
NASA Astrophysics Data System (ADS)
Scrivano, Simona; Gaggero, Laura; Gisbert Aguilar, Josep
2016-04-01
Porosity is the main physical feature dealing with rocks durability and storage capacity. The analysis of this parameter is key factor in predicting rock performances (Molina et al., 2011). There are several techniques that can be applied to acquire the widest information range possible about pores (e.g. size, shape, distribution), leading to a better understanding of decay processes and trapping capacity. The coupling of a detailed minero-petrographic analysis with physical measures such as ultrasounds and mercury intrusion porosimetry (MIP) proved to be a valid tool for understanding the porous network and its evolution during weathering processes. Both fresh and salt-weathered samples were analysed to investigate the modification triggered in the porous network by crystallization. The ageing process was induced using a Na2SO4 saturated saline solution with the partial continuous immersion method (Benavente et al., 2001). The study was addressed to four sedimentary lithotypes: 1) Arenaria Macigno, a greywacke made up of thickened clasts of quartz, plagioclase and K-feldspar cemented by micritic calcite and phyllosilicates; 2) Breccia Aurora, a calcareous breccia with nodules of compact limestone and micritic cement joints; 3) Rosso Verona, a biomicrite where the compact bio-micrite matrix is cut by clay minerals veins; and 4) Vicenza Stone, an organogenic limestone rich in micro- and macro foraminifera, algae, bryozoans and remains of echinoderms, with iron oxides. An appropriate description of the porous network variation and recognition of the origin of secondary porosity was attained. The study defined that the pore shape and distribution (anisotropy coefficient K) has a fluctuation up to the 50% after weathering treatments and pore-size distribution (defined in a range between 0,0025 - 75 μm), allowing modelling the mechanisms of water transport and evaluating decay susceptibility of these lithotypes. Molina E, Cultrone G, Sebastián E, Alonso FJ, Carrizo L, Gisbert J, et al. The pore system of sedimentary rocks as a key factor in the durability of building materials. Eng Geol 118 (2011) 110-21. D. Benavente, M.A. Garcia del Cura, A. Bernabeu, S. Ordonez. Quantification of salt weathering in porous stones using an experimental continuous partial immersion method. Eng Geol 59 (2001) 313-325.
Size effects of pore density and solute size on water osmosis through nanoporous membrane.
Zhao, Kuiwen; Wu, Huiying
2012-11-15
Understanding the behavior of osmotic transport across nanoporous membranes at molecular level is critical to their design and applications, and it is also beneficial to the comprehension of the mechanism of biological transmembrane transport processes. Pore density is an important parameter for nanoporous membranes. To better understand the influence of pore density on osmotic transport, we have performed systematic molecular dynamics simulations on water osmosis across nanoporous membranes with different pore densities (i.e., number of pores per unit area of membrane). The simulation results reveal that significant size effects occur when the pore density is so high that the center-to-center distance between neighboring nanopores is comparable to the solute size. The size effects are independent of the pore diameter and solute concentration. A simple quantitative correlation between pore density, solute size, and osmotic flux has been established. The results are excellently consistent with the theoretical predictions. It is also shown that solute hydration plays an important role in real osmotic processes. Solute hydration strengthens the size effects of pore density on osmotic processes due to the enlarged effective solute size induced by hydration. The influence of pore density, solute size, and solute hydration on water osmosis through nanoporous membranes can be introduced to eliminate the deviations of real osmotic processes from ideal behavior.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Beaver, J.L. Jr.
Suniland field is located in the west Texas Permian basin. Production is primarily from peritidal shelf dolomites of the Permian (Guadalupian) San Andres Formation. San Andres deposition was highly cyclical, with at least two upward-shoaling megacycles comprising the lower 600 ft (183 m) of the formation; many smaller cycles occur within the megacycles. The field consists of an elongate, low-relief, east-west-trending anticline formed from draping over a pre-San Andres structural high. Hydrocarbon trapping is controlled primarily by structural closure and discontinuity of San Andres reservoir facies. Anhydrite cement precipitation also may cause an updip (northerly) permeability loss. Reservoirs occur inmore » thin, permeable oolitic grainstone intervals possessing primary intergranular porosity in combination with vugular and moldic pore systems. These grainstones interfinger with porous but generally impermeable oolitic packstones. Adjacent wackestones and mudstones are generally nonporous and impermeable. Porosity occlusion is primarily from precipitation of late dolomite cements. Anhydrite cements do not occlude porosity to a high degree. Oil production from the San Andres Formation at Suniland field is from nine separate reservoirs comprising two major pay categories, designated Sand Andres and lower San Andres. Pay depths range from 3,755 to 4,211 ft (1,144 to 1,283 m). Cumulative oil production to January 1986 is 7.35 million bbl from 69 wells. Permian (Leonardian) Glorieta production accounts for about 16% of total production. Reservoirs produce from solution gas expansion at low gas-to-oil ratios and high water cuts. Effective porosity in pay zones averages 14%; permeability averages 17 md.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Mielczarek, W.; Copper, P.
1986-08-01
About 300 bioherms are known in the Llandoverian Manitoulin Formation of eastern Manitoulin Island. In the South Bay area, the large Leask Piont bioherm and Charlton Bay patch-reef complex lack a distinct skeletal growth framework. Bioherms consist of mudstone and wackestone, with isolated lenses of bafflestone, boundstone, floatstone. Fossils are scarce, but crinozoans and bryozoans comprise about 90% of the bioclasts. Other fauna include stromatoporoids, corals, brachiopods, gastropods, trilobites, and probable algae (algae are difficult to identify and may have played a significant role). Faunal ratios remained relatively constant during mound growth. Soft substrates with sedimentation rates of a fewmore » millimeters per year are suggested by bedding type and morphologic dominance of lamellar and tabular corals and stromatoporoids. An increased sedimentation rate, resulting from shoaling, is indicated by more overturned, broadly conical corals in the upper parts of the mounds. Shoaling may be responsible for cessation of mound growth. Lithoclasts are more common in the upper parts of the mounds. They formed when semiconsolidated muds were disturbed and redeposited during storms. Megarippled interreef surface areas, largely devoid of coral growth, indicate mud instability at Charlton Bay. Lack of suitable stable substrates may have hampered coral development. Dolomitization was postdepositional. The diagenetic sequence occurred in three stages: 1)selective pyritization and silicification, formation of an early muddy dolomite replacing the mud fraction of the dolostone, lithification and formation of rare calcite cement and neomorphic syntaxial rims; 2)clear, coarse dolomite replacing pore-filling calcite cement, syntaxial rims, and unaltered macrofossils, stylolitization, grain-to-grain dissolution; and 3)a late dolomite found mainly as fine rhombs in stylolites, solution seams, and intraskeletal pore space.« less
NASA Astrophysics Data System (ADS)
Gruyaert, Elke; Debbaut, Brenda; Snoeck, Didier; Díaz, Pilar; Arizo, Alejandro; Tziviloglou, Eirini; Schlangen, Erik; De Belie, Nele
2016-08-01
Superabsorbent polymers (SAPs) have potential to be used as healing agent in self-healing concrete due to their property to attract moisture from the environment and their capacity to promote autogenous healing. A possible drawback, however, is their uptake of mixing water during concrete manufacturing, resulting in an increased volume of macro-pores in the hardened concrete. To limit this drawback, newly developed SAPs with a high swelling and pH-sensitiveness were developed and tested within the FP7 project HEALCON. Evaluation of their self-sealing performance occurred through a water permeability test via water flow, a test method also developed within HEALCON. Three different sizes of the newly developed SAP were compared with a commercial SAP. Swelling tests in cement filtrate solution indicated that the commercial and in-house synthesized SAPs performed quite similar, but the difference between the swelling capacity at pH 9 and pH 13 is more pronounced for the self-synthesized SAPs. Moreover, in comparison to the commercial SAPs, less macro-pores are formed in the cement matrix of mixes with self-synthesized SAPs and the effect on the mechanical properties is lower, but not negligible, when using high amounts of SAPs. Although the immediate sealing effect of cracks in mortar was the highest for the commercial SAPs, the in-house made SAPs with a particle size between 400 and 600 μm performed the best with regard to crack closure (mainly CaCO3 precipitation) and self-sealing efficiency, after exposing the specimens to 28 wet-dry cycles. Some specimens could even withstand a water pressure of 2 bar.
Effect of Nano-SiO₂ on the Early Hydration of Alite-Sulphoaluminate Cement.
Sun, Jinfeng; Xu, Zhiqiang; Li, Weifeng; Shen, Xiaodong
2017-05-03
The impact of nano-SiO₂ on the early hydration properties of alite-sulphoaluminate (AC$A) cement was investigated with a fixed water to solid ratio ( w / s ) of one. Nano-SiO₂ was used in partial substitution of AC$A cement at zero, one and three wt %. Calorimetry, X-ray diffraction (XRD), thermogravimetric/derivative thermogravimetric (TG/DTG), mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM) analyses were used to characterize the hydration and hydrates of the blended cement. The hydration of the AC$A cement was significantly promoted, resulting in an increase of the heat released with the addition of nano-SiO₂. Phase development composition analysis showed that nano-SiO₂ had no effect on the type of crystalline hydration products of the AC$A cement. Moreover, nano-SiO₂ showed significant positive effects on pore refinement where the total porosity decreased by 54.09% at three days with the inclusion of 3% nano-SiO₂. Finally, from the SEM observations, nano-SiO₂ was conducive to producing a denser microstructure than that of the control sample.
Investigating permeability and carbonation behavior of sustainable cements
NASA Astrophysics Data System (ADS)
White, C.; Blyth, A.; Scherer, G. W.; Morandeau, A. E.
2015-12-01
The durability of new sustainable cementitious materials is intimately linked with the ability for these materials to prevent the ingress of aggressive ions through their percolated pore networks. However, it is also important to be able to control and limit the detrimental chemical degradation mechanisms that occur to the cement binder once the ions have diffused through the pore network. Here, alkali-activated materials will be discussed, and recent research on measuring the permeability of this class of cements using the beam-bending method will be presented. It will be shown that the permeability can be controlled by tailoring the activator chemistry, and that the addition of free silica in the activator has a strong (favorable) influence on the resulting percolated pore network. Carbonation is one type of chemical degradation process that is known to severely shorten the service life of concrete, especially in environments containing elevated CO2 levels. However, the exact atomic structural changes that occur to the main binder phase (calcium-silicate-hydrate gel) during carbonation remain largely unknown. Here, X-ray pair distribution function analysis is used to elucidate the local atomic structural changes that occur during carbonation of calcium-silicate-hydrate gel and calcium-aluminosilicate-hydrate gel (alkali-activated slag binder), where distinct differences in the extent of gel decalcification are measured according to the chemistry of the starting precursor material. The results will be discussed in the context of limiting the extent of carbonation in cementitious materials, with potential applications of alkali-activated materials in geological storage of CO2 due to their increased resistance to carbonation.
Souza, Júlio C. M.; Silva, Joel B.; Aladim, Andrea; Carvalho, Oscar; Nascimento, Rubens M.; Silva, Filipe S.; Martinelli, Antonio E.; Henriques, Bruno
2016-01-01
Background: Glass-ionomer cements perform a protective effect on the dentin-pulp complex considering the F ions release and chemical bonding to the dental structures. On the other hand, those materials have poor physic-mechanical properties in comparison with the restorative resin composite. The main aim of this work was to evaluate the influence of zirconia and/or alumina fillers on the microstructure and strength of a resin modified glass-ionomer cement after thermal cycling. Methods: An in vitro experimental study was carried out on 9 groups (n = 10) of cylindrical samples (6 x 4 mm) made from resin modified glass-ionomer (Vitremer, 3M, USA) with different contents of alumina and/or zirconia fillers. A nano-hybrid resin composite was tested as a control group. Samples were mechanically characterized by axial compressive tests and electron scanning microscopy (SEM) coupled to energy dispersive X-ray spectrophotometry (EDS), before and after thermal cycling. Thermal cycling procedures were performed at 3000, 6000 and 10000 cycles in Fusayama´s artificial saliva at 5 and 60 oC. Results: An improvement of compressive strength was noticed on glass-ionomer reinforced with alumina fillers in comparison with the commercial glass ionomer. SEM images revealed the morphology and distribution of alumina or zirconia in the microstructure of glass-ionomers. Also, defects such as cracks and pores were detected on the glass-ionomer cements. The materials tested were not affected by thermal cycling in artificial saliva. Conclusion: Addition of inorganic particles at nano-scale such as alumina can increase the mechanical properties of glass-ionomer cements. However, the presence of cracks and pores present in glass-ionomer can negatively affect the mechanical properties of the material because they are areas of stress concentration. PMID:27053969
DOE Office of Scientific and Technical Information (OSTI.GOV)
Schwartz, D.E.
1990-05-01
The intermixing and interbedding of biogenically derived siliceous sediment with terrigenous clastic sediment in reservoirs of upper Miocene age provides both reservoir rock and seal and influences productivity by affecting porosity and permeability. Miocene reservoirs commonly contain either biogenic-dominated cyclic diatomite, porcelanite, or chert (classic Monterey Formation) or clastic-dominated submarine fan sequences with interbedded or intermixed siliceous members of biogenic origin. Biogenic-clastic cycles, 30-180 ft thick, at South Belridge field were formed by episodic influx of clastic sediment from distant submarine fans mixing with slowly accumulating diatomaceous ooze. The cycles consist of basal silt and pelletized massive diatomaceous mudstone, overlainmore » by burrowed, faintly bedded clayey diatomite and topped by laminated diatomite. Cycle tops have higher porosity and permeability, lower grain density, and higher oil saturation than clay and silt-rich portions of the cycles. Submarine fan sediments forming reservoirs at the Beta field are comprised of interbedded sands and silts deposited in a channelized middle fan to outer fan setting. Individual turbidites display fining-upward sequences, with oil-bearing sands capped by wet micaceous silts. Average sands are moderately to poorly sorted, fine- to medium-grained arkosic arenites. Sands contain pore-filling carbonate and porcelaneous cements. Porcelaneous cement consists of a mixture of opal-A, opal-CT, and chert with montmorillonite and minor zeolite. This cement is an authigenic material precipitated in intergranular pore space. The origin of the opal is biogenic, with recrystallization of diatom frustules (opal-A) into opal-CT lepispheres and quartz crystals. Porcelaneous cement comprises 4-21% of the bulk volume of the rock. Seventy percent of the bulk volume of the cement is micropore space.« less
Cement paste prior to setting: A rheological approach
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bellotto, Maurizio, E-mail: maurizio.bellotto@bozzetto.it
2013-10-15
The evolution of cement paste during the dormant period is analyzed via small amplitude oscillation rheological measurements. Cement paste, from the very first moments after mixing cement and water, shows the formation of an elastic gel whose strength is rapidly increasing over time. Up to the onset of Portlandite precipitation G′(t) increases by more than 2 orders of magnitude and in the acceleratory period G′(t) continues steadily to increase. A microstructural modification is likely to occur between the dormant and the acceleratory period. At low deformations in the linearity domain the storage modulus G′(ω) exhibits a negligible frequency dependence. Atmore » higher deformations cement paste shows a yield stress which increases on increasing paste concentration. The presence of superplasticizers decreases the yield stress and increases the gelation threshold of the paste. Above the gelation threshold the evolution of cement paste with superplasticizers follows similar trends to the neat paste. -- Highlights: •The gelation of cement paste during the dormant period is analyzed via rheometry. •The observed evolution is proposed to be related to the pore structure refinement. •Similarities are observed with colloidal gels and colloidal glasses.« less
McMahon, Peter B.; Chapelle, Francis H.
1991-01-01
Stable isotope data for dissolved inorganic carbon (DIC), carbonate shell material and cements, and microbial CO2 were combined with organic and inorganic chemical data from aquifer and confining-bed pore waters to construct geochemical reaction models along a flowpath in the Black Creek aquifer of South Carolina. Carbon-isotope fractionation between DIC and precipitating cements was treated as a Rayleigh distillation process. Organic matter oxidation was coupled to microbial fermentation and sulfate reduction. All reaction models reproduced the observed chemical and isotopic compositions of final waters. However, model 1, in which all sources of carbon and electron-acceptors were assumed to be internal to the aquifer, was invalidated owing to the large ratio of fermentation CO2 to respiration CO2 predicted by the model (5–49) compared with measured ratios (two or less). In model 2, this ratio was reduced by assuming that confining beds adjacent to the aquifer act as sources of dissolved organic carbon and sulfate. This assumption was based on measured high concentrations of dissolved organic acids and sulfate in confining-bed pore waters (60–100 μM and 100–380 μM, respectively) relative to aquifer pore waters (from less than 30 μM and 2–80 μM, respectively). Sodium was chosen as the companion ion to organic-acid and sulfate transport from confining beds because it is the predominant cation in confining-bed pore waters. As a result, excessive amounts of Na-for-Ca ion exchange and calcite precipitation (three to four times more cement than observed in the aquifer) were required by model 2 to achieve mass and isotope balance of final water. For this reason, model 2 was invalidated. Agreement between model-predicted and measured amounts of carbonate cement and ratios of fermentation CO2 to respiration CO2 were obtained in a reaction model that assumed confining beds act as sources of DIC, as well as organic acids and sulfate. This assumption was supported by measured high concentrations of DIC in confining beds (2.6–2.7 mM). Results from this study show that geochemical models of confined aquifer systems must incorporate the effects of adjacent confining beds to reproduce observed groundwater chemistry accurately.
McMahon, Peter B.; Chapelle, Francis H.
1991-01-01
Stable isotope data for dissolved inorganic carbon (DIC), carbonate shell material and cements, and microbial CO2 were combined with organic and inorganic chemical data from aquifer and confining-bed pore waters to construct geochemical reaction models along a flowpath in the Black Creek aquifer of South Carolina. Carbon-isotope fractionation between DIC and precipitating cements was treated as a Rayleigh distillation process. Organic matter oxidation was coupled to microbial fermentation and sulfate reduction. All reaction models reproduced the observed chemical and isotopic compositions of final waters. However, model 1, in which all sources of carbon and electron-acceptors were assumed to be internal to the aquifer, was invalidated owing to the large ratio of fermentation CO2 to respiration CO2 predicted by the model (5–49) compared with measured ratios (two or less). In model 2, this ratio was reduced by assuming that confining beds adjacent to the aquifer act as sources of dissolved organic carbon and sulfate. This assumption was based on measured high concentrations of dissolved organic acids and sulfate in confining-bed pore waters (60–100 μM and 100–380 μM, respectively) relative to aquifer pore waters (from less than 30 μM and 2–80 μM, respectively). Sodium was chosen as the companion ion to organic-acid and sulfate transport from confining beds because it is the predominant cation in confining-bed pore waters. As a result, excessive amounts of Na-for-Ca ion exchange and calcite precipitation (three to four times more cement than observed in the aquifer) were required by model 2 to achieve mass and isotope balance of final water. For this reason, model 2 was invalidated. Agreement between model-predicted and measured amounts of carbonate cement and ratios of fermentation CO2 to respiration CO2 were obtained in a reaction model that assumed confining beds act as sources of DIC, as well as organic acids and sulfate. This assumption was supported by measured high concentrations of DIC in confining beds (2.6–2.7 mM). Results from this study show that geochemical models of confined aquifer systems must incorporate the effects of adjacent confining beds to reproduce observed groundwater chemistry accurately.
NASA Astrophysics Data System (ADS)
Wu, Baoye; Liu, Peng; Wang, Xizhao; Zhang, Fei; Deng, Leimin; Duan, Jun; Zeng, Xiaoyan
2018-05-01
Due to excellent properties, Cr12MoV mold steel, 9Cr18 stainless steel and H13A cemented carbide are widely used in industry. In this paper, the effect of absorption of laser light on ablation efficiency and roughness have been studied using a picosecond pulse Nd:YVO4 laser. The experimental results reveal that laser wavelength, original surface roughness and chemical composition play an important role in controlling ablation efficiency and roughness. Firstly, higher ablation efficiency with lower surface roughness is achieved on the ablation of 9Cr18 at 532, comparing with 1064 nm. Secondly, the ablation efficiency increases while the Ra of the ablated region decreases with the decrease of original surface roughness on ablation of Cr12MoV mold steel at 532 nm. Thirdly, the ablation efficiency of H13A cemented carbide is much higher than 9Cr18 stainless steel and Cr12MoV mold steel at 1064 nm. Scanning electron microscopy images reveals the formation of pores on the surface of 9Cr18 stainless steel and Cr12MoV mold steel at 532 nm while no pores are formed at 1064 nm. As to H13A cemented carbide, worm-like structure is formed at 1064 nm. The synergetic effects of the heat accumulation, plasma shielding and ablation threshold on laser ablation efficiency and machining quality were analyzed and discussed systematically in this paper.
NASA Astrophysics Data System (ADS)
Hu, Peng; Yu, Xinghe; Shan, Xin; Su, Dongxu; Wang, Jiao; Li, Yalong; Shi, Xin; Xu, Liqiang
2016-04-01
The Ordos Basin, situated in west-central China, is one of the oldest and most important fossil-fuel energy base, which contains large reserves of coal, oil and natural gas. The Upper Palaeozoic strata are widely distributed with rich gas-bearing and large natural gas resources, whose potential is tremendous. Recent years have witnessed a great tight gas exploration improvement of the Upper Paleozoic in Southeastern Ordos basin. The Carboniferous Benxi Formation, mainly buried more than 2,500m, is the key target strata for hydrocarbon exploration, which was deposited in a barrier island and tidal flat environment. The sandy bars and flats are the favorable sedimentary microfacies. With an integrated approach of thin-section petrophysics, constant velocity mercury injection test, scanning electron microscopy and X-ray diffractometry, diagenesis and porosity evolution of tight sand reservoirs of Benxi Formation were analyzed in detail. The result shows that the main lithology of sandstone in this area is dominated by moderately to well sorted quartz sandstone. The average porosity and permeability is 4.72% and 1.22mD. The reservoirs of Benxi Formation holds a variety of pore types and the pore throats, with obvious heterogeneity and poor connection. Based on the capillary pressure curve morphological characteristics and parameters, combined with thin section and phycical property data, the reservoir pore structure of Benxi Formation can be divided into 4 types, including mid pore mid throat type(I), mid pore fine throat type(II), small pore fine throat type(III) and micro pro micro throat type(Ⅳ). The reservoirs primarily fall in B-subsate of middle diagenesis and late diagenesis, which mainly undergo compaction, cmentation, dissolution and fracturing process. Employing the empirical formula of different sorting for unconsolideated sandstone porosity, the initial sandstone porosity is 38.32% on average. Quantitative evaluation of the increase and decrease of porosity caused by different diagenesis reveals that mechanical compaction and chemical cementation are the main mechanisms for destroying primary pores, which contribute 19.61% and 8.75% to the loss of primary posoity, respectively. Dissolution of volcanic fragments and feldspar increased reservoir porosity by 4.14%. The pores were occluded by late minerals and carbonate cements, resulting in a reduction of 9.38%. Overall, the dual influence of compaction and cementation is the key of the key, controlling formation of tight gas sandstone reservoirs. Keywords: diagenesis, porosity evolution, tight sandstone, Benxi Formation, Southeast Ordos Basin Acknowledgements: We greatfully acknowledge Yanchang Petroleum for providing the samples and data access and for permission to publish this work. The first author, Peng Hu, would like to thank the support from Prof. Xinghe Yu.
NASA Astrophysics Data System (ADS)
Li, Zhaoqi; Goldstein, Robert H.; Franseen, Evan K.
2017-03-01
A dolomitized Upper Miocene carbonate system in southeast Spain contains extensive upper and lower zones of calcite cementation that cut across the stratigraphy. Cement textures including isopachous and circumgranular, which are consistent with phreatic-zone cementation. Cements in the upper cemented zone are non-luminescent, whereas those in the lower cemented zone exhibit multiple bands of luminescent and non-luminescent cements. In the upper cemented zone, isotopic data show two meteoric calcite lines (MCL) with mean δ18O at - 5.1‰ and - 5.8‰ VPDB, whereas no clear MCL is defined in the lower cemented zone where mean δ18O for calcite cement is at - 6.7‰ VPDB. δ13C values in both cement zones are predominantly negative, ranging from - 10 to + 2‰ VPDB, suggestive of carbon from soil gas or decayed organics. Measurements of Tm ice in primary fluid inclusions yield a mode of 0.0 °C in both zones, indicating calcite cementation from fresh water. These two zones define the positions of two different paleo-water tables that formed during a relative sea-level fall and erosional downcutting during the Plio-Pleistocene. The upper cemented zone pre-dated the lower cemented zone on the basis of known relative sea-level history. Meteoric calcite cementation reduced porosity and permeability, but measured values are inconsistent with simple filling of open pore space. Each texture, boundstone, grainstone, packstone, wackestone, produces a different relationship between percent calcite cement and porosity/permeability. Distribution of cements may be predictable on the basis of known sea-level history, and the effect of the cementation can be incorporated into subsurface geomodels by defining surfaces of rock boundaries that separate cemented zones from uncemented zones, and applying texture-specific relationships among cementation, porosity and permeability.
GEOLOGIC ASPECTS OF TIGHT GAS RESERVOIRS IN THE ROCKY MOUNTAIN REGION.
Spencer, Charles W.
1985-01-01
The authors describe some geologic characteristics of tight gas reservoirs in the Rocky Mountain region. These reservoirs usually have an in-situ permeability to gas of 0. 1 md or less and can be classified into four general geologic and engineering categories: (1) marginal marine blanket, (2) lenticular, (3) chalk, and (4) marine blanket shallow. Microscopic study of pore/permeability relationships indicates the existence of two varieties of tight reservoirs. One variety is tight because of the fine grain size of the rock. The second variety is tight because the rock is relatively tightly cemented and the pores are poorly connected by small pore throats and capillaries.
Residence times of reef-island sediments constrained by post-mortem precipitates
NASA Astrophysics Data System (ADS)
Mann, Thomas; Wizemann, André; Kench, Paul; Jompa, Jamaluddin; Westphal, Hildegard
2017-04-01
The precipitation of carbonate cements is a rapid process in tropical marine environments. Distinct from calcification, the onset of cementation coincides with the termination of 14C uptake within carbonate-sediment forming organisms. Here we show that this relationship presents new opportunities for examining the temporal lag between organism death and deposition in carbonate systems - the prerequisite for reliable depositional chronologies. We dated skeletal constituents collected from discretely stratified reef-island deposits in Indonesia. In each of the strata, internally least cemented segments of the calcifying green alga Halimeda yield the youngest ages. Complementary mesocosm experiments on cementation rates reveal that post-mortem cement growth initiates within months after transport commences. Continuous pore-filling cementation promptly stabilizes the initially fragile Halimeda skeleton. Furthermore, abrasion experiments show that such cementation significantly increases the durability of segments during transport. Implications of these findings are profound in two respects; first, evaluating residence times of skeletal carbonate constituents based on abrasion features is far from being adequate. Second, the absence of cements within sedimentary Halimeda segments signals that post-mortem transport through the intertidal zone occurred quasi-instantaneously. Radiometric ages from such specimens should minimize the temporal lag between organism death and deposition thus making them reliable indicators of sedimentation in supratidal environments.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Yoon, Hongkyu; Major, Jonathan; Dewers, Thomas
Dissolved CO 2 in the subsurface resulting from geological CO 2 storage may react with minerals in fractured rocks, confined aquifers, or faults, resulting in mineral precipitation and dissolution. The overall rate of reaction can be affected by coupled processes including hydrodynamics, transport, and reactions at the (sub) pore-scale. In this work pore-scale modeling of coupled fluid flow, reactive transport, and heterogeneous reactions at the mineral surface is applied to account for permeability alterations caused by precipitation-induced pore-blocking. This paper is motivated by observations of CO 2 seeps from a natural CO 2 sequestration analog, Crystal Geyser, Utah. Observations alongmore » the surface exposure of the Little Grand Wash fault indicate the lateral migration of CO 2 seep sites (i.e., alteration zones) of 10–50 m width with spacing on the order of ~100 m over time. Sandstone permeability in alteration zones is reduced by 3–4 orders of magnitude by carbonate cementation compared to unaltered zones. One granular porous medium and one fracture network systems are used to conceptually represent permeable porous media and locations of conduits controlled by fault-segment intersections and/or topography, respectively. Simulation cases accounted for a range of reaction regimes characterized by the Damköhler (Da) and Peclet (Pe) numbers. Pore-scale simulation results demonstrate that combinations of transport (Pe), geochemical conditions (Da), solution chemistry, and pore and fracture configurations contributed to match key patterns observed in the field of how calcite precipitation alters flow paths by pore plugging. This comparison of simulation results with field observations reveals mechanistic explanations of the lateral migration and enhances our understanding of subsurface processes associated with the CO 2 injection. In addition, permeability and porosity relations are constructed from pore-scale simulations which account for a range of reaction regimes characterized by the Da and Pe numbers. Finally, the functional relationships obtained from pore-scale simulations can be used in a continuum scale model that may account for large-scale phenomena mimicking lateral migration of surface CO 2 seeps.« less
Peculiarities of binding composition production in vortex jet mill
NASA Astrophysics Data System (ADS)
Zagorodnyuk, L. Kh; Lesovik, V. S.; Sumskoy, D. A.; Elistratkin, M. Yu; Makhortov, D. S.
2018-03-01
The article investigates the disintegration of perlite production waste in a vortex jet mill; the regularities of milling were established. Binding compositions were obtained at different ratios of cement vs. perlite sand production waste in the vortex jet mill in various milling regimes. The peculiarities of milling processes were studied, and technological and physicomechanical properties of the binding compositions were determined as well. The microstructure of the cement stones made of activated Portland cement and binding compositions in the vortex jet mill was elucidated by electron microscopy. The open pores of the cement-binding compositions prepared using perlite fillers were found to be filled by newgrowths at different stages of collective growth. The microstructure of the binding compositions is dense due to rationally proportioned composition, effective mineral filler— perlite waste — that creates additional substrates for internal composite microstructure formation, mechanochemical activation of raw mixture, which allows obtaining composites with required properties.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Keener, T.C.; Khang, S.J.
1996-07-31
This research was focused on evaluating hydrated cement sorbents in the U. C. pilot spray dryer. The main goal of this work was to determine the hydration conditions resulting in reactive hydrated cement sorbents. Hydration of cement was achieved by stirring or by grinding in a ball mill at either room temperature or elevated temperatures. Also, the effects of several additives were studied. Additives investigated include calcium chloride, natural diatomite, calcined diatomaceous earth, and fumed silica. The performance of these sorbents was compared with conventional slaked lime. Further, the specific surface area and pore volume of the dried SDA sorbentsmore » were measured and compared to reactivity. Bench-scale tests were performed to obtain a more detailed picture of the development of the aforementioned physical properties as a function of hydration time.« less
Utilization of municipal sewage sludge as additives for the production of eco-cement.
Lin, Yiming; Zhou, Shaoqi; Li, Fuzhen; Lin, Yixiao
2012-04-30
The effects of using dried sewage sludge as additive on cement property in the process of clinker burning were investigated in this paper. The eco-cement samples were prepared by adding 0.50-15.0% of dried sewage sludge to unit raw meal, and then the mixtures were burned at 1450 °C for 2 h. The results indicated that the major components in the eco-cement clinkers were similar to those in ordinary Portland cement. Although the C(2)S phase formation increased with the increase of sewage sludge content, it was also found that the microstructure of the mixture containing 15.0% sewage sludge in raw meal was significantly different and that a larger amount of pores were distributed in the clinker. Moreover, all the eco-cement pastes had a longer initial setting time and final setting time than those of plain cement paste, which increased as the sewage sludge content in the raw meal increased. All the eco-cement pastes had lower early flexural strengths, which increased as the sewage sludge content increased, while the compressive strengths decreased slightly. However, this had no significant effect on all the strengths at later stages. Furthermore, the leaching concentrations of all the types of eco-cement clinkers met the standard of Chinese current regulatory thresholds. Copyright © 2012 Elsevier B.V. All rights reserved.
Evolution of Micro-Pores in a Single-Crystal Nickel-Based Superalloy During Solution Heat Treatment
NASA Astrophysics Data System (ADS)
Li, Xiangwei; Wang, Li; Dong, Jiasheng; Lou, Langhong; Zhang, Jian
2017-06-01
Evolution of micro-pores in a third-generation single-crystal nickel-based superalloy during solution heat treatment at 1603 K (1330 °C) was investigated by X-ray computed tomography. 3D information including morphology, size, number, and volume fraction of micro-pores formed during solidification (S-pores) and solution (H-pores) was analyzed. The growth behaviors of both S-pores and H-pores can be related to the vacancy formation and diffusion during heat treatment.
Ghosh, P; Mandal, S; Pal, S; Bandyopadhyaya, G; Chattopadhyay, B D
2006-04-01
In the biosphere, bacteria can function as geo-chemical agents, promoting the dispersion, fractionation and/or concentration of materials. Microbial mineral precipitation is resulted from metabolic activities of microorganisms. Based on this biomineralogy concept, an attempt has been made to develop bioconcrete material incorporating of an enrichment culture of thermophilic and anaerobic bacteria within cement-sand mortar/concrete. The results showed a significant increase in compressive strength of both cement-sand mortar and concrete due to the development of filler material within the pores of cement sand matrix. Maximum strength was observed at concentration 10(5)cell/ml of water used in mortar/concrete. Addition of Escherichia coil or media composition on mortar showed no such improvement in strength.
NASA Astrophysics Data System (ADS)
Omer, Muhamed F.; Omer, Dilshad; Zebari, Bahroz Gh.
2014-12-01
A combination of high resolution cathodoluminsecnce-spectroscopy (HRS-CL) with spatial electron microprobe analysis and optical microscopy is used to determine paragenesis and history of cementation in the limestones and dolostones of Khurmala Formation which is exposed in many parts of Northern Iraq. Khurmala Formation was subjected to different diagenetic processes such as micritization, compaction, dissolution, neomorphism, pyritization and cementation that occurred during marine to shallow burial stages and culminated during intermediate to deep burial later stages. Five dolomite textures are recognized and classified according to crystal size distribution and crystal-boundary shape. Dolomitization is closely associated with the development of secondary porosity that pre-and postdates dissolution and corrosion; meanwhile such porosity was not noticed in the associated limestones. Microprobe analysis revealed three types of cement, calcite, dolomite and ankerite which range in their luminescence from dull to bright. Cathodoluminescence study indicated four main texture generations. These are (1) unzoned microdolomite of planar and subhedral shape, with syntaxial rim cement of echinoderm that show dull to red luminescence, (2) equant calcite cements filling interparticle pores which shows dull luminescence and weak zonal growth, (3.1) homogenous intrinsic blue stoichiometric calcite with dull luminescence and without activators, (3.2) coarse blocky calcite cement with strong oscillatory zoning and bright orange luminescence which postdates other calcite cements, (4) ankerite cement with red to orange, non-luminescence growth zonation which is the last formed cement.
Effects of calcium leaching on diffusion properties of hardened and altered cement pastes
NASA Astrophysics Data System (ADS)
Kurumisawa, Kiyofumi; Haga, Kazuko; Hayashi, Daisuke; Owada, Hitoshi
2017-06-01
It is very important to predict alterations in the concrete used for fabricating disposal containers for radioactive waste. Therefore, it is necessary to understand the alteration of cementitious materials caused by calcium leaching when they are in contact with ground water in the long term. To evaluate the long-term transport characteristics of cementitious materials, the microstructural behavior of these materials should be considered. However, many predictive models of transport characteristics focus on the pore structure, while only few such models consider both, the spatial distribution of calcium silicate hydrate (C-S-H), portlandite, and the pore spaces. This study focused on the spatial distribution of these cement phases. The auto-correlation function of each phase of cementitious materials was calculated from two-dimensional backscattered electron imaging, and the three-dimensional spatial image of the cementitious material was produced using these auto-correlation functions. An attempt was made to estimate the diffusion coefficient of chloride from the three-dimensional spatial image. The estimated diffusion coefficient of the altered sample from the three-dimensional spatial image was found to be comparable to the measured value. This demonstrated that it is possible to predict the diffusion coefficient of the altered cement paste by using the proposed model.
Geochemical effects on the behavior of LLW radionuclides in soil/groundwater environments
DOE Office of Scientific and Technical Information (OSTI.GOV)
Krupka, K.M.; Sterne, R.J.
1995-12-31
Assessing the migration potential of radionuclides leached from low-level radioactive waste (LLW) and decommissioning sites necessitates information on the effects of sorption and precipitation on the concentrations of dissolved radionuclides. Such an assessment requires that the geochemical processes of aqueous speciation, complexation, oxidation/reduction, and ion exchange be taken into account. The Pacific Northwest National Laboratory (PNNL) is providing technical support to the U.S. Nuclear Regulatory Commission (NRC) for defining the solubility and sorption behavior of radionuclides in soil/ground-water environments associated with engineered cementitious LLW disposal systems and decommissioning sites. Geochemical modeling is being used to predict solubility limits for radionuclidesmore » under geochemical conditions associated with these environments. The solubility limits are being used as maximum concentration limits in performance assessment calculations describing the release of contaminants from waste sources. Available data were compiled regarding the sorption potential of radionuclides onto {open_quotes}fresh{close_quotes} cement/concrete where the expected pH of the cement pore waters will equal to or exceed 10. Based on information gleaned from the literature, a list of preferred minimum distribution coefficients (Kd`s) was developed for these radionuclides. The K{sub d} values are specific to the chemical environments associated with the evolution of the compositions of cement/concrete pore waters.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
McBride, E.F.
1988-02-01
White, elliptical, calcite-cemented concretion nuclei up to 1 m long contrast markedly in color, composition, and diagenetic history from more glauconite-rich concretion rinds and from dark-green glaucarenite host rocks. Concretion nuclei are loosely packed deposits of trilobite carapaces and minor quartz and glauconite that have intergranular volumes of 58%. The nuclei are shell-lag deposits that were cemented by calcite at the sea floor or after burial of a few meters. Concretion rinds, composed of subequal amounts of quartz and compactionally deformed glauconite, have an intergranular volume of only 32% and minor quartz overgrowths that preceded pore-occluding calcite cement. The rindsmore » underwent burial for several million years to tens of millions of years to depths of several hundred meters before they were cemented. The host rock is predominately glauconite with very minor quartz and calcite cement. Strontium isotopic ratios of host-rock calcite cement are variable (0.7084 to 0.7093), but the lowest value suggests precipitation during the Middle Ordovician. In the absence of significant amounts of carbonate cement, the host rock underwent complete dissolution of trilobite carapaces and maximum compaction with total loss of porosity through squashing of glauconite grains. Maximum burial during this stage was completed by the end of Ordovician time.« less
Effect of Nano-SiO2 on the Early Hydration of Alite-Sulphoaluminate Cement
Sun, Jinfeng; Xu, Zhiqiang; Li, Weifeng; Shen, Xiaodong
2017-01-01
The impact of nano-SiO2 on the early hydration properties of alite-sulphoaluminate (AC$A) cement was investigated with a fixed water to solid ratio (w/s) of one. Nano-SiO2 was used in partial substitution of AC$A cement at zero, one and three wt %. Calorimetry, X-ray diffraction (XRD), thermogravimetric/derivative thermogravimetric (TG/DTG), mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM) analyses were used to characterize the hydration and hydrates of the blended cement. The hydration of the AC$A cement was significantly promoted, resulting in an increase of the heat released with the addition of nano-SiO2. Phase development composition analysis showed that nano-SiO2 had no effect on the type of crystalline hydration products of the AC$A cement. Moreover, nano-SiO2 showed significant positive effects on pore refinement where the total porosity decreased by 54.09% at three days with the inclusion of 3% nano-SiO2. Finally, from the SEM observations, nano-SiO2 was conducive to producing a denser microstructure than that of the control sample. PMID:28467348
Rodriguez, Lucas C.; Chari, Jonathan; Aghyarian, Shant; Gindri, Izabelle M.; Kosmopoulos, Victor; Rodrigues, Danieli C.
2014-01-01
Powder-liquid poly (methyl methacrylate) (PMMA) bone cements are widely utilized for augmentation of bone fractures and fixation of orthopedic implants. These cements typically have an abundance of beneficial qualities, however their lack of bioactivity allows for continued development. To enhance osseointegration and bioactivity, calcium phosphate cements prepared with hydroxyapatite, brushite or tricalcium phosphates have been introduced with rather unsuccessful results due to increased cement viscosity, poor handling and reduced mechanical performance. This has limited the use of such cements in applications requiring delivery through small cannulas and in load bearing. The goal of this study is to design an alternative cement system that can better accommodate calcium-phosphate additives while preserving cement rheological properties and performance. In the present work, a number of brushite-filled two-solution bone cements were prepared and characterized by studying their complex viscosity-versus-test frequency, extrusion stress, clumping tendency during injection through a syringe, extent of fill of a machined void in cortical bone analog specimens, and compressive strength. The addition of brushite into the two-solution cement formulations investigated did not affect the pseudoplastic behavior and handling properties of the materials as demonstrated by rheological experiments. Extrusion stress was observed to vary with brushite concentration with values lower or in the range of control PMMA-based cements. The materials were observed to completely fill pre-formed voids in bone analog specimens. Cement compressive strength was observed to decrease with increasing concentration of fillers; however, the materials exhibited high enough strength for consideration in load bearing applications. The results indicated that partially substituting the PMMA phase of the two-solution cement with brushite at a 40% by mass concentration provided the best combination of the properties investigated. This alternative material may find applications in systems requiring highly injectable and viscous cements such as in the treatment of spinal fractures and bone defects. PMID:28788212
Leaching of Conductive Species: Implications to Measurements of Electrical Resistivity
Spragg, R; Jones, S; Bu, Y; Lu, Y; Bentz, D; Snyder, K; Weiss, J
2017-01-01
Electrical tests have been used to characterize the microstructure of porous materials, the measured electrical response being determined by the contribution of the microstructure (porosity and tortuosity) and the electrical properties of the solution (conductivity of the pore solution) inside the pores of the material. This study has shown how differences in concentration between the pore solution (i.e., the solution in the pores) and the storage solution surrounding the test specimen leads to significant transport (leaching) of the conductive ionic species between the pore solution and the storage solution. Leaching influences the resistivity of the pore solution, thereby influencing electrical measurements on the bulk material from either a surface or uniaxial bulk resistance test. This paper has three main conclusions: 1.) Leaching of conductive species does occur with concentration gradients and that a diffusion based approach can be used to estimate the time scale associated with this change. 2.) Leaching of ions in the pore solution can influence resistivity measurements, and the ratio of surface to uniaxial resistivity can be used as a method to assess the presence of leaching and 3.) An estimation of the magnitude of leaching for standardized tests of cementitious materials. PMID:28584407
Leaching of Conductive Species: Implications to Measurements of Electrical Resistivity.
Spragg, R; Jones, S; Bu, Y; Lu, Y; Bentz, D; Snyder, K; Weiss, J
2017-05-01
Electrical tests have been used to characterize the microstructure of porous materials, the measured electrical response being determined by the contribution of the microstructure (porosity and tortuosity) and the electrical properties of the solution (conductivity of the pore solution) inside the pores of the material. This study has shown how differences in concentration between the pore solution (i.e., the solution in the pores) and the storage solution surrounding the test specimen leads to significant transport (leaching) of the conductive ionic species between the pore solution and the storage solution. Leaching influences the resistivity of the pore solution, thereby influencing electrical measurements on the bulk material from either a surface or uniaxial bulk resistance test. This paper has three main conclusions: 1.) Leaching of conductive species does occur with concentration gradients and that a diffusion based approach can be used to estimate the time scale associated with this change. 2.) Leaching of ions in the pore solution can influence resistivity measurements, and the ratio of surface to uniaxial resistivity can be used as a method to assess the presence of leaching and 3.) An estimation of the magnitude of leaching for standardized tests of cementitious materials.
Physical barrier effect of geopolymeric waste form on diffusivity of cesium and strontium.
Jang, J G; Park, S M; Lee, H K
2016-11-15
The present study investigates the physical barrier effect of geopolymeric waste form on leaching behavior of cesium and strontium. Fly ash-based geopolymers and slag-blended geopolymers were used as solidification agents. The leaching behavior of cesium and strontium from geopolymers was evaluated in accordance with ANSI/ANS-16.1. The diffusivity of cesium and strontium in a fly ash-based geopolymer was lower than that in Portland cement by a factor of 10(3) and 10(4), respectively, showing significantly improved immobilization performance. The leaching resistance of fly ash-based geopolymer was relatively constant regardless of the type of fly ash. The diffusivity of water-soluble cesium and strontium ions were highly correlated with the critical pore diameter of the binder. The critical pore diameter of the fly ash-based geopolymer was remarkably smaller than those of Portland cement and slag-blended geopolymer; consequently, its ability physically to retard the diffusion of nuclides (physical barrier effect) was superior. Copyright © 2016 Elsevier B.V. All rights reserved.
Rossetti, V Alunno; Di Palma, L; Medici, F
2002-01-01
Results are presented of experiments performed to optimize the solidification/stabilization system for metallic elements in aqueous solution. This system involves mixing cement and a solution of metallic elements in a conventional mixer: the paste thus obtained is transferred drop by drop into a recipient filled with an aqueous solution of NaOH at 20% by weight, in which it solidifies immediately. The separate use of chloride solutions of Li+, Cr3+, Pb2+ and Zn2+ makes it possible to obtain granules displaying various levels of compressive strength. Three different inertization matrices were used in the experiments, the first consisting solely of Portland cement, the second of Portland cement and a superplasticizer additive, and the third of Portland cement partially replaced with silica-fume and superplasticizer. The results of the tests performed showed a very low level of leaching into the alkaline solidification solution for Cr3+, the quantity leached being under 2% as against higher levels for the other metallic elements. For all the considered elements, the best results were obtained by using silica-fume in the inertization matrix.
Shi, Hui-Sheng; Kan, Li-Li
2009-03-15
The study of cementitious activity of chromium residue (CR) was carried out to formulate the properties of chromium residue-cement matrices (CRCM) by blending CR with Ordinary Portland Cement (OPC). The particle size distribution, microstructures of CR were investigated by some apparatuses, and physical properties, leaching behavior of hexavalent chromium [Cr(VI)] of CRCM were also determined by some experiments. Three types of commonly used superplasticizers (sulphonated acetone formaldehyde superplasticizer (J1), polycarboxylate-based superplasticizer (J2) and naphthalene superplasticizer (J3)) were chosen to investigate their influences on the physical properties and the Cr(VI)-immobilisation in the leachate of the CRCM hardened pastes. The results show that the CR has a certain cementitious activity. The incorporation of CR improves the pore size distribution of CRCM. The Cr(VI) concentrations in the leachate of CRCM significantly decrease by incorporation of J2. Among three superplasticizers, J2 achieves lowest Cr(VI) leaching ratio. Based on this study, it is likely to develop CR as a potential new additive used in cement-based materials.
DOE Office of Scientific and Technical Information (OSTI.GOV)
King, D.E.; Meyers, W.J.
1985-02-01
The Lower Carboniferous Waulsortian Limestones, eastern Midlands, Republic of Ireland, contain 7 distinct luminescent zones in clear calcite cements that overlie inclusion-rich, marine cements in cavities and also fill fractures and aragonite-skeleton molds. The luminescent sequence, which records precipitation from increasingly reducing pore waters, is regionally and stratigraphically consistent over an interval more than 1200 ft thick. Zone 1 cements are nonluminescent; zone 2 cements are brightly luminescent; and zones 3-7 cements are ferroan with a moderate to dull luminescence. Zone 1 cements (mean -2.6% delta/sup 18/O/ +3.3% delta/sup 13/C PDB) are slightly depleted in oxygen relative to radiaxial-fibrous cementsmore » (mean -1.8% delta/sup 18/O/ +3.5% delta/sup 13/C PDB) which have a composition that reflects Lower Carboniferous seawater. Zone 4 cements (mean -4.1% delta/sup 18/O/ +3.1% delta/sup 13/C PDB) are depleted in oxygen relative to zone 1, whereas zone 5 cements (mean -11.8% delta/sup 18/O/ +1.1 delta/sup 13/C PDB) are extremely depleted in oxygen and somewhat in carbon. Locally intense dolomitization includes 2 regionally extensive generations of ferroan saddle dolomite. Petrographic relationships demonstrate these dolomite generations were replaced by zone 5 cement. Sulfide mineralization, principally pyrite and sphalerite, occurred after the precipitation of zone 5 cement. Much of diagenesis occurred during a brief period in the Lower Carboniferous. Zones 1-6 and saddle dolomites are contained in Chadian (upper Osagean), shallow-marine facies overlying the Waulsortian. Fractures filled by zone 5 cements are truncated at the margins of Waulsortian clasts contained in a conglomerate overlying an early Arundian (early Meramecian) unconformity.« less
Dissociation of sarin on a cement analogue surface: Effects of humidity and confined geometry
O’Brien, Christopher J.; Greathouse, Jeffery A.; Tenney, Craig M.
2016-11-22
Here, first-principles molecular dynamics simulations were used to investigate the dissociation of sarin (GB) on the calcium silicate hydrate (CSH) mineral tobermorite (TBM), a surrogate for cement. CSH minerals (including TBM) and amorphous materials of similar composition are the major components of Portland cement, the binding agent of concrete. Metadynamics simulations were used to investigate the effect of the TBM surface and confinement in a microscale pore on the mechanism and free energy of dissociation of GB. Our results indicate that both the adsorption site and the humidity of the local environment significantly affect the sarin dissociation energy. In particular,more » sarin dissociation in a low-water environment occurs via a dealkylation mechanism, which is consistent with previous experimental studies.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kanna, V.; Olson, R.A.; Jennings, H.M.
The effects of drying on mortars containing Portland cement blended with fly ash or slag on the shrinkage, extent of surface cracking, pore size distribution as measured by mercury intrusion porosimetry, flexural strength, fracture toughness, and Young`s modulus are reported. Specimens were exposed to conditions of 100% relative humidity (RH), 50% RH, and/or oven-drying at 105 C. Drying coarsened the pore structure and increased the density of surface cracks, but surprisingly increased the flexural strength and the fracture toughness, and as anticipated lowered the Young`s modulus. This was regardless of the content of mineral admixture.
A Model of Thermal Conductivity for Planetary Soils. 2; Theory for Cemented Soils
NASA Technical Reports Server (NTRS)
Piqueux, S.; Christensen, P. R.
2009-01-01
A numerical model of heat conduction through particulate media made of spherical grains cemented by various bonding agents is presented. The pore-filling gas conductivity, volume fraction, and thermal conductivity of the cementing phase are tunable parameters. Cement fractions <0.001-0.01% in volume have small effects on the soil bulk thermal conductivity. A significant conductivity increase (factor 3-8) is observed for bond fractions of 0.01 to 1% in volume. In the 1 to 15% bond fraction domain, the conductivity increases continuously but less intensely (25-100% conductivity increase compared to a 1% bond system). Beyond 15% of cements, the conductivity increases vigorously and the bulk conductivity rapidly approaches that of bedrock. The composition of the cements (i.e. conductivity) has little influence on the bulk thermal inertia of the soil, especially if the volume of bond <10%. These results indicate that temperature measurements are sufficient to detect cemented soils and quantify the amount of cementing phase, but the mineralogical nature of the bonds and the typical grain size are unlikely to be determined from orbit. On Mars, a widespread surface unit characterized by a medium albedo (0.19-0.26) and medium/high thermal inertia (200-600 J s(0.5)/sq m/K) has long been hypothesized to be associated with a duricrust. The fraction of cement required to fit the thermal data is less than approx.1-5% by volume. This small amount of material is consistent with orbital observations, confirming that soil cementation is an important factor controlling the thermal inertia of the Martian surface
A model of thermal conductivity for planetary soils: 2. Theory for cemented soils
NASA Astrophysics Data System (ADS)
Piqueux, S.; Christensen, P. R.
2009-09-01
A numerical model of heat conduction through particulate media made of spherical grains cemented by various bonding agents is presented. The pore-filling gas conductivity, volume fraction, and thermal conductivity of the cementing phase are tunable parameters. Cement fractions <0.001-0.01% in volume have small effects on the soil bulk thermal conductivity. A significant conductivity increase (factor 3-8) is observed for bond fractions of 0.01 to 1% in volume. In the 1 to 15% bond fraction domain, the conductivity increases continuously but less intensely (25-100% conductivity increase compared to a 1% bond system). Beyond 15% of cements, the conductivity increases vigorously and the bulk conductivity rapidly approaches that of bedrock. The composition of the cements (i.e. conductivity) has little influence on the bulk thermal inertia of the soil, especially if the volume of bond <10%. These results indicate that temperature measurements are sufficient to detect cemented soils and quantify the amount of cementing phase, but the mineralogical nature of the bonds and the typical grain size are unlikely to be determined from orbit. On Mars, a widespread surface unit characterized by a medium albedo (0.19-0.26) and medium/high thermal inertia (200-600 J s-0.5 m-2 K-1) has long been hypothesized to be associated with a duricrust. The fraction of cement required to fit the thermal data is less than ˜1-5% by volume. This small amount of material is consistent with orbital observations, confirming that soil cementation is an important factor controlling the thermal inertia of the Martian surface.
Intercomparison of 3D pore-scale flow and solute transport simulation methods
DOE Office of Scientific and Technical Information (OSTI.GOV)
Yang, Xiaofan; Mehmani, Yashar; Perkins, William A.
2016-09-01
Multiple numerical approaches have been developed to simulate porous media fluid flow and solute transport at the pore scale. These include methods that 1) explicitly model the three-dimensional geometry of pore spaces and 2) those that conceptualize the pore space as a topologically consistent set of stylized pore bodies and pore throats. In previous work we validated a model of class 1, based on direct numerical simulation using computational fluid dynamics (CFD) codes, against magnetic resonance velocimetry (MRV) measurements of pore-scale velocities. Here we expand that validation to include additional models of class 1 based on the immersed-boundary method (IMB),more » lattice Boltzmann method (LBM), smoothed particle hydrodynamics (SPH), as well as a model of class 2 (a pore-network model or PNM). The PNM approach used in the current study was recently improved and demonstrated to accurately simulate solute transport in a two-dimensional experiment. While the PNM approach is computationally much less demanding than direct numerical simulation methods, the effect of conceptualizing complex three-dimensional pore geometries on solute transport in the manner of PNMs has not been fully determined. We apply all four approaches (CFD, LBM, SPH and PNM) to simulate pore-scale velocity distributions and nonreactive solute transport, and intercompare the model results with previously reported experimental observations. Experimental observations are limited to measured pore-scale velocities, so solute transport comparisons are made only among the various models. Comparisons are drawn both in terms of macroscopic variables (e.g., permeability, solute breakthrough curves) and microscopic variables (e.g., local velocities and concentrations).« less
Development of fluorapatite cement for dental enamel defects repair.
Wei, Jie; Wang, Jiecheng; Shan, Wenpeng; Liu, Xiaochen; Ma, Jian; Liu, Changsheng; Fang, Jing; Wei, Shicheng
2011-06-01
In order to restore the badly carious lesion of human dental enamel, a crystalline paste of fluoride substituted apatite cement was synthesized by using the mixture of tetracalcium phosphate (TTCP), dicalcium phosphate anhydrous (DCPA) and ammonium fluoride. The apatite cement paste could be directly filled into the enamel defects (cavities) to repair damaged dental enamel. The results indicated that the hardened cement was fluorapatite [Ca(10)(PO(4))(6)F(2), FA] with calcium to phosphorus atom molar ratio (Ca/P) of 1.67 and Ca/F ratio of 5. The solubility of FA cement in Tris-HCl solution (pH = 5) was slightly lower than the natural enamel, indicating the FA cement was much insensitive to the weakly acidic solutions. The FA cement was tightly combined with the enamel surface, and there was no obvious difference of the hardness between the FA cement and natural enamel. The extracts of FA cement caused no cytotoxicity on L929 cells, which satisfied the relevant criterion on dental biomaterials, revealing good cytocompatibility. In addition, the results showed that the FA cement had good mechanical strength, hydrophilicity, and anti-bacterial adhesion properties. The study suggested that using FA cement was simple and promising approach to effectively and conveniently restore enamel defects.
Removal of copper powder from aqueous solution by cementation using an agitated vessel.
Amin, N K; El-Ashtouky, E-S Z; Abdelwahab, O
2014-01-01
The present study is concerned with the removal of copper powder from aqueous solution by cementation on a stationary disc placed inside an agitated vessel. The influence of several parameters on the rate of cementation, such as initial copper sulphate concentration, impeller rotational speed, presence of surfactant (Triton X-100), distance between the disc and the impeller, type of blade turbine and presence of baffles, has been investigated. The rate of cementation was found to increase with increasing impeller rotational speed and initial copper sulphate concentration. On the other hand, the rate decreases with increasing distance between the disc and the impeller. The rate of cementation was inhibited in solutions containing Triton X-100. Performance of a four-blade 90 degree turbine with regard to the rate of copper cementation was superior to the performance of a four-blade 45 degree pitched turbine. The present data can be correlated in terms of mass transfer coefficient of cementation as Sh = 0.905 Sc0.33 Re0.89 (d/l)0.41 (four-blade 90 degree turbine); Sh = 0.815 Sc0.33Re0.79 (d/l)0.47 (four-blade 45 degree pitched turbine), for the conditions 2035 < Sc < 2810 and 35,000 < Re < 179,000.
Jaekel, David J; Day, Judd S; Klein, Gregg R; Levine, Harlan; Parvizi, Javad; Kurtz, Steven M
2012-09-01
Implantation of an antibiotic bone cement spacer is used to treat infection of a TKA. Dynamic spacers fashioned with cement-on-cement articulating surfaces potentially facilitate patient mobility and reduce bone loss as compared with their static counterparts, while consisting of a biomaterial not traditionally used for load-bearing articulations. However, their direct impact on patient mobility and wear damage while implanted remains poorly understood. We characterized patient activity, surface damage, and porous structure of dynamic cement-on-cement spacers. We collected 22 dynamic and 14 static knee antibiotic cement spacers at revision surgeries at times ranging from 0.5 to 13 months from implantation. For these patients, we obtained demographic data and UCLA activity levels. We characterized surface damage using the Hood damage scoring method and used micro-CT analysis to observe the internal structure, cracking, and porosity of the cement. The average UCLA score was higher for patients with dynamic spacers than for patients with static spacers, with no differences in BMI or age. Burnishing was the only prevalent damage mode on all the bearing surfaces. Micro-CT analysis revealed the internal structure of the spacers was porous and highly inhomogeneous, including heterogeneous dispersion of radiopaque material and cavity defects. The average porosity was 8% (range, 1%-29%) and more than ½ of the spacers had pores greater than 1 mm in diameter. Our observations suggest dynamic, cement-on-cement spacers allow for increased patient activity without catastrophic failure. Despite the antibiotic loading and internal structural inhomogeneity, burnishing was the only prevalent damage mode that could be consistently classified with no evidence of fracture or delamination. The porous structure of the spacers varied highly across the surfaces without influencing the material failure.
Nanoindentation of dry and fluid-saturated micro-porous rocks
NASA Astrophysics Data System (ADS)
Mighani, S.; Bernabe, Y.; Schwartzman, A. F.; Evans, J. B.
2017-12-01
In this report we explore the ability of nanoindentation technique to evaluate the pore-scale solid-fluid interactions in micro-porous rocks. We measure the creep deformation of a porous rock sample over a period of 3 minutes under a constant maximum force. The indentation tip is instrumented with a nano-DMA transducer which efficiently compensates for the thermal drifts. The candidate rock is a carbonate with micro-porous micritic cement. Secondary Electron (SE) images revealed a bimodal pore structure for this rock-type: regions (A) of micritic cement with micropores, and (B) with large grains and vuggy pores. The experiments were performed on dry rock samples as well as saturated with water (1 cp and buffered with 30 ppm calcite powder) and silicone oil (100 cp). Thus, the fluids presented a wide variation in viscosity and chemical reactivity. We then explored the size (maximum forces of 2, 4, and 8 mN) and loading rate (0.2-2 mN/sec) dependency of the observed creep behavior. The amount of total deformation within the 3 minutes of creep showed a uniform increase with a tendency to reach an equilibrium depth with creep rates (dh/h) below 5×10-3. The indentations in the water-saturated carbonate showed a 6-fold decrease in the Young's modulus (from 38 to 6 GPa) and 2-fold increase in creep magnitude (from 59 to 119 nm) compared with the dry indentations. We attribute these large differences to the possible chemical reaction of water and carbonate. This is further confirmed by comparing the hardness values, which showed that water softened the rock matrix by a factor of 4 (from 0.87 to 0.22 GPa). The carbonate sample saturated with oil, on the other hand, showed a higher modulus (47 GPa) and greater hardness (1.39 GPa), while the creep magnitude (31 nm) was half that observed in dry rock. We attribute this behavior to the viscous displacement of the pore fluid during consolidation of the poroelastic matrix. The loading rate-dependency and size (maximum load) sensitivity of the observed creep appear consistent with poroelasticity. We used Agbezuge and Deresiewicz's (1974) solution to derive poroelastic constants based on the recorded amount of creep. The analysis yields estimates of the diffusivity constant of the rock and the equilibrium creep depth. (We would like to acknowledge The U.S. Department of Energy (DOE) for their support)
Revankar, Vanita D; Prathap, M S; Shetty, K Harish Kumar; Shahul, Azmin; Sahana, K
2017-11-01
Biomineralization is a process which leads to the formation of an interfacial layer with tag-like structures at the cement-dentin interface. It is due to interaction of mineral trioxide aggregate (MTA) and Portland cement with dentin in phosphate-buffered solution (PBS). This study is aimed to evaluate the effect of influence of biomineralization process on push-out bond strength of ProRoot MTA (Dentsply Tulsa Dental, Tulsa, OK, USA), MTA Branco (Angelus Soluc¸o˜es Odontolo´gicas, Londrina, PR, Brazil) and calcium phosphate cement (BioGraft CPC). The aim of this study was to evaluate the effect of biomineralization process on the push-out strength of ProRoot MTA, MTA Branco, and CPC after mixing with 0.2% chlorhexidine gluconate solution (0.2% CHX) and 2% lidocaine solution (2% LA) on the bond strength of MTA-dentin. Dentin discs with uniform cavities were restored with ProRoot MTA, MTA Branco, and calcium phosphate cement after mixing with 0.2% CHX solution and 2% lidocaine solution. The samples were uniformly distributed into two groups. Experimental group being immersed in PBS solution and control group being immersed in saline for 2 months. Instron testing machine (Model 4444; Instron Corp., Canton, MA, USA) was used to determine the bond strength. A two-way analysis of variance and post hoc analysis by Bonferroni test. All samples immersed in experimental group displayed a significantly greater resistance to displacement than that observed for the samples in control group ( P < 0.05). MTAs displayed a significantly greater resistance to displacement than calcium phosphate cements. The main conclusion of this study was that the push-out bond strength of the cements, mainly the MTA groups, was positively influenced by the biomineralization process.
Reinforced Portland cement porous scaffolds for load-bearing bone tissue engineering applications.
Higuita-Castro, Natalia; Gallego-Perez, Daniel; Pelaez-Vargas, Alejandro; García Quiroz, Felipe; Posada, Olga M; López, Luis E; Sarassa, Carlos A; Agudelo-Florez, Piedad; Monteiro, Fernando J; Litsky, Alan S; Hansford, Derek J
2012-02-01
Modified Portland cement porous scaffolds with suitable characteristics for load-bearing bone tissue engineering applications were manufactured by combining the particulate leaching and foaming methods. Non-crosslinked polydimethylsiloxane was evaluated as a potential reinforcing material. The scaffolds presented average porosities between 70 and 80% with mean pore sizes ranging from 300 μm up to 5.0 mm. Non-reinforced scaffolds presented compressive strengths and elastic modulus values of 2.6 and 245 MPa, respectively, whereas reinforced scaffolds exhibited 4.2 and 443 MPa, respectively, an increase of ∼62 and 80%. Portland cement scaffolds supported human osteoblast-like cell adhesion, spreading, and propagation (t = 1-28 days). Cell metabolism and alkaline phosphatase activity were found to be enhanced at longer culture intervals (t ≥ 14 days). These results suggest the possibility of obtaining strong and biocompatible scaffolds for bone repair applications from inexpensive, yet technologically advanced materials such as Portland cement. Copyright © 2011 Wiley Periodicals, Inc.
The Role of Natural Hydrate on the Strength of Sands: Load-bearing or Cementing?
NASA Astrophysics Data System (ADS)
Priest, J. A.; Hayley, J. L.
2017-12-01
The strength of hydrate bearing sands is a key parameter for simulating the long-term performance of hydrate reservoirs during gas production and assessing reservoir and wellbore stability. Historically this parameter has been determined from testing synthesized hydrate sand samples, which has led to significant differences in measured strength that appears to reflect different formation methods adopted. At present, formation methods can be grouped into either those that form hydrate at grain contacts leading to a high strength `cemented' sand, or those where the hydrate forms a `load-bearing' structure in which the hydrate grains reside in the pore space resulting in more subtle changes in strength. Recovered natural hydrate-bearing cores typically exhibit this `load-bearing' behavior, although these cores have generally undergone significant changes in temperature and pressure during recovery, which may have altered the structure of the hydrate and sediment. Recent drilling expeditions using pressure coring, such as NGHP2 offshore India, have enabled intact hydrate bearing sediments to be recovered that have maintained hydrostatic stresses minimizing any changes in the hydrate structure within the core. Triaxial testing on these samples highlight enhanced strength even at zero effective stresses. This suggests that the hydrate forms a connected framework within the pore space apparently `cementing' the sand grains in place: we differentiate here between true cementation where hydrate is sintered onto the sand grains and typical observed behavior for cemented sands (cohesion, peak strength, post-peak strain softening). This inter-connected hydrate, and its ability to increase strength of the sands, appears to occur even at hydrate saturations as low as 30%, where typical `load-bearing' hydrates just start to increase strength. The results from pressure cores suggest that hydrate formation techniques that lead to `load-bearing' behavior may not capture the true interaction between the hydrate and sand and thus further research is needed to form synthesized hydrate bearing samples that more realistically mimic the observed strength behavior of natural hydrate bearing cores.
Effect of confinement in nano-porous materials on the solubility of a supercritical gas
NASA Astrophysics Data System (ADS)
Hu, Yaofeng; Huang, Liangliang; Zhao, Shuangliang; Liu, Honglai; Gubbins, Keith E.
2016-11-01
By combining Gibbs Ensemble Monte Carlo simulations and density functional theory, we investigate the influence of confinement in a slit-shaped carbon pore on the solubility of a supercritical solute gas in a liquid solvent. In the cases studied here, competing adsorption of the solvent and solute determines whether the solubility is enhanced or suppressed for larger pores. We find that the solubility in the confined system is strongly dependent on pore width, and that molecular packing effects are important for small pore widths. In addition, the solubility decreases on increase in the temperature, as for the bulk mixture, but the rate of decrease is greater in the pore due to a decrease in the partial molar enthalpy of the solute in the pore; this effect becomes greater as pore width is decreased. The solubility is increased on increasing the bulk pressure of the gas in equilibrium with the pore, and obeys Henry's law at lower pressures. However, the Henry constant differs significantly from that for the bulk mixture, and the range of pressure over which Henry's law applies is reduced relative to that for the bulk mixture. The latter observation indicates that solute-solute interactions become more important in the pore than for the bulk at a given bulk pressure. Finally, we note that different authors use different definitions of the solubility in pores, leading to some confusion over the reported phenomenon of 'oversolubility'. We recommend that solubility be defined as the overall mole fraction of solute in the pores, since it takes into account the increase in density of the solvent in the pores, and avoids ambiguity in the definition of the pore volume.
The interaction of zinc oxide-based dental cements with aqueous solutions of potassium fluoride.
Pawluk, K; Booth, S E; Coleman, N J; Nicholson, J W
2008-09-01
The ability of zinc oxide-based dental cements (zinc phosphate and zinc polycarboxylate) to take up fluoride from aqueous solution has been studied. Only zinc phosphate cement was found to take up any measurable fluoride after 5 h exposure to the solutions. The zinc oxide filler of the zinc phosphate also failed to take up fluoride from solution. The key interaction for this uptake was thus shown to involve the phosphate groups of the set cement. However, whether this took the form of phosphate/fluoride exchange, or the formation of oxyfluoro-phosphate groups was not clear. Fluoride uptake followed radicaltime kinetics for about 2 h in some cases, but was generally better modelled by the Elovich equation, dq(t)/dt = alpha exp(-betaq(t)). Values for alpha varied from 3.80 to 2.48 x 10(4), and for beta from 7.19 x 10(-3) to 0.1946, though only beta showed any sort of trend, becoming smaller with increasing fluoride concentration. Fluoride was released from the zinc phosphate cements in processes that were diffusion based up to M(t)/M(infinity) of about 0.4. No further release occurred when specimens were placed in fresh volumes of deionised water. Only a fraction of the fluoride taken up was re-released, demonstrating that most of the fluoride taken up becomes irreversibly bound within the cement.
Zhou, Huan; Agarwal, Anand K; Goel, Vijay K; Bhaduri, Sarit B
2013-10-01
There are two interesting features of this paper. First, we report herein a novel microwave assisted technique to prepare phosphate based orthopedic cements, which do not generate any exothermicity during setting. The exothermic reactions during the setting of phosphate cements can cause tissue damage during the administration of injectable compositions and hence a solution to the problem is sought via microwave processing. This solution through microwave exposure is based on a phenomenon that microwave irradiation can remove all water molecules from the alkaline earth phosphate cement paste to temporarily stop the setting reaction while preserving the active precursor phase in the formulation. The setting reaction can be initiated a second time by adding aqueous medium, but without any exothermicity. Second, a special emphasis is placed on using this technique to synthesize magnesium phosphate cements for orthopedic applications with their enhanced mechanical properties and possible uses as drug and protein delivery vehicles. The as-synthesized cements were evaluated for the occurrences of exothermic reactions, setting times, presence of Mg-phosphate phases, compressive strength levels, microstructural features before and after soaking in (simulated body fluid) SBF, and in vitro cytocompatibility responses. The major results show that exposure to microwaves solves the exothermicity problem, while simultaneously improving the mechanical performance of hardened cements and reducing the setting times. As expected, the cements are also found to be cytocompatible. Finally, it is observed that this process can be applied to calcium phosphate cements system (CPCs) as well. Based on the results, this microwave exposure provides a novel technique for the processing of injectable phosphate bone cement compositions. © 2013.
30 CFR 250.427 - What are the requirements for pressure integrity tests?
Code of Federal Regulations, 2010 CFR
2010-07-01
... related hole-behavior observations, such as pore-pressure test results, gas-cut drilling fluid, and well... integrity tests? 250.427 Section 250.427 Mineral Resources MINERALS MANAGEMENT SERVICE, DEPARTMENT OF THE... Operations Casing and Cementing Requirements § 250.427 What are the requirements for pressure integrity tests...
Measurement of variation in soil solute tracer concentration across a range of effective pore sizes
Harvey, Judson W.
1993-01-01
Solute transport concepts in soil are based on speculation that solutes are distributed nonuniformly within large and small pores. Solute concentrations have not previously been measured across a range of pore sizes and examined in relation to soil hydrological properties. For this study, modified pressure cells were used to measure variation in concentration of a solute tracer across a range of pore sizes. Intact cores were removed from the site of a field tracer experiment, and soil water was eluted from 10 or more discrete classes of pore size. Simultaneous changes in water content and unsaturated hydraulic conductivity were determined on cores using standard pressure cell techniques. Bromide tracer concentration varied by as much as 100% across the range of pore sizes sampled. Immediately following application of the bromide tracer on field plots, bromide was most concentrated in the largest pores; concentrations were lower in pores of progressively smaller sizes. After 27 days, bromide was most dilute in the largest pores and concentrations were higher in the smaller pores. A sharp, threefold decrease in specific water capacity during elution indicated separation of two major pore size classes at a pressure of 47 cm H2O and a corresponding effective pore diameter of 70 μm. Variation in tracer concentration, on the other hand, was spread across the entire range of pore sizes investigated in this study. A two-porosity characterization of the transport domain, based on water retention criteria, only broadly characterized the pattern of variation in tracer concentration across pore size classes during transport through a macroporous soil.
Santana, Fernanda Ribeiro; Soares, Carlos José; Silva, Júlio Almeida; Alencar, Ana Helena Gonçalves; Renovato, Sara Rodrigues; Lopes, Lawrence Gonzaga; Estrela, Carlos
2015-07-01
To evaluate the effect of instrumentation techniques, irrigant solutions and specimen aging on fiberglass posts bond strength to intraradicular dentine. A total of 120 bovine teeth were prepared and randomized into control and experimental groups resulting from three study factors (instrumentation techniques, irrigant solutions, specimen aging). Posts were cemented with RelyX U100. Samples were submitted to push-out test and failure mode was evaluated under a confocal microscope. In specimens submitted to water artificial aging, nickel-titanium rotary instruments group presented higher bond strength values in apical third irrigated with NaOCl or chlorhexi-dine. Irrigation with NaOCl resulted in higher bond strength than ozonated water. Artificial aging resulted in significant bond strength increase. Adhesive cement-dentin failure was prevalent in all the groups. Root canal preparation with NiTi instruments associated with NaOCl irrigation and ethylenediaminetetra acetic acid (EDTA) increased bond strength of fiberglass posts cemented with self-adhesive resin cement to intraradicular dentine. Water artificial aging significantly increased post-Clinical significance: The understanding of factors that may influence the optimal bond between post-cement and cement-dentin are essential to the success of endodontically treated tooth restoration.
Shear bond strength between resin cement and colored zirconia made with metal chlorides.
Kim, Ga-Hyun; Park, Sang-Won; Lee, Kwangmin; Oh, Gye-Jeong; Lim, Hyun-Pil
2015-06-01
Although the application of zirconia in esthetic prostheses has increased, the shear bond strength (SBS) between colored zirconia and resin cement has not been investigated. The purpose of this study was to compare the SBS between resin cement and colored zirconia made with metal chlorides. Sixty-four zirconia specimens were divided into 2 groups: one in which the specimens were bonded with resin cement, including 4-META (4-methacryloxyethyl trimellitic anhydride), and one in which the specimens were bonded with resin cement (SEcure, Sun Medical) after being processed with zirconia primer (Zirconia Liner), including 4-META. Each group was then divided into 4 subgroups depending on the coloring liquid. The subgroups were noncolored (control), commercial coloring liquid VITA In-Ceram 2000 YZ LL1, aqueous chromium chloride solution 0.1 wt%, and aqueous molybdenum chloride solution 0.1 wt%. Composite resin cylinders (Filtek Z250, 3M ESPE) were fabricated and bonded to the surface of the zirconia specimen with resin cement (SEcure). All specimens were stored in 37°C distilled water for 24 hours, and the SBS was measured with a universal testing machine. All data were analyzed statistically with 2-way ANOVA and tested post hoc with the Tukey test (α=.05). Significant differences were observed among the SBS values of the colored zirconia depending on the coloring liquid (P<.001) and whether they were processed with zirconia primer (P<.001). The SBS between colored zirconia and resin cement was significantly higher than that of noncolored zirconia and resin cement in groups processed with zirconia primer (P<.05). Colored zirconia immersed in aqueous molybdenum chloride solution showed a significantly higher SBS. Coloring liquid enhanced the SBS between resin cement and zirconia processed with zirconia primer. In particular, colored zirconia immersed in aqueous molybdenum chloride solution showed the highest SBS. Copyright © 2015 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Cil, Mehmet B.; Xie, Minwei; Packman, Aaron I.
Synchrotron X-ray microtomography was used to track the spatiotemporal evolution of mineral precipitation and the consequent alteration of the pore structure. Column experiments were conducted by injecting CaCl2 and NaHCO3 solutions into granular porous media either as a premixed supersaturated solution (external mixing) or as separate solutions that mixed within the specimen (internal mixing). The two mixing modes produced distinct mineral growth patterns. While internal mixing promoted transverse heterogeneity with precipitation at the mixing zone, external mixing favored relatively homogeneous precipitation along the flow direction. The impact of precipitation on pore water flow and permeability was assessed via 3-D flowmore » simulations, which indicated anisotropic permeability evolution for both mixing modes. Under both mixing modes, precipitation decreased the median pore size and increased the skewness of the pore size distribution. Such similar pore-scale evolution patterns suggest that the clogging of individual pores depends primarily on local supersaturation state and pore geometry.« less
NASA Astrophysics Data System (ADS)
Léonide, Philippe; Fournier, François; Reijmer, John J. G.; Vonhof, Hubert; Borgomano, Jean; Dijk, Jurrien; Rosenthal, Maelle; van Goethem, Manon; Cochard, Jean; Meulenaars, Karlien
2014-06-01
The Urgonian limestones of Late Barremian/Early Aptian from Provence (SE, France) are characterized by the occurrence of microporous limestones at regional scale alternating with tight carbonates. This study, based on petrographical (sediment texture, facies) and diagenetical analyses (cement stratigraphy, porosity and isotope geochemistry) of more than 800 limestone samples provides insight into the parameters controlling the genesis, preservation or occlusion of microporosity along an inner platform to outer shelf transect. The tight and microporous Urgonian limestones from Provence can be grouped into 5 rock-types based on textures, associated depositional environments, porosity and pore-type, being: (1) tight inner-platform: TIP; (2) porous inner platform: PIP; (3) tight outer platform: TOP; (4) porous outer platform: POP and (5) tight outer shelf: TOS. In tight (TIP, TOP and TOS types) limestones intergranular and intragranular pore spaces were entirely occluded by early marine and/or early meteoric cementation, whereas in microporous (PIP, POP) limestones a significant fraction of the intergranular macroporosity was preserved during early and shallow burial diagenesis. Micrite neomorphism (hybrid Ostwald ripening process) occurred during meteoric shallow burial diagenesis in PIP and POP limestones during the regional Durancian Uplift event (Albian-Lower Cenomanian). This process resulted in microporosity enhancement and preservation. Circulation of meteoric fluids during exhumation produces intercrystalline microporosity enhancement and moldic porosity development. The present study documents the important role that both early diagenetic and depositional cycles and long-term tectonic processes have on pore space evolution and distribution in Mesozoic platform carbonates.
Lv, Shenghua; Hu, Haoyan; Zhang, Jia; Luo, Xiaoqian; Lei, Ying; Sun, Li
2017-12-18
Original graphene oxide (GO) nanosheets were prepared using the Hummers method and found to easily aggregate in aqueous and cement composites. Using carboxymethyl chitosan (CCS) as a dispersant, few-layered GO nanosheets (1-2 layers) were obtained by forming CCS/GO intercalation composites. The testing results indicated that the few-layered GO nanosheets could uniformly spread, both in aqueous and cement composites. The cement composites were prepared with GO dosages of 0.03%, 0.05% and 0.07% and we found that they had a compact microstructure in the whole volume. A special feature was determined, namely that the microstructures consisted of regular-shaped crystals created by self-crosslinking. The X-ray diffraction (XRD) results indicated that there was a higher number of cement hydration crystals in GO/cement composites. Meanwhile, we also found that partially-amorphous Calcium-Silicate-Hydrate (C-S-H) gel turned into monoclinic crystals. At 28 days, the GO/cement composites reached the maximum compressive and flexural strengths at a 0.05% dosage. These strengths were 176.64 and 31.67 MPa and, compared with control samples, their increased ratios were 64.87% and 149.73%, respectively. Durability parameters, such as penetration, freeze-thaw, carbonation, drying-shrinkage value and pore structure, showed marked improvement. The results indicated that it is possible to obtain cement composites with a compact microstructure and with high performances by introducing CCS/GO intercalation composites.
Lv, Shenghua; Hu, Haoyan; Zhang, Jia; Luo, Xiaoqian; Lei, Ying; Sun, Li
2017-01-01
Original graphene oxide (GO) nanosheets were prepared using the Hummers method and found to easily aggregate in aqueous and cement composites. Using carboxymethyl chitosan (CCS) as a dispersant, few-layered GO nanosheets (1–2 layers) were obtained by forming CCS/GO intercalation composites. The testing results indicated that the few-layered GO nanosheets could uniformly spread, both in aqueous and cement composites. The cement composites were prepared with GO dosages of 0.03%, 0.05% and 0.07% and we found that they had a compact microstructure in the whole volume. A special feature was determined, namely that the microstructures consisted of regular-shaped crystals created by self-crosslinking. The X-ray diffraction (XRD) results indicated that there was a higher number of cement hydration crystals in GO/cement composites. Meanwhile, we also found that partially-amorphous Calcium-Silicate-Hydrate (C-S-H) gel turned into monoclinic crystals. At 28 days, the GO/cement composites reached the maximum compressive and flexural strengths at a 0.05% dosage. These strengths were 176.64 and 31.67 MPa and, compared with control samples, their increased ratios were 64.87% and 149.73%, respectively. Durability parameters, such as penetration, freeze-thaw, carbonation, drying-shrinkage value and pore structure, showed marked improvement. The results indicated that it is possible to obtain cement composites with a compact microstructure and with high performances by introducing CCS/GO intercalation composites. PMID:29258271
NASA Astrophysics Data System (ADS)
Jeans, Christopher V.; Long, Dee; Hu, Xiu-Fang; Mortimore, Rory N.
2014-12-01
The regional hardening of the Late Cenomanian to Early Turonian Chalk of the Northern Province of eastern England has been investigated by examining the pattern of trace elements and stable carbon and oxygen isotopes in the bulk calcite of two extensive and stratigraphically adjacent units each 4 to 5 m thick of hard chalk in Lincolnshire and Yorkshire. These units are separated by a sequence, 0.3-1.3 m thick, of variegated marls and clayey marls. Modelling of the geochemistry of the hard chalk by comparison with the Standard Louth Chalk, combined with associated petrographic and geological evidence, indicates that (1) the hardening is due to the precipitation of a calcite cement, and (2) the regional and stratigraphical patterns of geochemical variation in the cement are largely independent of each other and have been maintained by the impermeable nature of the thin sequence of the clay-rich marls that separate them. Two phases of calcite cementation are recognised. The first phase was microbially influenced and did not lithify the chalk. It took place predominantly in oxic and suboxic conditions under considerable overpressure in which the Chalk pore fluids circulated within the units, driven by variations in compaction, temperature, pore fluid pressure and local tectonics. There is evidence in central and southern Lincolnshire of the loss of Sr and Mgenriched pore fluids to the south during an early part of this phase. The second phase of calcite precipitation was associated with the loss of overpressure in probably Late Cretaceous and in Cenozoic times as the result of fault movement in the basement penetrating the overlying Chalk and damaging the seal between the two chalk units. This greatly enhanced grain pressures, resulting in grain welding and pressure dissolution, causing lithification with the development of stylolites, marl seams, and brittle fractures. Associated with this loss of overpressure was the penetration of the chalk units by allochthonous fluids, rich in sulphate and hydrocarbons, derived probably from the North Sea Basin. Microbial sulphate-reduction under anoxic conditions within these allochthonous fluids has been responsible for dissolving the fine-grained iron and manganese oxides within the chalk, locally enriching the Fe and Mn content of the calcite cement. The possibility is discussed that the pattern of cementation preserved in these regionally hard chalks of Late Cenomanian and Early Turonian age may be different from that preserved in the younger (late Turonian to Campanian) more basinal chalks of eastern England.
NASA Astrophysics Data System (ADS)
Abdoulghafour, H.; Luquot, L.; Gouze, P.
2012-12-01
So far, cement alteration was principally studied experimentally using batch reactor (with static or renewed fluid). All exhibit similar carbonation mechanisms. The acidic solution, formed by the dissolution of the CO2 into the pore water or directly surrounding the cement sample, diffuses into the cement and induces dissolution reactions of the cement hydrates in particular portlandite and CSH. The calcium released by the dissolution of these calcium bearing phases combining with carbonate ions of the fluid forms calcium carbonates. The cement pH, initially around 13, falls to values where carbonate ion is the most dominant element (pH ~ 9), then CaCO3 phases can precipitate. These studies mainly associate carbonation process with a reduction of porosity and permeability. Indeed an increase of volume (about 10%) is expected during the formation of calcite from portlandite (equation 2) assuming a stoichiometric reaction. Here we investigated the cement alteration mechanisms in the frame of a controlled continuous renewal of CO2-rich fluid in a fracture. This situation is that expected when seepage is activated by the mechanical failure of the cement material that initially seals two layers of distinctly different pressure: the storage reservoir and the aquifer above the caprock, for instance. We study the effect of flow rates from quasi-static flow to higher flow rates for well-connected fractures. In the quasi-static case we observed an extensive conversion of portlandite (Ca(OH)2) to calcite in the vicinity of the fracture similar to that observed in the published batch experiments. Eventually, the fracture was almost totally healed. The experiments with constant flow revealed a different behaviour triggered by the continuous renewing of the reactants and withdrawal of reaction products. We showed that calcite precipitation is more efficient for low flow rate. With intermediate flow rate, we measured that permeability increases slowly at the beginning of the experiment and then remains constant due to calcite precipitation in replacement of CSH and CH into fracture border. With higher flow rate, we measured a constant permeability which can be explained by the development of a highly hydrated Si-rich zone which maintains the initial fracture aperture during all over the experiment while noticeable mass is released from the sample. These preliminary results emphasize that more complex behaviours than that envisaged from batch experiments may take place in the vicinity of flowing fractures. We demonstrated that if only micro-cracks appear in the cement well, carbonation reaction may heal these micro-cracks and mitigate leakage whereas conductive fractures allowing high flow may represent a risk of perennial leakage because the net carbonation process, including the calcite precipitation and its subsequent re-dissolution, is sufficiently to heal the fracture. However, the precipitation of Si-rich amorphous phases may maintain the initial fracture aperture and limit the leakage rate. Keywords: leakage, cement alteration, flow rate, fracture, permeability changes, reaction processes.
Stress fields around two pores in an elastic body: exact quadrature domain solutions.
Crowdy, Darren
2015-08-08
Analytical solutions are given for the stress fields, in both compression and far-field shear, in a two-dimensional elastic body containing two interacting non-circular pores. The two complex potentials governing the solutions are found by using a conformal mapping from a pre-image annulus with those potentials expressed in terms of the Schottky-Klein prime function for the annulus. Solutions for a three-parameter family of elastic bodies with two equal symmetric pores are presented and the compressibility of a special family of pore pairs is studied in detail. The methodology extends to two unequal pores. The importance for boundary value problems of plane elasticity of a special class of planar domains known as quadrature domains is also elucidated. This observation provides the route to generalization of the mathematical approach here to finding analytical solutions for the stress fields in bodies containing any finite number of pores.
The Performance of Geopolymers Activated by Sodium Hydroxide.
Hong, Hyeontaek; Kang, Seunggu
2015-08-01
Geopolymers, a group of promising environmentally friendly materials that can work as cement substitutes, should be fabricated from SiO2-Al2O3-CaO mixtures containing large amounts of amorphous phases to ensure optimal chemical and physical properties. In this study, it was shown that geopolymers with enhanced mechanical strengths, as high as 115 MPa, could be obtained from perfectly amorphous slag from spent catalyst (SSC) discharged during automobile catalyst recycling. Geopolymer processing involved alkali-activation using a 16 M NaOH solution of pH13. The varying SSC grain size was the main experimental factor of interest, in combination with curing temperature and aging time. Variations in the mechanical strengths of the resulting geopolymers are explained by the occurrence of 10-50 nm-sized crystals and the presence of voids and pores dozens to hundreds of micrometers in size.
Mignon, Arn; Devisscher, Dries; Vermeulen, Jolien; Vagenende, Maxime; Martins, José; Dubruel, Peter; De Belie, Nele; Van Vlierberghe, Sandra
2017-07-15
Smart pH-responsive superabsorbent polymers (SAPs) could be useful for self-healing of cracks in mortar. They will swell minimally during the alkaline conditions of mixing, leading to only small macro-pores but will swell stronger with a lower pH when water enters the cracks. As such, polysaccharides (alginate, chitosan and agarose) were methacrylated and cross-linked with amine-based monomers (dimethylaminoethyl methacrylate and dimethylaminopropyl methacrylamide) to induce a varying pH-sensitivity. These materials showed a strong cross-linking efficiency and induced moisture uptake capacities up to 122% at 95% relative humidity with a negligible hysteresis. Additionally, interesting pH-responsive swelling capacities were obtained, especially for SAPs based on chitosan and agarose with values up to 110gwater/gSAP. Most of these materials showed limited hydrolysis in cement filtrate solutions, making them very promising for use in mortar. Copyright © 2017 Elsevier Ltd. All rights reserved.
Determination of the cement content of hardened concrete by selective solution : final report.
DOT National Transportation Integrated Search
1972-01-01
The method of selective solution by methanolic maleic acid, developed by Tabikh et. al for the determination of cement content in hardened concrete, was evaluated. It was found to be relatively simple and inexpensive, and is accurate to within 1 pe...
NASA Astrophysics Data System (ADS)
Gautham, S.; Sindu, B. S.; Sasmal, Saptarshi
2017-10-01
Properties and distribution of the products formed during the hydration of cementitious composite at the microlevel are investigated using a nanoindentation technique. First, numerical nanoindentation using nonlinear contact mechanics is carried out on three different phase compositions of cement paste, viz. mono-phase Tri-calcium Silicate (C3S), Di-calcium Silicate (C2S) and Calcium-Silicate-Hydrate (CSH) individually), bi-phase (C3S-CSH, C2S-CSH) and multi-phase (more than 10 individual phases including water pores). To reflect the multi-phase characteristics of hydrating cement composite, a discretized multi-phase microstructural model of cement composite during the progression of hydration is developed. Further, a grid indentation technique for simulated nanoindentation is established, and employed to evaluate the mechanical characteristics of the hydrated multi-phase cement paste. The properties obtained from the numerical studies are compared with those obtained from experimental grid nanoindentation. The influence of composition and distribution of individual phase properties on the properties obtained from indentation are closely investigated. The study paves the way to establishing the procedure for simulated grid nanoindentation to evaluate the mechanical properties of heterogeneous composites, and facilitates the design of experimental nanoindentation.
NASA Astrophysics Data System (ADS)
Orhan, Hükmü
1992-04-01
The importance of dust storms on geological processes has only been studied recently. Case-hardening, desert-varnish formation, duricrust development, reddening and cementation of sediments and caliche formation, are some important geological processes related to dust storms. Dust storms can also be a major source for cements in aeolian sandstones. The Jurassic aeolian Entrada Formation in the Ghost Ranch area is composed of quartz with minor amounts of feldspar and rock fragments, and is cemented with smectite as grain coatings and calcite and kaolinite as pore fillings. Smectite shows a crinkly and honeycomb-like morphology which points to an authigenic origin. The absence of smectite as framework grains and the presence of partially dissolved grains, coated with smectite and smectite egg-shells, indicate an external source. Clay and fine silt-size particles are believed to be the major source for cements, smectite and calcite in the Entrada Formation. The common association of kaolinite with altered feldspar, and the absence of kaolinite in spots heavily cemented with calcite, lead to the conclusions that the kaolinite formation postdates carbonates and that framework feldspar grains were the source of kaolinite.
Gandolfi, M G; Taddei, P; Siboni, F; Modena, E; Ginebra, M P; Prati, C
2011-10-01
To test the chemical-physical properties and apatite-forming ability of experimental fluoride-doped calcium silicate cements designed to create novel bioactive materials for use in endodontics and oral surgery. A thermally treated calcium silicate cement (wTC) containing CaCl(2) 5%wt was modified by adding NaF 1%wt (FTC) or 10%wt (F10TC). Cements were analysed by environmental scanning electron microscopy with energy-dispersive X-ray analysis, IR and micro-Raman spectroscopy in wet conditions immediately after preparation or after ageing in a phosphate-containing solution (Dulbecco's phosphate-buffered saline). Calcium and fluoride release and pH of the storage solution were measured. The results obtained were analysed statistically (Tukey's HSD test and two-way anova). The formation of calcium phosphate precipitates (spherulites) was observed on the surface of 24 h-aged cements and the formation of a thick bone-like B-type carbonated apatite layer (biocoating) on 28 day-aged cements. The rate of apatite formation was FTC>F10TC>wTC. Fluorapatite was detected on FTC and F10TC after 1 day of ageing, with a higher fluoride content on F10TC. All the cements released calcium ions. At 5 and 24 h, the wTC had the significantly highest calcium release (P<0.001) that decreased significantly over the storage time. At 3-28 days, FTC and F10TC had significantly higher calcium release than wTC (P<0.05). The F10TC had the significantly highest fluoride release at all times (P<0.01) that decreased significantly over storage time. No significant differences were observed between FTC and wTC. All the cements had a strong alkalinizing activity (OH(-) release) that remained after 28 days of storage. The addition of sodium fluoride accelerated apatite formation on calcium silicate cements. Fluoride-doped calcium silicate cements had higher bioactivity and earlier formation of fluorapatite. Sodium fluoride may be introduced in the formulation of mineral trioxide aggregate cements to enhance their biological behaviour. F-doped calcium silicate cements are promising bone cements for clinical endodontic use. © 2011 International Endodontic Journal.
Solidification/stabilization of dredged marine sediments for road construction.
Wang, Dong Xing; Abriak, Nor Edine; Zentar, Rachid; Xu, WeiYa
2012-01-01
Cement/lime-based solidification is an environmentally sound solution for the management of dredged marine sediments, instead of traditional solutions such as immersion. Based on the mineralogical composition and physical characteristics of Dunkirk sediments, the effects of cement and lime are assessed through Atterberg limits, modified Proctor compaction, unconfined compressive strength and indirect tensile strength tests. The variation of Atterberg limits and the improvement in strength are discussed at different binder contents. The potential of sediments solidified with cement or lime for road construction is evaluated through a proposed methodology from two aspects: I-CBR value and material classification. The test results show the feasibility of solidified dredged sediments for beneficial use as a material in road construction. Cement is superior to lime in terms of strength improvement, and adding 6% cement is an economic and reasonable method to stabilize fine sediments.
Cui, Xu; Huang, Wenhai; Zhang, Yadong; Huang, Chengcheng; Yu, Zunxiong; Wang, Lei; Liu, Wenlong; Wang, Ting; Zhou, Jie; Wang, Hui; Zhou, Nai; Wang, Deping; Pan, Haobo; Rahaman, Mohamed N
2017-04-01
There is a need for synthetic biomaterials to heal bone defects using minimal invasive surgery. In the present study, an injectable cement composed of bioactive borate glass particles and a chitosan bonding solution was developed and evaluated for its capacity to heal bone defects in a rabbit femoral condyle model. The injectability and setting time of the cement in vitro decreased but the compressive strength increased (8±2MPa to 31±2MPa) as the ratio of glass particles to chitosan solution increased (from 1.0gml -1 to 2.5gml -1 ). Upon immersing the cement in phosphate-buffered saline, the glass particles reacted and converted to hydroxyapatite, imparting bioactivity to the cement. Osteoblastic MC3T3-E1 cells showed enhanced proliferation and alkaline phosphatase activity when incubated in media containing the soluble ionic product of the cement. The bioactive glass cement showed a better capacity to stimulate bone formation in rabbit femoral condyle defects at 12weeks postimplantation when compared to a commercial calcium sulfate cement. The injectable bioactive borate glass cement developed in this study could provide a promising biomaterial to heal bone defects by minimal invasive surgery. Copyright © 2016 Elsevier B.V. All rights reserved.
Impedance methodology: A new way to characterize the setting reaction of dental cements.
Villat, Cyril; Tran, Xuan-Vinh; Tran, V X; Pradelle-Plasse, Nelly; Ponthiaux, Pierre; Wenger, François; Grosgogeat, Brigitte; Colon, Pierre
2010-12-01
Impedance spectroscopy is a non-destructive, quantitative method, commonly used nowadays for industrial research on cement and concrete. The aim of this study is to investigate the interest of impedance spectroscopy in the characterization of setting process of dental cements. Two types of dental cements are used in this experiment: a new Calcium Silicate cement Biodentine™ (Septodont, Saint Maur-des Fossés, France) and a glass ionomer cement resin modified or not (Fuji II(®) LC Improved Capsules and Fuji IX(®) GP Fast set Capsules, GC Corp., Tokyo, Japan). The conductivity of the dental cements was determined by impedance spectroscopy measurements carried out on dental cement samples immersed in a 0.1M potassium chloride solution (KCl) in a "like-permeation" cell connected to a potentiostat and a Frequency Response Analyzer. The temperature of the solution is 37°C. From the moment of mixing of powder and liquid, the experiments lasted 2 weeks. The results obtained for each material are relevant of the setting process. For GIC, impedance values are stabilized after 5 days while at least 14 days are necessary for the calcium silicate based cement. In accordance with the literature regarding studies of cements and concrete, impedance spectroscopy can characterize ion mobility, porosity and hardening process of dental hydrogel materials. Copyright © 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
Femtosecond laser ablation of cemented carbides: properties and tribological applications
NASA Astrophysics Data System (ADS)
Dumitru, G.; Romano, V.; Weber, H. P.; Gerbig, Y.; Haefke, H.; Bruneau, S.; Hermann, J.; Sentis, M.
Laser ablation with fs laser pulses was performed in air on cobalt cemented tungsten carbide by means of a Ti : sapphire laser (800 nm, 100 fs). Small and moderate fluences (2, 5, 10 J/cm2) and up to 5×104 pulses per irradiated spot were used to drill holes with aspect ratios up to 10. Cross-section cuts from laser-irradiated samples were produced and they were analysed with optical microscopy and SEM. EDX analyses were carried out on selected zones. Quasi-cylindrical holes were found for 2 J/cm2, whereas for 5 and 10 J/cm2 irregular shapes (lobes, bottoms wider than hole entrances) were found to occur after a given number of incident pulses. Layers with modified structure were evidenced at pore walls. SEM revealed a denser structure, while EDX analyses showed uniform and almost similar contents of W, C, and Co in these layers. As a direct application, patterning of coated WC-Co was carried out with 2 J/cm2 and 100 pulses per pore. The resulted surfaces were tribologically tested and these tests revealed an improved friction and wear behaviour.
Characterization of Calcite Mineral Precipitation Process by EICP in Porous Media
NASA Astrophysics Data System (ADS)
Kim, D.; Mahabadi, N.; Hall, C.; Jang, J.; van Paassen, L. A.
2017-12-01
One of the most prevalent ground improvement techniques is injection of synthetic materials, such as cement grout or silicates into the pore space to create cementing bonds between soil particles. Besides these traditional ground improvement methods, several biological processes have been developed to improve soil properties. Enzyme induced carbonate precipitation (EICP) is a biological process in which urea hydrolyzes into ammonia and inorganic carbon, and promotes carbonate mineral precipitation. Different morphologies and patterns of calcite mineral precipitation, such as particle surface coating, pore filling, and soil particles bonding, have been observed in the previous studies. Most of the researches have detected precipitated minerals after the completion of the treatment using SEM (Scanning Electron Microscope) imaging and XRD (X-ray Diffractometer) structural analysis. In this research, an EICP reaction medium is injected into a microfluidic chip to observe the entire process of carbonate precipitation through several cycles of EICP treatment in the porous medium. Once the process of mineral precipitation is completed, water is injected into the microfluidic chip with different flow rates to evaluate the stability of carbonates during fluid flow injection.
Review: Role of chemistry, mechanics, and transport on well integrity in CO 2 storage environments
Carroll, Susan A.; Carey, William J.; Dzombak, David; ...
2016-03-22
Among the various risks associated with CO 2 storage in deep geologic formations, wells are important potential pathways for fluid leaks and groundwater contamination. Injection of CO 2 will perturb the storage reservoir and any wells that penetrate the CO 2 or pressure footprints are potential pathways for leakage of CO 2 and/or reservoir brine. Well leakage is of particular concern for regions with a long history of oil and gas exploration because they are top candidates for geologic CO 2storage sites. This review explores in detail the ability of wells to retain their integrity against leakage with careful examinationmore » of the coupled physical and chemical processes involved. Understanding time-dependent leakage is complicated by the changes in fluid flow, solute transport, chemical reactions, and mechanical stresses over decade or longer time frames for site operations and monitoring. Almost all studies of the potential for well leakage have been laboratory based, as there are limited data on field-scale leakage. When leakage occurs by diffusion only, laboratory experiments show that while CO 2 and CO 2-saturated brine react with cement and casing, the rate of degradation is transport-limited and alteration of cement and casing properties is low. When a leakage path is already present due to cement shrinkage or fracturing, gaps along interfaces (e.g. casing/cement or cement/rock), or casing failures, chemical and mechanical alteration have the potential to decrease or increase leakage risks. Laboratory experiments and numerical simulations have shown that mineral precipitation or closure of strain-induced fractures can seal a leak pathway over time or conversely open pathways depending on flow-rate, chemistry, and the stress state. Experiments with steel/cement and cement/rock interfaces have indicated that protective mechanisms such as metal passivation, chemical alteration, mechanical deformation, and pore clogging can also help mitigate leakage. The specific rate and nature of alteration depends on the cement, brine, and injected fluid compositions. For example, the presence of co-injected gases (e.g. O 2, H 2S, and SO 2) and pozzolan amendments (fly ash) to cement influences the rate and the nature of cement reactions. A more complete understanding of the coupled physical-chemical mechanisms involved with sealing and opening of leakage pathways is needed. An important challenge is to take empirically based chemical, mechanical, and transport models reviewed here and assess leakage risk for carbon storage at the field scale. Furthermore, field observations to accompany laboratory and modeling studies are critical to validating understanding of leakage risk. Long-term risk at the field scale is an area of active research made difficult by the large variability of material types (cement, geologic material, casing), field conditions (pressure, temperature, gradient in potential, residence time), and leaking fluid composition (CO 2, co-injected gases, brine). Of particular interest are the circumstances when sealing and other protective mechanisms are likely to be effective, when they are likely to fail, and the zone of uncertainty between these two extremes.« less
Den Buijs, Jorn Op; Dragomir-Daescu, Dan; Ritman, Erik L
2009-08-01
Nutrient supply and waste removal in porous tissue engineering scaffolds decrease from the periphery to the center, leading to limited depth of ingrowth of new tissue into the scaffold. However, as many tissues experience cyclic physiological strains, this may provide a mechanism to enhance solute transport in vivo before vascularization of the scaffold. The hypothesis of this study was that pore cross-sectional geometry and interconnectivity are of major importance for the effectiveness of cyclic deformation-induced solute transport. Transparent elastic polyurethane scaffolds, with computer-programmed design of pore networks in the form of interconnected channels, were fabricated using a 3D printing and injection molding technique. The scaffold pores were loaded with a colored tracer for optical contrast, cyclically compressed with deformations of 10 and 15% of the original undeformed height at 1.0 Hz. Digital imaging was used to quantify the spatial distribution of the tracer concentration within the pores. Numerical simulations of a fluid-structure interaction model of deformation-induced solute transport were compared to the experimental data. The results of experiments and modeling agreed well and showed that pore interconnectivity heavily influences deformation-induced solute transport. Pore cross-sectional geometry appears to be of less relative importance in interconnected pore networks. Validated computer models of solute transport can be used to design optimal scaffold pore geometries that will enhance the convective transport of nutrients inside the scaffold and the removal of waste, thus improving the cell survivability deep inside the scaffold.
The dissolution mechanisms of silicate and glass-ionomer dental cements.
Kuhn, A T; Wilson, A D
1985-11-01
The mechanism of dissolution of two dental cements of the acid-base setting types (silicate and glass-ionomer) is considered. Dissolution is incongruent, probably because most of the leached species can derive both from the matrix (polysalt gel) and the partly reacted glass particles. The release occurs by means of three discrete mechanisms, surface wash-off, diffusion through pores and cracks or diffusion through the bulk. Such behaviour is shown to be capable of being modelled with extremely high goodness-of-fit values, using equations such as y = const + at1/2 + bt. Analogies with research from the fields of geochemistry and nuclear fuel storage are made and these systems obey similar relationships. The dental cement systems differ, however, in that their dissolution is to some extent reversible. This is explained in terms of formation of insoluble complexes, either by reaction of the constituent ions, or by replacement of OH-, for example, with F-.
Dickens, Sabine H; Flaim, Glenn M
2008-09-01
To test whether fluoride in a resin-based Ca-PO4 ion releasing cement or coating with an acidic bonding agent for improved adhesion compromised the cement remineralization potential. Cements were formulated without fluoride (Cement A) or with fluoride (Cement B). The treatment groups were A=Cement A; A2=Cement A+bonding agent; B=Cement B; B2=Cement B+bonding agent. The calcium, phosphate, and fluoride ion release in saliva-like solution (SLS) was determined from hardened cement disks without or with a coating of bonding agent. For the remineralization, two cavities were prepared in dentin of extracted human molars and demineralized. One cavity received composite resin (control); the other received treatment A, A2, B or B2. After 6 week incubation in SLS, 180 microm cross-sections were cut. The percentage remineralization was determined by transverse microradiography comparing the dentin mineral density under the cement to that under the control. The percentage of remineralization (mean+/-S.D.) was A (39+/-14)=B (37+/-18), A2 (23+/-13), B2 (14+/-7). Two-way analysis of variance (ANOVA) and Holm-Sidak test showed a significant effect from the presence of bonding agent (p<0.05), but not from fluoride (p>0.05). The ion solution concentrations of all groups showed undersaturation with respect to dicalcium phosphate dihydrate and calcium fluoride and supersaturation for fluorapatite and hydroxyapatite suggesting a positive remineralization potential. Compared to the control all treatments resulted in mineral increase. The remineralization was negatively affected by the presence of the bonding agent.
Wu, Bo; Chun, Byong-Wa; Gu, Le; Kuhl, Tonya L
2018-05-09
Poly(carboxylate ether)-based (PCE) superplasticizers consist of a carboxylic acid backbone and grafted poly(ethylene glycol) (PEG) side chains. Ca 2+ ion bridging mechanism is commonly purported to control PCE's adsorption on negatively charged cement particle surfaces in cement suspension, thus PCE was expected to adsorb on negatively charged surfaces in synthetic pore solutions via Ca 2+ /COO - interactions. Adsorption behaviors of a commercial PCE on negatively charged mica were studied in aqueous electrolyte solutions by a surface forces apparatus. Direct force measurements indicated that the PCE adsorbed onto mica from 0.1 M K 2 SO 4 due to K + ion chelation by the ether oxygen units CH 2 CH 2 O on the PEG chains, but surprisingly did not adsorb from either 0.1 M K 2 SO 4 with saturated Ca(OH) 2 or 0.1 M Ca(NO 3 ) 2 . The adsorption in K 2 SO 4 was weak, enabling the adsorbed PCE layers to be squeezed out under modest compression. Upon separating the surfaces, the PCE immediately achieved an identical re-adsorption. In high-calcium conditions, the PCE was highly positively charged due to Ca 2+ ion chelation by PEG chains and backbone carboxylic groups COO - , and mica also underwent charge reversal due to electrostatic adsorption/binding of Ca 2+ ions. Consequently, the interaction between mica and PCE was electrostatically repulsive and no PCE adsorption occurred. These findings can be explained by the complex interplay of ion chelation by PEG chains, electrostatic binding and screening interactions with charged surfaces in the presence of monovalent and divalent counterions, and ultimately charge reversal of both the charged surfaces and polyelectrolyte in high divalent ion conditions. Copyright © 2018 Elsevier Inc. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Brunet, Jean-Patrick Leopold; Li, Li; Karpyn, Zuleima T
2013-08-01
Assessing the possibility of CO{sub 2} leakage is one of the major challenges for geological carbon sequestration. Injected CO{sub 2} can react with wellbore cement, which can potentially change cement composition and transport properties. In this work, we develop a reactive transport model based on experimental observations to understand and predict the property evolution of cement in direct contact with CO{sub 2}-saturated brine under diffusion-controlled conditions. The model reproduced the observed zones of portlandite depletion and calcite formation. Cement alteration is initially fast and slows down at later times. This work also quantified the role of initial cement properties, inmore » particular the ratio of the initial portlandite content to porosity (defined here as φ), in determining the evolution of cement properties. Portlandite-rich cement with large φ values results in a localized “sharp” reactive diffusive front characterized by calcite precipitation, leading to significant porosity reduction, which eventually clogs the pore space and prevents further acid penetration. Severe degradation occurs at the cement–brine interface with large φ values. This alteration increases effective permeability by orders of magnitude for fluids that preferentially flow through the degraded zone. The significant porosity decrease in the calcite zone also leads to orders of magnitude decrease in effective permeability, where fluids flow through the low-permeability calcite zone. The developed reactive transport model provides a valuable tool to link cement–CO{sub 2} reactions with the evolution of porosity and permeability. It can be used to quantify and predict long-term wellbore cement behavior and can facilitate the risk assessment associated with geological CO{sub 2} sequestration.« less
Mechanical properties of cement concrete composites containing nano-metakaolin
NASA Astrophysics Data System (ADS)
Supit, Steve Wilben Macquarie; Rumbayan, Rilya; Ticoalu, Adriana
2017-11-01
The use of nano materials in building construction has been recognized because of its high specific surface area, very small particle sizes and more amorphous nature of particles. These characteristics lead to increase the mechanical properties and durability of cement concrete composites. Metakaolin is one of the supplementary cementitious materials that has been used to replace cement in concrete. Therefore, it is interesting to investigate the effectiveness of metakaolin (in nano scale) in improving the mechanical properties including compressive strength, tensile strength and flexural strength of cement concretes. In this experiment, metakaolin was pulverized by using High Energy Milling before adding to the concrete mixes. The pozzolan Portland cement was replaced with 5% and 10% nano-metakaolin (by wt.). The result shows that the optimum amount of nano-metakaolin in cement concrete mixes is 10% (by wt.). The improvement in compressive strength is approximately 123% at 3 days, 85% at 7 days and 53% at 28 days, respectively. The tensile and flexural strength results also showed the influence of adding 10% nano-metakaolin (NK-10) in improving the properties of cement concrete (NK-0). Furthermore, the Backscattered Electron images and X-Ray Diffraction analysis were evaluated to support the above findings. The results analysis confirm the pores modification due to nano-metakaolin addition, the consumption of calcium hydroxide (CH) and the formation of Calcium Silicate Hydrate (CSH) gel as one of the beneficial effects of amorphous nano-metakaolin in improving the mechanical properties and densification of microstructure of mortar and concrete.
Intercomparison of 3D pore-scale flow and solute transport simulation methods
Mehmani, Yashar; Schoenherr, Martin; Pasquali, Andrea; ...
2015-09-28
Multiple numerical approaches have been developed to simulate porous media fluid flow and solute transport at the pore scale. These include 1) methods that explicitly model the three-dimensional geometry of pore spaces and 2) methods that conceptualize the pore space as a topologically consistent set of stylized pore bodies and pore throats. In previous work we validated a model of the first type, using computational fluid dynamics (CFD) codes employing a standard finite volume method (FVM), against magnetic resonance velocimetry (MRV) measurements of pore-scale velocities. Here we expand that validation to include additional models of the first type based onmore » the lattice Boltzmann method (LBM) and smoothed particle hydrodynamics (SPH), as well as a model of the second type, a pore-network model (PNM). The PNM approach used in the current study was recently improved and demonstrated to accurately simulate solute transport in a two-dimensional experiment. While the PNM approach is computationally much less demanding than direct numerical simulation methods, the effect of conceptualizing complex three-dimensional pore geometries on solute transport in the manner of PNMs has not been fully determined. We apply all four approaches (FVM-based CFD, LBM, SPH and PNM) to simulate pore-scale velocity distributions and (for capable codes) nonreactive solute transport, and intercompare the model results. Comparisons are drawn both in terms of macroscopic variables (e.g., permeability, solute breakthrough curves) and microscopic variables (e.g., local velocities and concentrations). Generally good agreement was achieved among the various approaches, but some differences were observed depending on the model context. The intercomparison work was challenging because of variable capabilities of the codes, and inspired some code enhancements to allow consistent comparison of flow and transport simulations across the full suite of methods. This paper provides support for confidence in a variety of pore-scale modeling methods and motivates further development and application of pore-scale simulation methods.« less
Intercomparison of 3D pore-scale flow and solute transport simulation methods
DOE Office of Scientific and Technical Information (OSTI.GOV)
Yang, Xiaofan; Mehmani, Yashar; Perkins, William A.
2016-09-01
Multiple numerical approaches have been developed to simulate porous media fluid flow and solute transport at the pore scale. These include 1) methods that explicitly model the three-dimensional geometry of pore spaces and 2) methods that conceptualize the pore space as a topologically consistent set of stylized pore bodies and pore throats. In previous work we validated a model of the first type, using computational fluid dynamics (CFD) codes employing a standard finite volume method (FVM), against magnetic resonance velocimetry (MRV) measurements of pore-scale velocities. Here we expand that validation to include additional models of the first type based onmore » the lattice Boltzmann method (LBM) and smoothed particle hydrodynamics (SPH), as well as a model of the second type, a pore-network model (PNM). The PNM approach used in the current study was recently improved and demonstrated to accurately simulate solute transport in a two-dimensional experiment. While the PNM approach is computationally much less demanding than direct numerical simulation methods, the effect of conceptualizing complex three-dimensional pore geometries on solute transport in the manner of PNMs has not been fully determined. We apply all four approaches (FVM-based CFD, LBM, SPH and PNM) to simulate pore-scale velocity distributions and (for capable codes) nonreactive solute transport, and intercompare the model results. Comparisons are drawn both in terms of macroscopic variables (e.g., permeability, solute breakthrough curves) and microscopic variables (e.g., local velocities and concentrations). Generally good agreement was achieved among the various approaches, but some differences were observed depending on the model context. The intercomparison work was challenging because of variable capabilities of the codes, and inspired some code enhancements to allow consistent comparison of flow and transport simulations across the full suite of methods. This study provides support for confidence in a variety of pore-scale modeling methods and motivates further development and application of pore-scale simulation methods.« less
NASA Astrophysics Data System (ADS)
abdelghafour, H.; Luquot, L.; Gouze, P.
2013-12-01
So far, cement alteration was principally studied experimentally using batch reactor (with static or renewed fluid). All exhibit similar carbonation mechanisms. The acidic solution, formed by the dissolution of the CO2 into the pore water or directly surrounding the cement sample, diffuses into the cement and induces dissolution reactions of the cement hydrates in particular portlandite and CSH. The calcium released by the dissolution of these calcium bearing phases combining with carbonate ions of the fluid forms calcium carbonates. The cement pH, initially around 13, falls to values where carbonate ion is the most dominant element (pH ~ 9), then CaCO3 phases can precipitate. These studies mainly associate carbonation process with a reduction of porosity and permeability. Indeed an increase of volume (about 10%) is expected during the formation of calcite from portlandite assuming a stoichiometric reaction. Here we investigated the cement alteration mechanisms in the frame of a controlled continuous renewal of CO2-rich fluid in a fracture. This situation is that expected when seepage is activated by the mechanical failure of the cement material that initially seals two layers of distinctly different pressure: the storage reservoir and the aquifer above the caprock, for instance. We study the effect of flow rates from quasi-static flow to higher flow rates for well-connected fractures. In the quasi-static case we observed an extensive conversion of portlandite (Ca(OH)2) to calcite in the vicinity of the fracture similar to that observed in the published batch experiments. Eventually, the fracture was almost totally healed. The experiments with constant flow revealed a different behavior triggered by the continuous renewing of the reactants and withdrawal of the reaction products. We showed that calcite precipitation is more efficient for low flow rate. With intermediate flow rate, we measured that permeability increases slowly at the beginning of the experiment and then remains constant due to calcite precipitation in replacement of CSH and CH into fracture border. With higher flow rate, we measured a constant permeability which can be explained by the development of a highly hydrated Si-rich zone which maintains the initial fracture aperture during all over the experiment while noticeable mass is released from the sample. These results emphasize that more complex behaviors than that envisaged from batch experiments may take place in the vicinity of flowing fractures. We demonstrated that if only micro-cracks appear in the cement well, carbonation reaction may heal these micro-cracks and mitigate leakage whereas conductive fractures allowing high flow may represent a risk of perennial leakage because the net carbonation process, including the calcite precipitation and its subsequent re-dissolution, is sufficiently to heal the fracture. However, the precipitation of Si-rich amorphous phases may maintain the initial fracture aperture and limit the leakage rate.
Op Den Buijs, Jorn; Dragomir-Daescu, Dan; Ritman, Erik L.
2014-01-01
Nutrient supply and waste removal in porous tissue engineering scaffolds decrease from the periphery to the center, leading to limited depth of ingrowth of new tissue into the scaffold. However, as many tissues experience cyclic physiological strains, this may provide a mechanism to enhance solute transport in vivo before vascularization of the scaffold. The hypothesis of this study was that pore cross-sectional geometry and interconnectivity are of major importance for the effectiveness of cyclic deformation-induced solute transport. Transparent elastic polyurethane scaffolds, with computer-programmed design of pore networks in the form of interconnected channels, were fabricated using a 3D printing and injection molding technique. The scaffold pores were loaded with a colored tracer for optical contrast, cyclically compressed with deformations of 10 and 15% of the original undeformed height at 1.0 Hz. Digital imaging was used to quantify the spatial distribution of the tracer concentration within the pores. Numerical simulations of a fluid–structure interaction model of deformation-induced solute transport were compared to the experimental data. The results of experiments and modeling agreed well and showed that pore interconnectivity heavily influences deformation-induced solute transport. Pore cross-sectional geometry appears to be of less relative importance in interconnected pore networks. Validated computer models of solute transport can be used to design optimal scaffold pore geometries that will enhance the convective transport of nutrients inside the scaffold and the removal of waste, thus improving the cell survivability deep inside the scaffold. PMID:19466547
NASA Astrophysics Data System (ADS)
Doungkaew, N.; Eichhubl, P.
2015-12-01
Processes of fracture formation control flow of fluid in the subsurface and the mechanical properties of the brittle crust. Understanding of fundamental fracture growth mechanisms is essential for understanding fracture formation and cementation in chemically reactive systems with implications for seismic and aseismic fault and fracture processes, migration of hydrocarbons, long-term CO2 storage, and geothermal energy production. A recent study on crack-seal veins in deeply buried sandstone of east Texas provided evidence for non-linear fracture growth, which is indicated by non-elliptical kinematic fracture aperture profiles. We hypothesize that similar non-linear fracture growth also occurs in other geologic settings, including under higher temperature where solution-precipitation reactions are kinetically favored. To test this hypothesis, we investigate processes of fracture growth in quartzitic sandstone of the Campito Formation, eastern California, by combining field structural observations, thin section petrography, and fluid inclusion microthermometry. Fracture aperture profile measurements of cemented opening-mode fractures show both elliptical and non-elliptical kinematic aperture profiles. In general, fractures that contain fibrous crack-seal cement have elliptical aperture profiles. Fractures filled with blocky cement have linear aperture profiles. Elliptical fracture aperture profiles are consistent with linear-elastic or plastic fracture mechanics. Linear aperture profiles may reflect aperture growth controlled by solution-precipitation creep, with the aperture distribution controlled by solution-precipitation kinetics. We hypothesize that synkinematic crack-seal cement preserves the elliptical aperture profiles of elastic fracture opening increments. Blocky cement, on the other hand, may form postkinematically relative to fracture opening, with fracture opening accommodated by continuous solution-precipitation creep.
Ratier, A; Gibson, I R; Best, S M; Freche, M; Lacout, J L; Rodriguez, F
2001-05-01
Calcium phosphate cements are used for bone defect filling and they may also be used as delivery systems for active agents. The physicochemical behaviour of an ionic cement, with a final composition of hydroxyapatite, containing tetracycline hydrochloride was investigated. Chemical characterisation, X-ray diffraction analysis, compressive strength and tensile strength were performed. It is known that the antibiotic can be adsorbed on calcium phosphate compounds and the presence of chloride ions can strongly influence the behaviour of the cement. Adding more than 1% (w/w) of 95% pure tetracycline hydrochloride in the solid phase led to a cement with poor mechanical properties, but which, in addition to hydroxyapatite, contained residual starting reagents. For this reason, experiments were also performed with tetracycline previously treated with a calcium sulphate solution. Using a treated tetracycline, it was possible to introduce at least 7% (w/w) of active ingredient whilst still allowing the reaction to proceed to completion i.e. the formation of hydroxyapatite with good mechanical properties. Therefore, treating the tetracycline HCI with calcium sulphate solution prior to reaction conserved the activity of the antibiotic, limited the influence of the antibiotic on the cement evolution and retained the physical properties of the cement.
Correa, Daniel; Almirall, Amisel; García-Carrodeguas, Raúl; dos Santos, Luis Alberto; De Aza, Antonio H; Parra, Juan; Delgado, José Ángel
2014-10-01
β-dicalcium silicate (β-Ca₂ SiO₄, β-C₂ S) is one of the main constituents in Portland cement clinker and many refractory materials, itself is a hydraulic cement that reacts with water or aqueous solution at room/body temperature to form a hydrated phase (C-S-H), which provides mechanical strength to the end product. In the present investigation, β-C₂ S was synthesized by sol-gel process and it was used as powder to cement preparation, named CSiC. In vitro bioactivity and biocompatibility studies were assessed by soaking the cement samples in simulated body fluid solutions and human osteoblast cell cultures for various time periods, respectively. The results showed that the sol-gel process is an available synthesis method in order to obtain a pure powder of β-C₂ S at relatively low temperatures without chemical stabilizers. A bone-like apatite layer covered the material surface after soaking in SBF and its compressive strength (CSiC cement) was comparable with that of the human trabecular bone. The extracts of this cement were not cytotoxic and the cell growth and relative cell viability were comparable to negative control. © 2013 Wiley Periodicals, Inc.
Accelerated ageing of blended OPC cements
DOE Office of Scientific and Technical Information (OSTI.GOV)
Quillin, K.C.; Duerden, S.L.; Majumdar, A.J.
1994-12-31
An accelerated experimental technique using high water:cement ratios has been developed to study the long term hydration of blended cements that may be used in a repository for the disposal of radioactive waste. This technique has been used to investigate the hydration reactions of Ordinary Portland Cement (OPC) blended with ground granulated blastfurnace slag (ggbs) or pulverised fuel ash (pfa). The effects of high sulphate-bearing and high carbonate-bearing ground waters on the compounds formed on hydration were investigated. Solid/solution compositional data were collected during the course of the hydration process for periods up to 2 years. Thomsonite, thaumasite, afwillite andmore » a tobermorite-like phase were found in addition to the expected cement hydration products. The pH of the aqueous solution in contact with 60 pfa:40 OPC blends hydrated at 90{degrees}C fell to below 8. This is lower than the value required to inhibit the corrosion of steel canisters in a repository. The pH of the aqueous solution in contact with OPC and 75 ggbs:25 OPC blends remained above 11, although if the ground waters in contact with the OPC/ggbs blends were periodically replaced the pH eventually fell below 10.« less
Camilleri, J; Cutajar, A; Mallia, B
2011-08-01
Zirconium oxide can be added to dental materials rendering them sufficiently radiopaque. It can thus be used to replace the bismuth oxide in mineral trioxide aggregate (MTA). Replacement of Portland cement with 30% zirconium oxide mixed at a water/cement ratio of 0.3 resulted in a material with adequate physical properties. This study aimed at investigating the microstructure, pH and leaching in physiological solution of Portland cement replaced zirconium oxide at either water-powder or water-cement ratios of 0.3 for use as a root-end filling material. The hydration characteristics of the materials which exhibited optimal behavior were evaluated. Portland cement replaced by zirconium oxide in varying amounts ranging from 0 to 50% in increments of 10 was prepared and divided into two sets. One set was prepared at a constant water/cement ratio while the other set at a constant water/powder ratio of 0.3. Portland cement and MTA were used as controls. The materials were analyzed under the scanning electron microscope (SEM) and the hydration products were determined. X-ray energy dispersive analysis (EDX) was used to analyze the elemental composition of the hydration products. The pH and the amount of leachate in Hank's balanced salt solution (HBSS) were evaluated. A material that had optimal properties that satisfied set criteria and could replace MTA was selected. The microstructure of the prototype material and Portland cement used as a control was assessed after 30 days using SEM and atomic ratio diagrams of Al/Ca versus Si/Ca and S/Ca versus Al/Ca were plotted. The hydration products of Portland cement replaced with 30% zirconium oxide mixed at water/cement ratio of 0.3 were calcium silicate hydrate, calcium hydroxide and minimal amounts of ettringite and monosulphate. The calcium hydroxide leached in HBSS solution resulted in an increase in the pH value. The zirconium oxide acted as inert filler and exhibited no reaction with the hydration by-products of Portland cement. A prototype dental material composed of Portland cement replaced with 30% zirconium oxide as radiopacifier leached calcium ions on hydration which reacted with phosphates present in simulated tissue fluids. This resulted in bioactive cement that could prospectively be used as a root-end filling material. The zirconium oxide acted as inert filler and did not participate in the hydration reaction of the Portland cement. Copyright © 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
Chloride Ion Adsorption Capacity of Anion Exchange Resin in Cement Mortar.
Lee, Yunsu; Lee, Hanseung; Jung, Dohyun; Chen, Zhengxin; Lim, Seungmin
2018-04-05
This paper presents the effect of anion exchange resin (AER) on the adsorption of chloride ions in cement mortar. The kinetic and equilibrium behaviors of AER were investigated in distilled water and Ca(OH)₂ saturated solutions, and then the adsorption of chloride ions by the AER in the mortar specimen was determined. The AER was used as a partial replacement for sand in the mortar specimen. The mortar specimen was coated with epoxy, except for an exposed surface, and then immersed in a NaCl solution for 140 days. The chloride content in the mortar specimen was characterized by energy dispersive X-ray fluorescence analysis and electron probe microanalysis. The results showed that the AER could adsorb the chloride ions from the solution rapidly but had a relatively low performance when the pH of its surrounding environment increased. When the AER was mixed in the cement mortar, its chloride content was higher than that of the cement matrix around it, which confirms the chloride ion adsorption capacity of the AER.
On the Utilization of Pozzolanic Wastes as an Alternative Resource of Cement
Karim, Md. Rezaul; Hossain, Md. Maruf; Khan, Mohammad Nabi Newaz; Zain, Muhammad Fauzi Mohd; Jamil, Maslina; Lai, Fook Chuan
2014-01-01
Recently, as a supplement of cement, the utilization of pozzolanic materials in cement and concrete manufacturing has increased significantly. This study investigates the scope to use pozzolanic wastes (slag, palm oil fuel ash and rice husk ash) as an alkali activated binder (AAB) that can be used as an alternative to cement. To activate these materials, sodium hydroxide solution was used at 1.0, 2.5 and 5.0 molar concentration added into the mortar, separately. The required solution was used to maintain the flow of mortar at 110% ± 5%. The consistency and setting time of the AAB-paste were determined. Mortar was tested for its flow, compressive strength, porosity, water absorption and thermal resistance (heating at 700 °C) and investigated by scanning electron microscopy. The experimental results reveal that AAB-mortar exhibits less flow than that of ordinary Portland cement (OPC). Surprisingly, AAB-mortars (with 2.5 molar solution) achieved a compressive strength of 34.3 MPa at 28 days, while OPC shows that of 43.9 MPa under the same conditions. Although water absorption and porosity of the AAB-mortar are slightly high, it shows excellent thermal resistance compared to OPC. Therefore, based on the test results, it can be concluded that in the presence of a chemical activator, the aforementioned pozzolans can be used as an alternative material for cement. PMID:28788277
On the Utilization of Pozzolanic Wastes as an Alternative Resource of Cement.
Karim, Md Rezaul; Hossain, Md Maruf; Khan, Mohammad Nabi Newaz; Zain, Muhammad Fauzi Mohd; Jamil, Maslina; Lai, Fook Chuan
2014-12-05
Recently, as a supplement of cement, the utilization of pozzolanic materials in cement and concrete manufacturing has increased significantly. This study investigates the scope to use pozzolanic wastes (slag, palm oil fuel ash and rice husk ash) as an alkali activated binder (AAB) that can be used as an alternative to cement. To activate these materials, sodium hydroxide solution was used at 1.0, 2.5 and 5.0 molar concentration added into the mortar, separately. The required solution was used to maintain the flow of mortar at 110% ± 5%. The consistency and setting time of the AAB-paste were determined. Mortar was tested for its flow, compressive strength, porosity, water absorption and thermal resistance (heating at 700 °C) and investigated by scanning electron microscopy. The experimental results reveal that AAB-mortar exhibits less flow than that of ordinary Portland cement (OPC). Surprisingly, AAB-mortars (with 2.5 molar solution) achieved a compressive strength of 34.3 MPa at 28 days, while OPC shows that of 43.9 MPa under the same conditions. Although water absorption and porosity of the AAB-mortar are slightly high, it shows excellent thermal resistance compared to OPC. Therefore, based on the test results, it can be concluded that in the presence of a chemical activator, the aforementioned pozzolans can be used as an alternative material for cement.
Pore shape of honeycomb-patterned films: modulation and interfacial behavior.
Wan, Ling-Shu; Ke, Bei-Bei; Zhang, Jing; Xu, Zhi-Kang
2012-01-12
The control of the pore size of honeycomb-patterned films has been more or less involved in most work on the topic of breath figures. Modulation of the pore shape was largely ignored, although it is important to applications in replica molding, filtration, particle assembly, and cell culture. This article reports a tunable pore shape for patterned films prepared from commercially available polystyrene (PS). We investigated the effects of solvents including tetrahydrofuran (THF) and chloroform (CF) and hydrophilic additives including poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA), poly(ethylene glycol) (PEG), and poly(N-vinyl pyrrolidone) (PVP). Water droplets on/in the polymer solutions were observed and analyzed for simulating the formation and stabilization of breath figures. Interfacial tensions of the studied systems were measured and considered as a main factor to modulate the pore shape. Results indicate that the pores gradually change from near-spherical to ellipsoidal with the increase of additive content when using CF as the solvent; however, only ellipsoidal pores are formed from the THF solution. It is demonstrated that the aggregation of the additives at the water/polymer solution interface is more efficient in the THF solution than that in the CF solution. This aggregation decreases the interfacial tension, stabilizes the condensed water droplets, and shapes the pores of the films. The results may facilitate our understanding of the dynamic breath figure process and provide a new pathway to prepare patterned films with different pore structures.
NASA Astrophysics Data System (ADS)
Wigger, Cornelia; Van Loon, Luc R.
2018-06-01
The effect of the pore water composition on the diffusive anion transport was studied for two different argillaceous, low permeability sedimentary rocks, Opalinus Clay (OPA) and Helvetic Marl (HM). The samples were saturated with different solutions with varying molar concentration and different main cations in the solution: NaCl based pore solutions and CaCl2 based pore solutions. The total porosity was measured by through-diffusion experiments with the neutral tracer HTO. Experiments performed in NaCl solutions resulted in a porosity of 0.12 for OPA and 0.03 for HM, and are consistent with results of the experiments in CaCl2 solutions. The total porosity was independent of the molar concentration, in contrast to the measured anion porosity, which increased with increasing molar concentration. It could further be observed that the pore solution based on the bivalent cation calcium shielded the negative surface charge stronger than the monovalent cation sodium, resulting in a larger measureable anion-accessible porosity in the case of CaCl2 solutions. The data was modelled based on an adapted Donnan approach of Birgersson and Karnland (2009). The model had to be adjusted with a permanent free, uncharged porosity, as well as with structural information on the permanent anion exclusion because of so-called bottleneck pores. Both parameters can only be evaluated from experiments. Nevertheless, taking these two adaptions into account, the effect of varying pore water compositions on the anion-accessible porosity of the investigated argillaceous rocks could be satisfactorily described.
Wigger, Cornelia; Van Loon, Luc R
2018-06-01
The effect of the pore water composition on the diffusive anion transport was studied for two different argillaceous, low permeability sedimentary rocks, Opalinus Clay (OPA) and Helvetic Marl (HM). The samples were saturated with different solutions with varying molar concentration and different main cations in the solution: NaCl based pore solutions and CaCl 2 based pore solutions. The total porosity was measured by through-diffusion experiments with the neutral tracer HTO. Experiments performed in NaCl solutions resulted in a porosity of 0.12 for OPA and 0.03 for HM, and are consistent with results of the experiments in CaCl 2 solutions. The total porosity was independent of the molar concentration, in contrast to the measured anion porosity, which increased with increasing molar concentration. It could further be observed that the pore solution based on the bivalent cation calcium shielded the negative surface charge stronger than the monovalent cation sodium, resulting in a larger measureable anion-accessible porosity in the case of CaCl 2 solutions. The data was modelled based on an adapted Donnan approach of Birgersson and Karnland (2009). The model had to be adjusted with a permanent free, uncharged porosity, as well as with structural information on the permanent anion exclusion because of so-called bottleneck pores. Both parameters can only be evaluated from experiments. Nevertheless, taking these two adaptions into account, the effect of varying pore water compositions on the anion-accessible porosity of the investigated argillaceous rocks could be satisfactorily described. Copyright © 2018 Elsevier B.V. All rights reserved.
Shiozawa, Maho; Takahashi, Hidekazu; Iwasaki, Naohiko; Uo, Motohiro
2013-01-01
The objective of this study was to evaluate the effect of the concentration of calcium chloride (CaCl2) solution on the surface hardness of restorative glass ionomer cements (GICs). Two high-viscosity GICs, Fuji IX GP and GlasIonomer FX-II, were immersed in several concentrations of CaCl2 solution for 1 day and 1 week. The immersed specimen surfaces were evaluated using microhardness testing, grazing incidence X-ray diffraction, and energy-dispersive X-ray spectroscopy. Immersion in a higher concentration of CaCl2 solution produced a greater increase in the surface hardness. No crystalline substance was observed on the immersed surface. Calcium ions were selectively absorbed in the matrix of the GIC surface after immersion. They reacted with the non-reacted carboxylic acid groups remaining in the cement matrix. These reactions were considered to cause an increase in the surface hardness of the GICs.
Gandolfi, Maria Giovanna; Taddei, Paola; Tinti, Anna; De Stefano Dorigo, Elettra; Rossi, Piermaria Luigi; Prati, Carlo
2010-12-01
The bioactivity of calcium silicate mineral trioxide aggregate (MTA) cements has been attributed to their ability to produce apatite in presence of phosphate-containing fluids. This study evaluated surface morphology and chemical transformations of an experimental accelerated calcium-silicate cement as a function of soaking time in different phosphate-containing solutions. Cement discs were immersed in Dulbecco's phosphate-buffered saline (DPBS) or Hank's balanced salt solution (HBSS) for different times (1-180 days) and analysed by scanning electron microscopy connected with an energy dispersive X-ray analysis (SEM-EDX) and micro-Raman spectroscopy. SEM-EDX revealed Ca and P peaks after 14 days in DPBS. A thin Ca- and P-rich crystalline coating layer was detected after 60 days. A thicker multilayered coating was observed after 180 days. Micro-Raman disclosed the 965-cm(-1) phosphate band at 7 days only on samples stored in DPBS and later the 590- and 435-cm(-1) phosphate bands. After 60-180 days, a layer approximately 200-900 μm thick formed displaying the bands of carbonated apatite (at 1,077, 965, 590, 435 cm(-1)) and calcite (at 1,088, 713, 280 cm(-1)). On HBSS-soaked, only calcite bands were observed until 90 days, and just after 180 days, a thin apatite-calcite layer appeared. Micro-Raman and SEM-EDX demonstrated the mineralization induction capacity of calcium-silicate cements (MTAs and Portland cements) with the formation of apatite after 7 days in DPBS. Longer time is necessary to observe bioactivity when cements are immersed in HBSS.
Saturation-dependent solute dispersivity in porous media: Pore-scale processes
NASA Astrophysics Data System (ADS)
Raoof, A.; Hassanizadeh, S. M.
2013-04-01
It is known that in variably saturated porous media, dispersion coefficient depends on Darcy velocity and water saturation. In one-dimensional flow, it is commonly assumed that the dispersion coefficient is a linear function of velocity. The coefficient of proportionality, called the dispersivity, is considered to depend on saturation. However, there is not much known about its dependence on saturation. In this study, we investigate, using a pore network model, how the longitudinal dispersivity varies nonlinearly with saturation. We schematize the porous medium as a network of pore bodies and pore throats with finite volumes. The pore space is modeled using the multidirectional pore-network concept, which allows for a distribution of pore coordination numbers. This topological property together with the distribution of pore sizes are used to mimic the microstructure of real porous media. The dispersivity is calculated by solving the mass balance equations for solute concentration in all network elements and averaging the concentrations over a large number of pores. We have introduced a new formulation of solute transport within pore space, where we account for different compartments of residual water within drained pores. This formulation makes it possible to capture the effect of limited mixing due to partial filling of the pores under variably saturated conditions. We found that dispersivity increases with the decrease in saturation, it reaches a maximum value, and then decreases with further decrease in saturation. To show the capability of our formulation to properly capture the effect of saturation on solute dispersion, we applied it to model the results of a reported experimental study.
3D plotting of growth factor loaded calcium phosphate cement scaffolds.
Akkineni, Ashwini Rahul; Luo, Yongxiang; Schumacher, Matthias; Nies, Berthold; Lode, Anja; Gelinsky, Michael
2015-11-01
Additive manufacturing allows to widely control the geometrical features of implants. Recently, we described the fabrication of calcium phosphate cement (CPC) scaffolds by 3D plotting of a storable CPC paste based on water-immiscible carrier liquid. Plotting and hardening is conducted under mild conditions allowing the (precise and local) integration of biological components. In this study, we have developed a procedure for efficient loading of growth factors in the CPC scaffolds during plotting and demonstrated the feasibility of this approach. Bovine serum albumin (BSA) or vascular endothelial growth factor (VEGF), used as model proteins, were encapsulated in chitosan/dextran sulphate microparticles which could be easily mixed into the CPC paste in freeze-dried state. In order to prevent leaching of the proteins during cement setting, usually carried out by immersion in aqueous solutions, the plotted scaffolds were aged in water-saturated atmosphere (humidity). Setting in humidity avoided early loss of loaded proteins but provided sufficient amount of water to allow cement setting, as indicated by XRD analysis and mechanical testing in comparison to scaffolds set in water. Moreover, humidity-set scaffolds were characterised by altered, even improved properties: no swelling or crack formation was observed and accordingly, surface topography, total porosity and compressive modulus of the humidity-set scaffolds differed from those of the water-set counterparts. Direct cultivation of mesenchymal stem cells on the humidity-set scaffolds over 21days revealed their cytocompatibility. Maintenance of the bioactivity of VEGF during the fabrication procedure was proven in indirect and direct culture experiments with endothelial cells. Additive manufacturing techniques allow the fabrication of implants with defined architecture (inner pore structure and outer shape). Especially printing technologies conducted under mild conditions allow additionally the (spatially controlled) integration of biological components such as drugs or growth factors. That enables the generation of individualized implants which can better meet the requirements of a patient and of tissue engineering constructs. To our knowledge, simultaneous printing of biological components was up to now only described for hydrogel/biopolymer-based materials which suffer from poor mechanical properties. In contrast, we have developed a procedure (based on 3D plotting of a calcium phosphate cement paste) for the fabrication of designed and growth factor loaded calcium-phosphate-based scaffolds applicable for bone regeneration. Copyright © 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Study of leaching mechanisms of caesium ions incorporated in Ordinary Portland Cement.
Papadokostaki, Kyriaki G; Savidou, Anastasia
2009-11-15
In this work, a study of the leaching kinetics of Cs(+) ions from cement paste solids, containing inactive Cs(2)SO(4), is presented, involving (i) the parallel performance of leaching experiments at two temperatures (30 degrees C and 70 degrees C); (ii) the performance of leaching tests with intermediate changes in temperature between 30 degrees C and 70 degrees C; (iii) the use of specimens of two different thicknesses and (iv) the determination of the distribution of Cs(+) in the cement specimen at various stages of the leaching test. The results of leaching studies at 30 degrees C with cement solids simulating the composition of real radioactive wastes, containing NaNO(3), small amounts of inactive CsNO(3) and traces of (137)Cs(+) are also reported. Concentration profiles of Cs(+) in inactive specimens showed that part of the Cs(+) (20-30%) tends to be immobilized in the matrix, while elution of the readily leachable portion follows Fick's law reasonably well. No immobilized Cs(+) was detected in the samples containing considerable amounts of NaNO(3). Long-term leaching experiments (up to 8 years) revealed acceleration of the elution process (not detectable in short-term tests), attributable to increase in porosity caused by erosion of the cement matrix. Sorption experiments of Cs(+) ions by cement granules indicated that adsorption on cement pore surfaces is not significant. On the other hand, the leaching tests at two different temperatures or with intermediate changes in temperature between 30 degrees C and 70 degrees C, yielded activation energies that indicated a more complicated kinetic behavior.
The Effect of Micrite on Velocity, Its Sensitivity to Pressure, and Dissolution of Carbonates
NASA Astrophysics Data System (ADS)
El Husseiny, A.; Vanorio, T.
2014-12-01
This study investigates the effect of micrite on the acoustic properties of well-controlled microstructures created in the laboratory to closely mimic carbonate rocks. In particular, we examine the effect of micrite content on the elastic stiffness rock, its sensitivity to pressure, and induced dissolution upon saturation with a reactive fluid. We followed Dunham's classification and fabricated the samples by mixing coarse (sand size) and very fine (micrite size) calcite grains in different ratios, with the addition of cement and then cold-compressing the mixture. The acoustic velocities were measured under bench-top conditions and as functions of confining pressure before and after the injection of a CO2aqueous solution. Our bench-top measurements indicated that micrite makes the frame of the carbonate samples stiffer. Since the sensitivity of the elastic stiffness to pressure decreases as the content of micrite increases (see figure 1), we hypothesize a stiffer pore structure (i.e., rounder pores) in micrite-richer fabrics. Furthermore, the presence of micrite makes the carbonate sample more reactive upon dissolution. The concentration of Ca+2 cations in the fluid measured at the outlet after the injection of the CO2 aqueous solution shows larger dissolution in the micrite-rich samples likely due to the higher surface area of the micrite aggregates. The content of micrite also seems to affect the evolution of stiffness as dissolution proceeds. As the content of micrite increases, the enhanced dissolution translates into a marked softening of the rock frame. We conclude that the content of micrite can play an important role in the complex rock-fluid interaction of carbonates as well as when comparing Gassmann's predictions to velocity measurements of saturated carbonates.
Guide to cement-based integrated pavement solutions.
DOT National Transportation Integrated Search
2011-08-01
This guide provides a clear, concise, and cohesive presentation of cement-bound materials options for 10 : specific engineering pavement applications: new concrete pavements, concrete overlays, pervious concrete, : precast pavements, roller-compacted...
NASA Astrophysics Data System (ADS)
Yuan, Lijian
This thesis investigates the structure-property relations for the calcium silicate hydrate (C-S-H) gel phase in hardened cement pastes (HCP). Studies were performed with the purpose of gaining insight into the origin of the electromechanical behavior and exploring the dynamic nature of the pore structures of HCP during water transport by using an electrically induced strain method. Emphasis was placed on the fundamental characteristics of the electrically induced strains, the role that electrically stimulated water transport through the interconnecting pore structures in HCP plays, as well as the mechanism underlying the induced strains. Reversible and irreversible components of the induced strains were distinguished under ac electric field. Evidence showed that the reversible strains were due to redistribution of water along the structure of the pore network of specimens, whereas the irreversible strains were related to long-range water transport toward the surface of specimens. In contrast, the contractive strains were found following the water loss during measurements. Investigations as a function of measurement frequency revealed a strong relaxation of the induced strains in the frequency range from 6.7 × 10sp{-3} to 1 Hz. The strong relaxation in the induced strains with electric field was found to be due to space charge polarization and a creep-like deformation. The induced strains were shown to be strongly affected by changes in the gel pore structures. The magnitude of the induced strains was found to be significantly dependent on the moisture content adsorbed. Evidence of a critical percolation of pore solution was also observed. A strong decrease in the induced strains was observed with decreasing temperature due to the influence of ice formation. This decrease was interpreted in terms of a decrease in the electroosmotic volumetric flux and hydraulic permeability with decreasing temperature. The strong non-linearity in the induced strains was found with respect to the electric field strength. The presence of non-linear electric streaming current vs. electric field characteristics was examined, which was modeled by using an electrokinetic equation of state. Evidence of an anomalous temperature dependence in both electrical conductivity and dielectric permitivity was observed, indicating the presence of anomalies associated with a percolation-like transition.
A pilot study of the marginal adaptation and surface morphology of glass-cermet cements.
Chu, C H; King, N M; Lee, A M; Yiu, C K; Wei, S H
1996-07-01
This study investigated changes in the marginal adaptation and surface morphology of Ketac-Silver and Chelon-Silver glass-current cements over time. Dispersalloy amalgam was used as a control. Contralateral pairs of carious primary molars were restored with the test materials and amalgam. Clinical evaluations were scheduled at 12, 18, and 24 months after placement. Gold-plated replicas of the restorations were observed with scanning electron microscopy. Fractures and cracks in the surface of the Dispersalloy and Chelon-Silver increased the surface roughness; however, the damage was superficial and self-limiting in the Dispersalloy restorations, while in Chelon-Silver the fractures caused the material to break down in layers. A substantial quantity of pores, usually smaller than 50 microns in diameter, were observed throughout the surface of the Chelon-Silver restorations. The pores in the surface of Ketac-Silver were fewer and smaller. The incidence of cavomarginal breakdown increased with time. Chelon-Silver restorations had a higher rate of cavomarginal breakdown than did Ketac-Silver and Dispersalloy restorations up to 18 months. However, there was no statistically significant difference in the marginal adaptation of the three groups at 24 months.
NASA Astrophysics Data System (ADS)
Papatzani, Styliani; Grammatikos, Sotirios; Adl-Zarrabi, Bijan; Paine, Kevin
2018-04-01
In the present paper, the effect of three different types of nano-montmorillonite dispersions (nMt) on the (i) microstructure as witnessed by Scanning Electron Microscopy, (ii) long term density measurements and (iii) pore structure as determined via Mercury Intrusion Porosimetry of Portland - limestone cement formulations have been compared, in an effort to determine the upper and lower bound of nMt addition in cementitious nanocomposites. The reference formulation, contained 60% PC and 40% LS by mass of binder aiming at the minimization of clinker and maximization of other constituents. Two aqueous organomodified NMt dispersions (one dispersed with non-ionic fatty alcohol and the other with anionic alkyl aryl sulphonate) and one aqueous inorganic NMt dispersion (dispersed with sodium tripolyphosphate) were added at 0.5, 1, 2, 4 and 5.5% by mass of solids as replacement of Portland cement. The water to solids ratio was kept constant at 0.3. The inorganic nMt showed the greatest potentials for microstructural enhancement. The way in which the level of the nMt platelet separation affected the pastes was discussed. The research reported was part of a much broader project supported by the EU.
Can the three pore model correctly describe peritoneal transport of protein?
Waniewski, Jacek; Poleszczuk, Jan; Antosiewicz, Stefan; Baczynński, Daniel; Gałach, Magda; Pietribiasi, Mauro; Wanńkowicz, Zofia
2014-01-01
The three pore model (3PM) includes large pores for the description of protein leak to the peritoneal cavity during peritoneal dialysis. However, the reliability of this description has been not fully tested against clinical data yet. Peritoneal transport parameters were estimated using 3PM, extended 3p model (with estimation of fraction of large pores, ext3PM), ext3PM with modified size of pores and proteins (mext3PM), and simplified two pore (2PM, small and ultrasmall pores) models for 32 patients on peritoneal dialysis investigated using the sequential peritoneal equilibration test (consecutive peritoneal equilibration test [PET]: glucose 2.27%, 4 h, and miniPET: glucose 3.86%, 1 h). Urea, creatinine, glucose, sodium, phosphate, albumin, and IgM concentrations were measured in dialysis fluid and plasma. Ext3PM and mext3PM, with large pore fraction of about 0.14, provided a good description of fluid and small solute kinetics, but their predictions for albumin transport were less accurate. Two pore model precisely described the data on fluid and small solute transport. The 3p models could not describe the diffusive-convective transport of albumin as precisely as the transport of fluid, small solutes, and IgM. The 2p model (not applicable for proteins) was an efficient tool for modeling fluid and small solute transport.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Stulajterova, R., E-mail: rstulajterova@saske.sk
Tetracalcium phosphate/nanomonetite (TTCPMH) cement composites with 7.5 and 15 wt% addition of melt-derived 45S5 bioactive glass were prepared by mechanical homogenization of powder components and 2% NaH{sub 2}PO{sub 4} solution was used as a hardening liquid. The properties of composites with the acidic (Ca/P ratio equal 1.5) or basic (Ca/P ratio equal 1.67) TTCPMH component were compared. Addition of glass component caused rapid rise in pH of composites up to 10. In microstructure of basic cement composite, the large bioglass particles weakly bounded to surrounding cement matrix were found contrary to a more compact microstructure of acidic cement composites withmore » the high number of spherical silica particles. Both the significant refinement of hydroxyapatite particles and the change to needle-like morphology with rise in the content of bioglass were identified in hydroxyapatite coatings created during soaking of composites in phosphate buffered saline. In acidic cement mixtures, the increase of compressive strength with an amount of bioglass was found whereas the opposite tendency was revealed in the case of basic cement mixtures. The higher concentrations of ions were verified in solutions after immersion of acidic cement composites. The severe cytotoxicity of extracts and composite cement substrates containing 15 wt% of bioglass demonstrated adverse effects of both the ionic concentrations and unappropriate surface texture on proliferation of mesenchymal stem cells. The enhanced ALP activities of cells cultured on composite cements confirmed the positive effect of bioactive glass addition on differentiation of mesenchymal stem cells. - Highlights: • Novel B45S5 bioglass/tetracalcium phosphate/nanomonetite cement composites • Cement basicity negatively affected their microstructure. • Acid composite cements had higher compressive strengths than basic composites. • Fast differentiation of MSC to osteoblast line on composite with 7.5 wt% of bioglass • Severe cytotoxicity of 24 h extracts from composites with 15 wt% of bioglass.« less
An, Jie; Leeuwenburgh, Sander C G; Wolke, Joop G C; Jansen, John A
2015-11-01
In vitro degradation rates of calcium phosphate bioceramics are investigated using a large variation of soaking protocols that do not all match the dynamic conditions of the perfused physiological environment. Therefore, we studied the effect of stirring and fluid perfusion on the in vitro degradation rate of apatitic calcium phosphate cements (CPC) containing poly(lactic-co-glycolic acid) (PLGA) microspheres. The composites were soaked in phosphate-buffered saline up to 6 weeks under unstirred, stirred, or perfused conditions followed by analysis of mass loss, compression strength, porosity, crystal phase composition, and morphology of the cement composites. The results showed that fluid perfusion reduced the decrease in pH and corresponding degradation rates, while nonperfused soaking conditions (i.e., stirred and unstirred conditions) resulted into more extensive acidification, the rate of which increased with stirring. After 2 weeks, the formation of a secondary brushite phase was observed for cement composites soaked under nonperfused (i.e., stirred and unstirred) conditions, whereas this phase was not detected in cements soaked under perfused conditions. The degradation rate of cement composites decreased in the order unstirred>stirred>perfused, as evidenced by quantification of mass loss, compression strength, and pore morphology. To summarize, we have demonstrated that soaking conditions strongly affected the in vitro degradation process of CPCs. As a consequence, it can be concluded that the experimental design of current in vitro degradation studies does not allow for correlation to (pre-)clinical studies.
Dong, Jingjing; Cui, Geng; Bi, Long; Li, Jie; Lei, Wei
2013-01-01
In order to improve the mechanical and biological properties of calcium phosphate cement (CPC, nanometer-biomaterial) for bone reconstruction in the rabbit femoral defect model, fibrin glue (FG, the natural product, purified from the blood) was introduced at three different ratios. The CPC powder and the FG solution were mixed, respectively, at the powder/liquid (P/L) ratios (g/mL) of 1:1, 3:1, and 5:1 (g/mL), and pure CPC was used as a control. After being implanted into the femoral defect in rabbit, the healing process was evaluated by micro-computed tomography scan, biomechanical testing, and histological examination. By micro-computed tomography analysis, the P/L ratio of 1:1 (g/mL) group indicated the largest quantity of new bone formation at 4 weeks, 8 weeks, and 12 weeks after implantation, respectively. Bone volume per trabecular volume of the 1:1 group was highest in the four groups, which was 1.45% ± 0.42%, 7.35% ± 1.45%, and 29.10% ± 1.67% at 4 weeks, 8 weeks, and 12 weeks after the operation, respectively. In the biomechanical tests, the compressive strength and the elastic modulus of the three CPC–FG groups were much higher than those of the pure CPC group at the determined time point (P < 0.05). The histological evaluation also showed the best osseointegration in the 1:1 group at 4 weeks, 8 weeks, and 12 weeks after the operation, respectively. In the 1:1 group, the bone grew into the pore of the cement in the laminar arrangement and connected with the cement tightly at the 12th week after the operation. This present study indicated that the CPC–FG composite at the P/L ratio of 1:1 (g/mL) stimulated bone regeneration better than any other designed group, which suggested that CPC–FG at the P/L ratio of 1:1 has significant potential as the bioactive material for the treatment of bone defects. PMID:23576869
Diagenesis and porosity preservation in Eocene microporous limestones, South Florida, USA
NASA Astrophysics Data System (ADS)
Maliva, Robert G.; Missimer, Thomas M.; Clayton, Edward A.; Dickson, J. A. D.
2009-05-01
Microporous limestones may contain immobile, capillary-bound (irreducible) water that is only in diffusional contact with mobile pore waters or in some reservoirs may contain producible hydrocarbons. The preservation and distribution of microporosity impact both subsurface fluid flow and solute transport. The diagenesis of microporous limestones has received relatively little attention because their very fine grains and cements are not amenable to standard analytical methods. The Ocala Limestone (Upper Eocene) and upper Avon Park Formation (Middle Eocene) in South Florida contain microporous micritic limestones (mudstones to packstones) that are at an intermediate stage of diagenesis. The limestones have been exposed to the active near-surface environment, but have not yet reached a burial depth sufficient for intense chemical compaction and associated porosity reduction. Nuclear magnetic resonance (NMR) logging allowed for the quantification of total porosity, pore-size distribution, and permeability. The Ocala Limestone and Avon Park Formation have different predominant microfacies and porosity size distributions, but yet both retain total porosities predominantly between 35% and 37%. Estimated microporosities range mostly between 12% and 45%. The mudstones and wackestones of the Ocala Limestone have significantly lower permeabilities (mostly 3 to 12 md) than the wackestones to grainstones of the Avon Park Formation (commonly in the 100 to 3000 md range), which have more mixed and overall coarser pore sizes. Computer modeling using carbon and oxygen stable data indicates that the studied microporous limestones underwent only a low degree of chemical diagenetic alteration, despite likely experiencing episodes of freshwater flushing associated with post-depositional sea-level lowstands. The Ocala Limestone and Avon Park Formation limestones illustrate the general concept that total porosity is often largely preserved through early diagenesis (although may undergo intra-formational redistribution) and that confined aquifers are diagenetic quiescent environments.
Jang, Jae-Kyeong; Kim, Hong-Gi; Kim, Jun-Hyeong; Ryou, Jae-Suk
2018-05-14
Concrete systems exposed to deicers are damaged in physical and chemical ways. In mitigating the damage from CaCl₂ deicers, the usage of ground slag cement and MgO are investigated. Ordinary Portland cement (OPC) and slag cement are used in different proportions as the binding material, and MgO in doses of 0%, 5%, 7%, and 10% are added to the systems. After 28 days of water-curing, the specimens are immersed in 30% CaCl₂ solution by mass for 180 days. Compressive strength test, carbonation test, chloride penetration test, chloride content test, XRD analysis, and SEM-EDAX analysis are conducted to evaluate the damage effects of the deicing solution. Up to 28 days, plain specimens with increasing MgO show a decrease in compressive strength, an increase in carbonation resistance, and a decrease in chloride penetration resistance, whereas the S30- and S50- specimens show a slight increase in compressive strength, an increase in carbonation resistance, and a slight increase in chloride penetration resistance. After 180 days of immersion in deicing solution, specimens with MgO retain their compressive strength longer and show improved durability. Furthermore, the addition of MgO to concrete systems with slag cement induces the formation of magnesium silicate hydrate (M-S-H) phases.
Influence of Hemostatic Solution on Bond Strength and Physicochemical Properties of Resin Cement.
Araújo, Isabela Sousa de; Prado, Célio Jesus do; Raposo, Luís Henrique Araújo; Soares, Carlos José; Zanatta, Rayssa Ferreira; Torres, Carlos Rocha Gomes; Ruggiero, Reinaldo; Silva, Gisele Rodrigues da
2017-01-01
The aim of this study was to evaluate the degree of conversion, color stability, chemical composition, and bond strength of a light-cured resin cement contaminated with three different hemostatic solutions. Specimens were prepared for the control (uncontaminated resin cement) and experimental groups (resin cement contaminated with one of the hemostatic solutions) according to the tests. For degree of conversion, DC (n = 5) and color analyses (n = 10), specimens (3 mm in diameter and 2 mm thick) were evaluated by Fourier transform infrared spectroscopy (FTIR) and CIELAB spectrophotometry (L*, a*, b*), respectively. For elemental chemical analysis (n = 1), specimens (2 mm thick and 6 mm in diameter) were evaluated by x-ray energy-dispersive spectroscopy (EDS). The bond strengths of the groups were assessed by the microshear test (n = 20) in a leucite-reinforced glass ceramic substrate, followed by failure mode analysis by scanning electron microscopy (SEM). The mean values, except for the elemental chemical evaluation and failure mode, were evaluated by ANOVA and Tukey's HSD test. The color stability was influenced by storage time (p<0.001) and interaction between contamination and storage time (p<0.001). Hemostop and Viscostat Clear contamination did not affect the DC, however Viscostat increased the DC. Bond strength of the resin cement to ceramic was negatively affected by the contaminants (p<0.001). Contamination by hemostatic agents affected the bond strength, degree of conversion, and color stability of the light-cured resin cement tested.
Ye, Rongda; Fang, Xiaoming; Zhang, Zhengguo; Gao, Xuenong
2015-01-01
Here we demonstrate the mechanical properties, thermal conductivity, and thermal energy storage performance of construction elements made of cement and form-stable PCM-Rubitherm® RT 28 HC (RT28)/expanded perlite (EP) composite phase change materials (PCMs). The composite PCMs were prepared by adsorbing RT28 into the pores of EP, in which the mass fraction of RT28 should be limited to be no more than 40 wt %. The adsorbed RT28 is observed to be uniformly confined into the pores of EP. The phase change temperatures of the RT28/EP composite PCMs are very close to that of the pure RT28. The apparent density and compression strength of the composite cubes increase linearly with the mass fraction of RT28. Compared with the thermal conductivity of the boards composed of cement and EP, the thermal conductivities of the composite boards containing RT28 increase by 15%–35% with the mass fraction increasing of RT28. The cubic test rooms that consist of six boards were built to evaluate the thermal energy storage performance, it is found that the maximum temperature different between the outside surface of the top board with the indoor temperature using the composite boards is 13.3 °C higher than that of the boards containing no RT28. The thermal mass increase of the built environment due to the application of composite boards can contribute to improving the indoor thermal comfort and reducing the energy consumption in the buildings. PMID:28793671
NASA Astrophysics Data System (ADS)
Marsaglia, K. M.; Carozzi, A. V.
The Basal Salina Formation is a lower Eocene transgressive sequence consisting of interbedded shales, siltstones, and conglomeratic sandstones. This formation occurs in the Talara basin of northwestern Peru and is one of a series of complexly faulted hydrocarbon-producing formations within this extensional forearc basin. These sediments were probably deposited in a fan-delta complex that developed along the ancestral Amotape Mountains during the early Eocene. Most of the sediment was derived from the low-grade metamorphic and plutonic rocks that comprise the Amotape Mountains, and their sedimentary cover. Detrital modes of these sandstones reflect the complex tectonic history of the area, rather than the overall forearc setting. Unlike most forearc sediments, these are highly quartzose, with only minor percentages of volcanic detritus. This sand is variably indurated and cemented by chlorite, quartz, calcite, and kaolinite. Clay-mineral matrix assemblages show gradational changes with depth, from primarily detrital kaolinite to diagenetic chlorite and mixed-layered illite/smectite. Basal Salina sandstones exhibit a paragenetic sequence that may be tied to early meteoric influx or late-stage influx of thermally driven brines associated with hydrocarbon migration. Much of the porosity is secondary, resulting from a first-stage dissolution of silicic constituents (volcanic lithic fragments, feldspar, and fibrous quartz) and a later dissolution of surrounding carbonate cement. Types of pores include skeletal grains, grain molds, elongate pores, and fracture porosity. Measured porosity values range up to 24% and coarser samples tend to be more porous. Permeability is enhanced by fractures and deterred by clay-mineral cements and alteration residues.
Ye, Rongda; Fang, Xiaoming; Zhang, Zhengguo; Gao, Xuenong
2015-11-13
Here we demonstrate the mechanical properties, thermal conductivity, and thermal energy storage performance of construction elements made of cement and form-stable PCM-Rubitherm® RT 28 HC (RT28)/expanded perlite (EP) composite phase change materials (PCMs). The composite PCMs were prepared by adsorbing RT28 into the pores of EP, in which the mass fraction of RT28 should be limited to be no more than 40 wt %. The adsorbed RT28 is observed to be uniformly confined into the pores of EP. The phase change temperatures of the RT28/EP composite PCMs are very close to that of the pure RT28. The apparent density and compression strength of the composite cubes increase linearly with the mass fraction of RT28. Compared with the thermal conductivity of the boards composed of cement and EP, the thermal conductivities of the composite boards containing RT28 increase by 15%-35% with the mass fraction increasing of RT28. The cubic test rooms that consist of six boards were built to evaluate the thermal energy storage performance, it is found that the maximum temperature different between the outside surface of the top board with the indoor temperature using the composite boards is 13.3 °C higher than that of the boards containing no RT28. The thermal mass increase of the built environment due to the application of composite boards can contribute to improving the indoor thermal comfort and reducing the energy consumption in the buildings.
Using Natural Cementation Systems to Control Corrosion Dust on Un-surfaced Roads
2010-02-01
metallurgical slags ), volcanic glass , fly ash and low-fired clays • Can use waste alkali from manufacturing operations • No Portland cement is involved Soil...solidified with alkali- activated glass slag US Army Corps of Engineers 4 Pohakuloa Training Area (PTA) as a Test Site • Serious dust problem at site...Conventional Cement? • Glass can be both the aggregate and form the cementing phase • Waste glass ( slag , fly ash) can be used • More alkaline solution is
Phosphate-bonded calcium aluminate cements
Sugama, Toshifumi
1993-01-01
A method is described for making a rapid-setting phosphate-bonded cementitious material. A powdered aluminous cement is mixed with an aqueous solution of ammonium phosphate. The mixture is allowed to set to form an amorphous cementitious material which also may be hydrothermally treated at a temperature of from about 120.degree. C. to about 300.degree. C. to form a crystal-containing phosphate-bonded material. Also described are the cementitious products of this method and the cement composition which includes aluminous cement and ammonium polyphosphate.
Phosphate-bonded calcium aluminate cements
Sugama, T.
1993-09-21
A method is described for making a rapid-setting phosphate-bonded cementitious material. A powdered aluminous cement is mixed with an aqueous solution of ammonium phosphate. The mixture is allowed to set to form an amorphous cementitious material which also may be hydrothermally treated at a temperature of from about 120 C to about 300 C to form a crystal-containing phosphate-bonded material. Also described are the cementitious products of this method and the cement composition which includes aluminous cement and ammonium polyphosphate. 10 figures.
Electrical conductivity modeling in fractal non-saturated porous media
NASA Astrophysics Data System (ADS)
Wei, W.; Cai, J.; Hu, X.; Han, Q.
2016-12-01
The variety of electrical conductivity in non-saturated conditions is important to study electric conduction in natural sedimentary rocks. The electrical conductivity in completely saturated porous media is a porosity-function representing the complex connected behavior of single conducting phases (pore fluid). For partially saturated conditions, the electrical conductivity becomes even more complicated since the connectedness of pore. Archie's second law is an empirical electrical conductivity-porosity and -saturation model that has been used to predict the formation factor of non-saturated porous rock. However, the physical interpretation of its parameters, e.g., the cementation exponent m and the saturation exponent n, remains questionable. On basis of our previous work, we combine the pore-solid fractal (PSF) model to build an electrical conductivity model in non-saturated porous media. Our theoretical porosity- and saturation-dependent models contain endmember properties, such as fluid electrical conductivities, pore fractal dimension and tortuosity fractal dimension (representing the complex degree of electrical flowing path). We find the presented model with non-saturation-dependent electrical conductivity datasets indicate excellent match between theory and experiments. This means the value of pore fractal dimension and tortuosity fractal dimension change from medium to medium and depends not only on geometrical properties of pore structure but also characteristics of electrical current flowing in the non-saturated porous media.
Erosion of water-based cements evaluated by volumetric and gravimetric methods.
Nomoto, Rie; Uchida, Keiko; Momoi, Yasuko; McCabe, John F
2003-05-01
To compare the erosion of glass ionomer, zinc phosphate and polycarboxylate cements using volumetric and gravimetric methods. For the volumetric method, the eroded depth of cement placed in a cylindrical cavity in PMMA was measured using a dial gauge after immersion in an eroding solution. For the gravimetric method, the weight of the residue of a solution in which a cylindrical specimen had been immersed was measured. 0.02 M lactic acid solution (0.02 M acid) and 0.1 M lactic acid/sodium lactate buffer solution (0.1 M buffer) were used as eroding solutions. The pH of both solutions was 2.74 and the test period was 24 h. Ranking of eroded depth and weight of residue was polycarboxylate>zinc phosphate>glass ionomers. Differences in erosion were more clearly defined by differences in eroded depth than differences in weight of residue. In 0.02 M acid, the erosion of glass ionomer using the volumetric method was effected by the hygroscopic expansion. In 0.1 M buffer, the erosion for polycarboxylate and zinc phosphate using the volumetric method was much greater than that using the gravimetric method. This is explained by cryo-SEM images which show many holes in the surface of specimens after erosion. It appears that zinc oxide is dissolved leaving a spongy matrix which easily collapses under the force applied to the dial gauge during measurement. The volumetric method that employs eroded depth of cement using a 0.1 M buffer solution is able to quantify erosion and to make material comparisons.
Chloride Ion Adsorption Capacity of Anion Exchange Resin in Cement Mortar
Lee, Hanseung; Jung, Dohyun; Chen, Zhengxin
2018-01-01
This paper presents the effect of anion exchange resin (AER) on the adsorption of chloride ions in cement mortar. The kinetic and equilibrium behaviors of AER were investigated in distilled water and Ca(OH)2 saturated solutions, and then the adsorption of chloride ions by the AER in the mortar specimen was determined. The AER was used as a partial replacement for sand in the mortar specimen. The mortar specimen was coated with epoxy, except for an exposed surface, and then immersed in a NaCl solution for 140 days. The chloride content in the mortar specimen was characterized by energy dispersive X-ray fluorescence analysis and electron probe microanalysis. The results showed that the AER could adsorb the chloride ions from the solution rapidly but had a relatively low performance when the pH of its surrounding environment increased. When the AER was mixed in the cement mortar, its chloride content was higher than that of the cement matrix around it, which confirms the chloride ion adsorption capacity of the AER. PMID:29621188
Yao, Yan; Lenhoff, Abraham M
2004-05-28
The macroscopic properties of porous chromatographic adsorbents are directly influenced by the pore structure, with the pore size distribution (PSD) playing a major role beyond simply the mean pore size. Inverse size-exclusion chromatography (ISEC), a widely used chromatographic method for determining the PSD of porous media, provides more relevant information on liquid chromatographic materials in situ than traditional methods, such as gas sorption and mercury intrusion. The fundamentals and applications of ISEC in the characterization of the pore structure are reviewed. The description of the probe solutes and the pore space, as well as theoretical models for deriving the PSD from solute partitioning behavior, are discussed. Precautions to ensure integrity of the experiments are also outlined, including accounting for probe polydispersity and minimization of solute-adsorbent interactions. The results that emerge are necessarily model-dependent, but ISEC nonetheless represents a powerful and non-destructive source of quantitative pore structure information that can help to elucidate chromatographic performance observations covering both retention and rate aspects.
Pore- and micro-structural characterization of a novel structural binder based on iron carbonation
DOE Office of Scientific and Technical Information (OSTI.GOV)
Das, Sumanta, E-mail: Sumanta.Das@asu.edu; Stone, David, E-mail: dajstone@gmail.com; Convey, Diana, E-mail: Diana.Convey@asu.edu
2014-12-15
The pore- and micro-structural features of a novel binding material based on the carbonation of waste metallic iron powder are reported in this paper. The binder contains metallic iron powder as the major ingredient, followed by additives containing silica and alumina to facilitate favorable reaction product formation. Compressive strengths sufficient for a majority of concrete applications are attained. The material pore structure is investigated primarily through mercury intrusion porosimetry whereas electron microscopy is used for microstructural characterization. Reduction in the overall porosity and the average pore size with an increase in carbonation duration from 1 day to 4 days ismore » noticed. The pore structure features are used in predictive models for gas and moisture transport (water vapor diffusivity and moisture permeability) through the porous medium which dictates its long-term durability when used in structural applications. Comparisons of the pore structure with those of a Portland cement paste are also provided. The morphology of the reaction products in the iron-based binder, and the distribution of constituent elements in the microstructure are also reported. - Highlights: • Carbonation of iron produces a dense microstructure. • Pore volume in iron carbonate lower, critical size higher than those in OPC pastes • Reaction product contains iron, carbon, silicon, aluminum and calcium. • Power-law for porosity-moisture permeability relationship was established.« less
NASA Astrophysics Data System (ADS)
Zhou, BeiBei; Wang, QuanJiu
2017-09-01
Studies on solute transport under different pore water velocity and solute input methods in undisturbed soil could play instructive roles for crop production. Based on the experiments in the laboratory, the effect of solute input methods with small pulse input and large pulse input, as well as four pore water velocities, on chloride transport in the undisturbed soil columns obtained from the Loess Plateau under controlled condition was studied. Chloride breakthrough curves (BTCs) were generated using the miscible displacement method under water-saturated, steady flow conditions. Using the 0.15 mol L-1 CaCl2 solution as a tracer, a small pulse (0.1 pore volumes) was first induced, and then, after all the solution was wash off, a large pulse (0.5 pore volumes) was conducted. The convection-dispersion equation (CDE) and the two-region model (T-R) were used to describe the BTCs, and their prediction accuracies and fitted parameters were compared as well. All the BTCs obtained for the different input methods and the four pore water velocities were all smooth. However, the shapes of the BTCs varied greatly; small pulse inputs resulted in more rapid attainment of peak values that appeared earlier with increases in pore water velocity, whereas large pulse inputs resulted in an opposite trend. Both models could fit the experimental data well, but the prediction accuracy of the T-R was better. The values of the dispersivity, λ, calculated from the dispersion coefficient obtained from the CDE were about one order of magnitude larger than those calculated from the dispersion coefficient given by the T-R, but the calculated Peclet number, Pe, was lower. The mobile-immobile partition coefficient, β, decreased, while the mass exchange coefficient increased with increases in pore water velocity.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Liu, Jun; Qiu, Qiwen; Chen, Xiaochi
An experimental study is carried out with the aim to understand the interacted mechanism between carbonation and chloride aerosol attack in ordinary Portland cement (OPC) concrete. Effects of carbonation on the chloride profile, the chloride binding capacity and the chloride diffusion coefficient are evaluated. Besides, effect of chloride aerosol attack on the carbonation rate is investigated. Concrete specimens with three water-to-cement ratios (0.38, 0.47 and 0.53) are fabricated in this work. Tested results demonstrate that carbonation remarkably affects the chloride profile, reduces the chloride binding capacity, and also accelerates the rate of chloride ion diffusion of concrete. Besides, the presencemore » of chloride aerosol can lead to lower the carbonation depth and increase the pH value of carbonated concrete. Microscopic properties such as morphology, porosity, and pore size distribution for the contaminated concretes are explored by scanning electron microscope and mercury intrusion porosimetry, which provide strong evidence to these research findings.« less
Onondage pinnacle reefs in New York State
DOE Office of Scientific and Technical Information (OSTI.GOV)
Friedman, G.M.
1995-09-01
Onondaga pinnacle reefs, part of the Onondaga Formation, developed in an epeiric setting of the lowermost Middle Devonian (Eifelian). The reefs were initiated as coral-crinoidal mounds in the Edgecliff Member of the formation. Whereas most Devonian reefs are composed of rugose corals. Coral is the predominant kind of fossil, followed by crinoids, brachiopods, mollusks, undifferentiated skeletal debris, and possible sponges. The initial mineralogy of the corals is inferred to have been calcite. The porosity of these reefs is almost unique among reef reservoirs. most reefs produce from secondary or diagenetic porosity; by contrast Onondaga reefs display primary intracoralline or frameworkmore » porosity. Between framework builders and/or skeletal particles cryptocrystalline/microcrystalline cement fills pores. As observed in modern reefs this kind of cement resembles micrite, but probable formed as high-magnesian calcite in a high-energy setting. Syntaxial or rim cement common lines crinoid particles. Some of these pinnacle reefs, formerly gas producers, are presently under development as gas-storage reservoirs.« less
The fracture strength and frictional strength of Weber Sandstone
Byerlee, J.D.
1975-01-01
The fracture strength and frictional strength of Weber Sandstone have been measured as a function of confining pressure and pore pressure. Both the fracture strength and the frictional strength obey the law of effective stress, that is, the strength is determined not by the confining pressure alone but by the difference between the confining pressure and the pore pressure. The fracture strength of the rock varies by as much as 20 per cent depending on the cement between the grains, but the frictional strength is independent of lithology. Over the range 0 2 kb, ??=0??5 + 0??6??n. This relationship also holds for other rocks such as gabbro, dunite, serpentinite, granite and limestone. ?? 1975.
Zuo, Yibing; Ye, Guang
2018-06-19
The pore structure of alkali-activated slag has a significant influence on its performance. However, the literature shows insufficient studies regarding the suitability of different techniques for characterizing the pore structure and the influences of Na₂O and curing age on pore structure development. In pursuit of a better understanding, the pore structure of sodium hydroxide activated slag paste was characterized by multiple techniques, e.g., mercury intrusion porosimetry (MIP), nitrogen (N₂) adsorption, and scanning electron microscopy (SEM) image analysis. The sodium hydroxide activated slag pastes were prepared with three different contents of Na₂O (Na₂O/slag = 4, 6, and 8%) and cured for different times up to 360 days. The microstructure observation reveals that outer C⁻(N⁻)A⁻S⁻H and inner C⁻(N⁻)A⁻S⁻H grow successively around the reacting slag grains, along with crystalline reaction products which are formed in the empty coarse pore space. The increase of Na₂O content and curing age lead to a finer pore structure. The MIP measurements show that the total porosity drops about 70% within the first day, and that one peak at most, corresponding to gel pores, was identified in the differential curves of all the investigated samples from 1 to 360 days. On the contrary, only one peak, corresponding to capillary pores, was identified by SEM-image analysis. The differential curves derived from N₂ adsorption generally reveal two peaks, and the trend that the pore diameters of those two peaks vary with curing age depends on the content of Na₂O. Compared to Portland cement, sodium hydroxide activated slag has a higher pore space filling capacity ( χ , V products / V slag-reacted ), while the capacity decreases with increasing Na₂O content and curing age.
Antiwashout behavior of calcium phosphate cement incorporated with Poly(ethylene glycol)
NASA Astrophysics Data System (ADS)
Hablee, S.; Sopyan, I.; Mel, M.; Salleh, H. M.; Rahman, M. M.
2018-01-01
The effect of powder-to-liquid ratio and addition of poly(ethylene glycol) on the antiwashout behavior of calcium phosphate cement has been investigated. Calcium hydroxide, Ca(OH)2, and diammonium hydrogen phosphate, (NH4)2HPO4, were used as precursors with distilled water as the solvent in the wet chemical precipitation synthesis of hydroxyapatite powder. Cement paste was prepared by mixing the as-synthesized powder with distilled water at certain ratios, varied at 1.0, 1.3, 1.5 and 1.6. Poly(ethylene glycol) was added into distilled water, varied at 1, 2, 3, 4 and 5 wt% using the powder-to-liquid ratio of 1.3. The antiwashout properties of the cement has been investigated by soaking in Ringer’s solution for 3 and 7 days. The evolution of compressive strength of calcium phosphate cement before and after soaking have been determined. After 7 days soaking, the strength of the cement increased by 94.4%, 2.98%, 11.39% and 111.29% for powder-to-liquid ratios 1.0, 1.3, 1.5 and 1.6 respectively. The addition of poly(ethylene glycol) up to 3% shows an increase in strength after 7 days soaking, with 57.75%, 16.4% and 19.97% increase for 1, 2 and 3% poly(ethylene glycol) contents respectively. The calcium phosphate cement produced in this current study shows excellent antiwashout behavior since no cement dissolution happened and the compressive strength of the cement increased with soaking time throughout 7 days soaking in Ringer’s solution.
Subsurface Endospore-Forming Bacteria Possess Bio-Sealant Properties.
Basha, Sreenivasulu; Lingamgunta, Lakshman Kumar; Kannali, Jayakumar; Gajula, Swarna Kumari; Bandikari, Ramesh; Dasari, Sreenivasulu; Dalavai, Veena; Chinthala, Paramageetham; Gundala, Prasada Babu; Kutagolla, Peera; Balaji, Vinodh Kumar
2018-04-24
Concrete is a strong and fairly inexpensive building substance, but has several disadvantages like cracking that allows corrosion, thus reducing its lifespan. To mitigate these complications, long-lasting microbial self-healing cement is an alternative that is eco-friendly and also actively repairs cracks. The present paper describes the detailed experimental investigation on compressive strength of cement mortars, mixed with six alkaliphilic bacteria, isolated from subsurface mica mines of high alkalinity. The experiments showed that the addition of alkaliphilic isolates at different cell concentrations (10 4 and 10 6 cells/ml) enhanced the compressive strength of cement mortar, because the rapid growth of bacteria at high alkalinity precipitates calcite crystals that lead to filling of pores and densifying the concrete mix. Thus, Bacillus subtilis (SVUNM4) showed the highest compressive strength (28.61%) of cement mortar at 10 4 cells/ml compared to those of other five alkaliphilic isolates (Brevibacillus sp., SVUNM15-22.1%; P. dendritiformis, SVUNM11-19.9%; B. methylotrophicus, SVUNM9-16%; B. licheniformis, SVUNM14-12.7% and S. maltophilia, SVUNM13-9.6%) and controlled cement mortar as well. This method resulted in the filling of cracks in concrete with calcite (CaCO 3 ), which was observed by scanning electron microscopy (SEM). Our results showed that the alkaliphilic bacterial isolates used in the study are effective in self-healing and repair of concrete cracks.
Skeletal aragonite dissolution from hypersaline seawater: a hypothesis
NASA Astrophysics Data System (ADS)
Qing Sun, S.
1992-05-01
Hypersaline seawater has often been invoked as a mechanism to explain the pervasive dolomitization of ancient platform carbonates, but its potential in causing skeletal aragonite dissolution of these carbonates has rarely been investigated. Previous experimental and theoretical studies have demonstrated that hypersaline seawater is undersaturated with respect to aragonite when evaporation reaches a certain degree. It is contended here that similar undersaturation could also have occurred in ancient evaporitic seas. Geological evidence from the Miocene carbonates of SE Spain, Gulf of Suez, Red Sea and Iraq suggests that this may have been the case. Despite differences in their geological settings, these carbonates have common diagenetic features including: (1) widespread dissolution of skeletal aragonite with little or no calcite cementation; and (2) pervasive dolomitization. Dolomite occurs as both a replacement of Mg calcite and mouldic pore-filling cement. The association of the dolomites with evaporites, their relatively heavy oxygen isotopic values and widespread distribution suggest a hypersaline seawater origin of these dolomites. Petrographic data indicate that skeletal aragonite was dissolved during dolomitization because the aragonite fossil moulds contain dolomite cements, but no pre-dolomitization calcite cements, implying that the dolomitizing fluids (hypersaline seawater) were probably undersaturated with respect to aragonite. The dissolved calcium may have been subsequently incorporated into the dolomite. This may help to explain the lack of calcite cementation despite the extensive skeletal aragonite dissolution.
Effect of temperature on the hydration of Portland cement blended with siliceous fly ash
DOE Office of Scientific and Technical Information (OSTI.GOV)
Deschner, Florian, E-mail: florian.deschner@gmail.com; Lothenbach, Barbara; Winnefeld, Frank
2013-10-15
The effect of temperature on the hydration of Portland cement pastes blended with 50 wt.% of siliceous fly ash is investigated within a temperature range of 7 to 80 °C. The elevation of temperature accelerates both the hydration of OPC and fly ash. Due to the enhanced pozzolanic reaction of the fly ash, the change of the composition of the C–S–H and the pore solution towards lower Ca and higher Al and Si concentrations is shifted towards earlier hydration times. Above 50 °C, the reaction of fly ash also contributes to the formation of siliceous hydrogarnet. At 80 °C, ettringitemore » and AFm are destabilised and the released sulphate is partially incorporated into the C–S–H. The observed changes of the phase assemblage in dependence of the temperature are confirmed by thermodynamic modelling. The increasingly heterogeneous microstructure at elevated temperatures shows an increased density of the C–S–H and a higher coarse porosity. -- Highlights: •The reaction of quartz powder at 80 °C strongly enhances the compressive strength. •Almost no strength increase of fly ash blended OPC at 80 °C was found after 2 days. •Siliceous hydrogarnet is formed upon the reaction of fly ash at high temperatures. •Temperature dependent change of the system was simulated by thermodynamic modelling. •Destabilisation of ettringite above 50 °C correlates with sulphate content of C–S–H.« less
Surface and microstructural properties of photocatalytic cements for pavement applications.
DOT National Transportation Integrated Search
2016-10-01
Thin concrete inlays incorporating flowable fibrous concrete (FFC) mix designs as well as titanium dioxide (TiO2)- containing photocatalytic cements are a promising pavement preservation solution. These multi-functional inlays offer enhanced construc...
Effects of Incorporating Carboxymethyl Chitosan into PMMA Bone Cement Containing Methotrexate
Liu, Bo-Ming; Li, Ming; Yin, Bao-Sheng; Zou, Ji-Yang; Zhang, Wei-Guo; Wang, Shou-Yu
2015-01-01
Treatment of bone metastases usually includes surgical resection with local filling of methotrexate (MTX) in polymethyl methacrylate (PMMA) cement. We investigated whether incorporating carboxymethyl chitosan (CMCS) in MTX-PMMA cement might overcome disadvantages associated with MTX. To determine the optimal CMCS+MTX concentration to suppress the viability of cancer cells, an integrated microfluidic chip culturing highly metastatic lung cancer cells (H460) was employed. The mechanical properties, microstructure, and MTX release of (CMCS+MTX)-PMMA cement were evaluated respectively by universal mechanical testing machine, scanning electron microscopy (SEM), and incubation in simulated body fluid with subsequent HPLC-MS. Implants of MTX-PMMA and (CMCS+MTX)-PMMA cement were evaluated in vivo in guinea pig femurs over time using spiral computed tomography with three-dimensional image reconstruction, and SEM at 6 months. Viability of H460 cells was significantly lowest after treatment with 57 μg/mL CMCS + 21 μg/mL MTX, which was thus used in subsequent experiments. Incorporation of 1.6% (w/w) CMCS to MTX-PMMA significantly increased the bending modulus, bending strength, and compressive strength by 5, 2.8, and 5.2%, respectively, confirmed by improved microstructural homogeneity. Incorporation of CMCS delayed the time-to-plateau of MTX release by 2 days, but increased the fraction released at the plateau from 3.24% (MTX-PMMA) to 5.34%. Relative to the controls, the (CMCS+MTX)-PMMA implants integrated better with the host bone. SEM revealed pores in the cement of the (CMCS+MTX)-PMMA implants that were not obvious in the controls. In conclusion, incorporation of CMCS in MTX-PMMA appears a feasible and effective modification for improving the anti-tumor properties of MTX-PMMA cement. PMID:26657526
Effects of Incorporating Carboxymethyl Chitosan into PMMA Bone Cement Containing Methotrexate.
Liu, Bo-Ming; Li, Ming; Yin, Bao-Sheng; Zou, Ji-Yang; Zhang, Wei-Guo; Wang, Shou-Yu
2015-01-01
Treatment of bone metastases usually includes surgical resection with local filling of methotrexate (MTX) in polymethyl methacrylate (PMMA) cement. We investigated whether incorporating carboxymethyl chitosan (CMCS) in MTX-PMMA cement might overcome disadvantages associated with MTX. To determine the optimal CMCS+MTX concentration to suppress the viability of cancer cells, an integrated microfluidic chip culturing highly metastatic lung cancer cells (H460) was employed. The mechanical properties, microstructure, and MTX release of (CMCS+MTX)-PMMA cement were evaluated respectively by universal mechanical testing machine, scanning electron microscopy (SEM), and incubation in simulated body fluid with subsequent HPLC-MS. Implants of MTX-PMMA and (CMCS+MTX)-PMMA cement were evaluated in vivo in guinea pig femurs over time using spiral computed tomography with three-dimensional image reconstruction, and SEM at 6 months. Viability of H460 cells was significantly lowest after treatment with 57 μg/mL CMCS + 21 μg/mL MTX, which was thus used in subsequent experiments. Incorporation of 1.6% (w/w) CMCS to MTX-PMMA significantly increased the bending modulus, bending strength, and compressive strength by 5, 2.8, and 5.2%, respectively, confirmed by improved microstructural homogeneity. Incorporation of CMCS delayed the time-to-plateau of MTX release by 2 days, but increased the fraction released at the plateau from 3.24% (MTX-PMMA) to 5.34%. Relative to the controls, the (CMCS+MTX)-PMMA implants integrated better with the host bone. SEM revealed pores in the cement of the (CMCS+MTX)-PMMA implants that were not obvious in the controls. In conclusion, incorporation of CMCS in MTX-PMMA appears a feasible and effective modification for improving the anti-tumor properties of MTX-PMMA cement.
NASA Astrophysics Data System (ADS)
French, M. E.; Goodwin, L. B.; Boutt, D. F.; Lilydahl, H.
2008-12-01
Natural hydraulic fractures (NHFs) are inferred to form where pore fluid pressure exceeds the least compressive stress; i.e., where the hydraulic fracture criterion is met. Although it has been shown that mechanical heterogeneities serve as nuclei for NHFs, the relative roles of mechanical anisotropy and hydrologic properties in initiating NHFs in porous granular media have not been fully explored. We designed an experimental protocol that produces a pore fluid pressure high enough to exceed the hydraulic fracture criterion, allowing us to initiate NHFs in the laboratory. Initially, cylindrical samples 13 cm long and 5 cm in diameter are saturated, σ1 is radial, and σ3 is axial. By dropping the end load (σ3) and pore fluid pressure simultaneously at the end caps, we produce a large pore fluid pressure gradient parallel to the long axis of the sample. This allows us to meet the hydraulic fracture criterion without separating the sample from its end caps. The time over which the pore fluid remains elevated is a function of hydraulic diffusivity. An initial test with a low diffusivity sandstone produced NHFs parallel to bedding laminae that were optimally oriented for failure. To evaluate the relative importance of mechanical heterogeneities such as bedding versus hydraulic properties, we are currently investigating variably cemented St. Peter sandstone. This quartz arenite exhibits a wide range of primary structures, from well developed bedding laminae to locally massive sandstone. Diagenesis has locally accentuated these structures, causing degree of cementation to vary with bedding, and the sandstone locally exhibits concretions that form elliptical rather than tabular heterogeneities. Bulk permeability varies from k=10-12 m2 to k=10-15 m2 and porosity varies from 5% to 28% in this suite of samples. Variations in a single sample are smaller, with permeability varying no more than an order of magnitude within a single core. Air minipermeameter and tracer tests document this variability at the cm scale. Experiments will be performed with σ3 and the pore pressure gradient both perpendicular and parallel to sub-cm scale bedding. The results of these tests will be compared to those of structurally homogeneous samples and samples with elliptical heterogeneities.
Hydration products and thermokinetic properties of cement-bentonite and cement-chalk mortars
DOE Office of Scientific and Technical Information (OSTI.GOV)
Klyusov, A.A.
1988-08-20
Bentonite and chalk are the most popular auxiliary additives to portland cement for borehole cementation. The authors studied by physicochemical analysis methods (x-ray phase, derivatographic, and scanning and electron microscopy in combination with microdiffraction) the newly formed solid-phase composition of cement-bentonite and cement-chalk mortars (binder-additive ratio 9:1) prepared from portland cement for cold boreholes and 8% calcium chloride solution at a water-mixing ratio of 0.9. The mechanism of the influence of Ca-bentonite and chalk additives on the portland cement hydration rate was ascertained from the heat evolution rate curves. It was found that the phase compositions of the hydration productsmore » are represented in the studied systems by newly formed substances typical for portland cement. It has been noted that Ca-bentonite interacts with the calcium hydroxide of hydrated cement with the formation of hexagonal and cubic calcium hydroaluminates. Unlike Ca-bentonite, chalk does not react with portland cement at normal and reduced temperatures, does not block hydrated cement particles, which, in turn, ensures all other conditions remaining equal, a higher initial rate of hydration of cement-chalk mortar.« less
NASA Astrophysics Data System (ADS)
Miserque, F.; Huet, B.; Azou, G.; Bendjaballah, D.; L'Hostis, V.
2006-11-01
In the context of the prediction of the long-term behaviour of reinforced concrete structures involved in the nuclear waste storage, the corrosion mechanisms of steels have to be assessed. When mild steel rebars are embedded in concrete, the chemical environment of the reinforcement is progressively modified, due to the carbonation of the concrete matrix. This modification leads to the variation of iron oxides properties formed at the steel/concrete interface, and the active corrosion can be initiated. The aim of this study is to evaluate the passivation behaviour and to provide insights into the depassivation of mild steel in concrete pore solution. In a young concrete, due to the alkalinity of the interstitial solution, steel reinforcement remains passive. Immersion tests of mild steel substrate in various alkaline solutions (from pH 13 to 10) have been performed. Due to the low thickness of the corrosion layers formed, X-ray photoelectron spectroscopy has been used to characterize them. In the passive domain, the corrosion products are similar for the various solutions. The corrosion layer is composed of a mixture of Fe3+ and Fe2+. A similar approach is used to determine the depassivation mechanism. The effect of various components such as carbonates, sulfates and silicates resulting from the dissolution of minerals of cement during the carbonation process is investigated. In addition to the surface analysis, the evolution of the electrochemical behaviour as function of the solution nature (pH) is evaluated with the help of electrochemical measurements (free corrosion potential, cyclic voltamperometry).
NASA Astrophysics Data System (ADS)
Beckingham, Lauren E.; Steefel, Carl I.; Swift, Alexander M.; Voltolini, Marco; Yang, Li; Anovitz, Lawrence M.; Sheets, Julia M.; Cole, David R.; Kneafsey, Timothy J.; Mitnick, Elizabeth H.; Zhang, Shuo; Landrot, Gautier; Ajo-Franklin, Jonathan B.; DePaolo, Donald J.; Mito, Saeko; Xue, Ziqiu
2017-05-01
The rates of mineral dissolution reactions in porous media are difficult to predict, in part because of a lack of understanding of mineral reactive surface area in natural porous media. Common estimates of mineral reactive surface area used in reactive transport models for porous media are typically ad hoc and often based on average grain size, increased to account for surface roughness or decreased by several orders of magnitude to account for reduced surface reactivity of field as opposed to laboratory samples. In this study, accessible mineral surface areas are determined for a sample from the reservoir formation at the Nagaoka pilot CO2 injection site (Japan) using a multi-scale image analysis based on synchrotron X-ray microCT, SEM QEMSCAN, XRD, SANS, and FIB-SEM. This analysis not only accounts for accessibility of mineral surfaces to macro-pores, but also accessibility through connected micro-pores in smectite, the most abundant clay mineral in this sample. While the imaging analysis reveals that most of the micro- and macro-pores are well connected, some pore regions are unconnected and thus inaccessible to fluid flow and diffusion. To evaluate whether mineral accessible surface area accurately reflects reactive surface area a flow-through core experiment is performed and modeled at the continuum scale. The core experiment is performed under conditions replicating the pilot site and the evolution of effluent solutes in the aqueous phase is tracked. Various reactive surface area models are evaluated for their ability to capture the observed effluent chemistry, beginning with parameter values determined as a best fit to a disaggregated sediment experiment (Beckingham et al., 2016) described previously. Simulations that assume that all mineral surfaces are accessible (as in the disaggregated sediment experiment) over-predict the observed mineral reaction rates, suggesting that a reduction of RSA by a factor of 10-20 is required to match the core flood experimental data. While the fit of the effluent chemistry (and inferred mineral dissolution rates) greatly improve when the pore-accessible mineral surface areas are used, it was also necessary to include highly reactive glass phases to match the experimental observations, in agreement with conclusions from the disaggregated sediment experiment. It is hypothesized here that the 10-20 reduction in reactive surface areas based on the limited pore accessibility of reactive phases in core flood experiment may be reasonable for poorly sorted and cemented sediments like those at the Nagaoka site, although this reflects pore rather than larger scale heterogeneity.
Integer programming of cement distribution by train
NASA Astrophysics Data System (ADS)
Indarsih
2018-01-01
Cement industry in Central Java distributes cement by train to meet daily demand in Yogyakarta and Central Java area. There are five destination stations. For each destination station, there is a warehouse to load cements. Decision maker of cement industry have a plan to redesign the infrastructure and transportation system. The aim is to determine how many locomotives, train wagons, and containers and how to arrange train schedules with subject to the delivery time. For this purposes, we consider an integer programming to minimize the total of operational cost. Further, we will discuss a case study and the solution the problem can be calculated by LINGO software.
Models for Gas Hydrate-Bearing Sediments Inferred from Hydraulic Permeability and Elastic Velocities
Lee, Myung W.
2008-01-01
Elastic velocities and hydraulic permeability of gas hydrate-bearing sediments strongly depend on how gas hydrate accumulates in pore spaces and various gas hydrate accumulation models are proposed to predict physical property changes due to gas hydrate concentrations. Elastic velocities and permeability predicted from a cementation model differ noticeably from those from a pore-filling model. A nuclear magnetic resonance (NMR) log provides in-situ water-filled porosity and hydraulic permeability of gas hydrate-bearing sediments. To test the two competing models, the NMR log along with conventional logs such as velocity and resistivity logs acquired at the Mallik 5L-38 well, Mackenzie Delta, Canada, were analyzed. When the clay content is less than about 12 percent, the NMR porosity is 'accurate' and the gas hydrate concentrations from the NMR log are comparable to those estimated from an electrical resistivity log. The variation of elastic velocities and relative permeability with respect to the gas hydrate concentration indicates that the dominant effect of gas hydrate in the pore space is the pore-filling characteristic.
Azamat, Jafar; Sattary, Batoul Shirforush; Khataee, Alireza; Joo, Sang Woo
2015-09-01
A computer simulation was performed to investigate the removal of Zn(2+) as a heavy metal from aqueous solution using the functionalized pore of a graphene nanosheet and boron nitride nanosheet (BNNS). The simulated systems were comprised of a graphene nanosheet or BNNS with a functionalized pore containing an aqueous ionic solution of zinc chloride. In order to remove heavy metal from an aqueous solution using the functionalized pore of a graphene nanosheet and BNNS, an external voltage was applied along the z-axis of the simulated box. For the selective removal of zinc ions, the pores of graphene and BNNS were functionalized by passivating each atom at the pore edge with appropriate atoms. For complete analysis systems, we calculated the potential of the mean force of ions, the radial distribution function of ion-water, the residence time of ions, the hydrogen bond, and the autocorrelation function of the hydrogen bond. Copyright © 2015 Elsevier Inc. All rights reserved.
Modification of Wood Fiber for Use in Cement Board
NASA Astrophysics Data System (ADS)
Han, F. Q.; Tan, X.; Zhao, F. Q.
2017-12-01
When ordinary Portland cement is used for wood fiber cement (WFC) board, the setting time is too long, even hard to solidify. Three methods can be used for wood fiber modification, i.e., soaking in water, treated with alkali solution and coated with some substances on the fiber surface. The results show that the proper water-cement ratio of WFC paste is 1:1.3 in the case of wood cement ratio being 1:1. The WFC board from modified wood fiber and cement is better than the control samples, in which the combined treatment, i.e. soaking in hot water and then coating with alkali-BFS-EVA slurry, behaves best. It is proved that ordinary Portland cement can be used to produce WFC board, with the modified wood fiber, which can greatly reduce production costs.
Jang, Jae-Kyeong; Kim, Hong-Gi; Kim, Jun-Hyeong
2018-01-01
Concrete systems exposed to deicers are damaged in physical and chemical ways. In mitigating the damage from CaCl2 deicers, the usage of ground slag cement and MgO are investigated. Ordinary Portland cement (OPC) and slag cement are used in different proportions as the binding material, and MgO in doses of 0%, 5%, 7%, and 10% are added to the systems. After 28 days of water-curing, the specimens are immersed in 30% CaCl2 solution by mass for 180 days. Compressive strength test, carbonation test, chloride penetration test, chloride content test, XRD analysis, and SEM-EDAX analysis are conducted to evaluate the damage effects of the deicing solution. Up to 28 days, plain specimens with increasing MgO show a decrease in compressive strength, an increase in carbonation resistance, and a decrease in chloride penetration resistance, whereas the S30- and S50- specimens show a slight increase in compressive strength, an increase in carbonation resistance, and a slight increase in chloride penetration resistance. After 180 days of immersion in deicing solution, specimens with MgO retain their compressive strength longer and show improved durability. Furthermore, the addition of MgO to concrete systems with slag cement induces the formation of magnesium silicate hydrate (M-S-H) phases. PMID:29758008
Bubble Formation Modeling in IE-911
DOE Office of Scientific and Technical Information (OSTI.GOV)
Fondeur, F.F.
2000-09-27
The author used diffusion modeling to determine the hydrogen and oxygen concentration inside IE-911. The study revealed gas bubble nucleation will not occur in the bulk solution inside the pore or on the pore wall. This finding results from the fast oxygen and hydrogen gas molecular diffusion and a very confined pore space. The net steady state concentration of these species inside the pore proves too low to drive bubble nucleation. This study did not investigate other gas bubble nucleating mechanism such as suspended particles in solution.
NASA Astrophysics Data System (ADS)
Verba, C.; Lieuallen, A.; Yang, J.; Torres, M. E.; Hakala, A.
2014-12-01
Ensuring wellbore integrity for hydraulically-fractured shale reservoirs is important for maintaining zonal isolation of gases and fluids within the reservoir. Chemical reactions between wellbore cements, the shale formation, formation fluids, and fracturing fluids could affect the ability for cement to form an adequate seal. This study focuses on experimental investigations to evaluate how cement, rock, brines, and fracturing fluids react under conditions similar to the perforated zone associated with the Marcellus shale (Greene County, Pennsylvania). Two pressure/temperature regimes were investigated- moderate (25 MPa, 50oC) and high (27.5 MPa, 90oC). Shale collected from the Lower Marcellus section was encased in Class A cement, cured for 24 hours, and then exposed to simulated conditions in experimental autoclave reactors. The simulated formation fluid was a synthetic brine, modeled after a flowback fluid contained 187,000 mg/l total dissolved solids and had a pH of 7.6. The effect of pH was probed to evaluate the potential for cement reactivity under different pH conditions, and the potential for contaminant or geochemical tracer release from the shale (e.g. arsenic and rare earth elements). In addition to dissolution reactions, sorption and precipitation reactions between solutes and the cement are being evaluated, as the cement could bond with solute-phase species during continued hydration. The cements are expected to show different reactivity under the two temperature conditions because the primary cement hydration product, calcium silicate hydrate (C-S-H) is heavily influenced by temperature. Results from these experimental studies will be used both to inform the potential changes in cement chemistry that may occur along a wellbore in the hydraulically-fractured portion of a reservoir, and the types of geochemical tracers that may be useful in tracking these reactions.
Díaz-Díaz, Floriberto; de J. Cano-Barrita, Prisciliano F.; Balcom, Bruce J.; Solís-Nájera, Sergio E.; Rodríguez, Alfredo O.
2013-01-01
In cement-based materials porosity plays an important role in determining their mechanical and transport properties. This paper describes an improved low–cost embeddable miniature NMR sensor capable of non-destructively measuring evaporable water loss and porosity refinement in low and high water-to-cement ratio cement-based materials. The sensor consists of two NdFeB magnets having their North and South poles facing each other, separated by 7 mm to allow space for a Faraday cage containing a Teflon tube and an ellipsoidal RF coil. To account for magnetic field changes due to temperature variations, and/or the presence of steel rebars, or frequency variation due to sample impedance, an external tuning circuit was employed. The sensor performance was evaluated by analyzing the transverse magnetization decay obtained with a CPMG measurement from different materials, such as a polymer phantom, fresh white and grey cement pastes with different w/c ratios and concrete with low (0.30) and high (0.6) w/c ratios. The results indicated that the sensor is capable of detecting changes in water content in fresh cement pastes and porosity refinement caused by cement hydration in hardened materials, even if they are prepared with a low w/c ratio (w/c = 0.30). The short lifetime component of the transverse relaxation rate is directly proportional to the compressive strength of concrete determined by destructive testing. The r2 (0.97) from the linear relationship observed is similar to that obtained using T2 data from a commercial Oxford Instruments 12.9 MHz spectrometer.
Osmotic water transport in aquaporins: evidence for a stochastic mechanism
Zeuthen, Thomas; Alsterfjord, Magnus; Beitz, Eric; MacAulay, Nanna
2013-01-01
We test a novel, stochastic model of osmotic water transport in aquaporins. A solute molecule present at the pore mouth can either be reflected or permeate the pore. We assume that only reflected solute molecules induce osmotic transport of water through the pore, while permeating solute molecules give rise to no water transport. Accordingly, the rate of water transport is proportional to the reflection coefficient σ, while the solute permeability, PS, is proportional to 1 –σ. The model was tested in aquaporins heterologously expressed in Xenopus oocytes. A variety of aquaporin channel sizes and geometries were obtained with the two aquaporins AQP1 and AQP9 and mutant versions of these. Osmotic water transport was generated by adding 20 mm of a range of different-sized osmolytes to the outer solution. The osmotic water permeability and the reflection coefficient were measured optically at high resolution and compared to the solute permeability obtained from short-term uptake of radio-labelled solute under isotonic conditions. For each type of aquaporin there was a linear relationship between solute permeability and reflection coefficient, in accordance with the model. We found no evidence for coupling between water and solute fluxes in the pore. In confirmation of molecular dynamic simulations, we conclude that the magnitude of the osmotic water permeability and the reflection coefficient are determined by processes at the arginine selectivity filter located at the outward-facing end of the pore. PMID:23959676
Prabhakar, A R; Mahantesh, T; Ahuja, Vipin
2010-01-01
The purpose of this study was to evaluate the efficacy of banding cements in terms of retentive capability and demineralization inhibition potential. We included 48 non-carious primary mandibular second molar teeth. Preformed stainless steel bands were adapted onto the teeth. All teeth were randomly assigned to four groups: Group I (Adaptation of bands without cementation), Group II (Cementation of bands using conventional Glass Ionomer Cement), Group III (Cementation of bands using Resin-modified Glass Ionomer Cement), Group IV (Cementation of bands using Resin cement), and placed in artificial saliva. Each day, specimens were taken from artificial saliva and suspended in an artificial caries solution for 35 minutes, every 8 hours. At the end of 3 months, retention of bands was estimated using an Instron Universal Testing Machine. The mode of failure was recorded and specimens were sectioned and examined under polarized microscope for demineralized lesions. The mean retention value was highest with resin cement, followed by RMGIC, GIC, and Control group respectively. The RMGIC group showed more favorable modes of failures. All the experimental groups showed significant demineralization inhibition potential. RMGIC is the preferable banding cement and can be used effectively to cement bands in primary dentition.
Adsorption of cesium on cement mortar from aqueous solutions.
Volchek, Konstantin; Miah, Muhammed Yusuf; Kuang, Wenxing; DeMaleki, Zack; Tezel, F Handan
2011-10-30
The adsorption of cesium on cement mortar from aqueous solutions was studied in series of bench-scale tests. The effects of cesium concentration, temperature and contact time on process kinetics and equilibrium were evaluated. Experiments were carried out in a range of initial cesium concentrations from 0.0103 to 10.88 mg L(-1) and temperatures from 278 to 313 K using coupons of cement mortar immersed in the solutions. Non-radioactive cesium chloride was used as a surrogate of the radioactive (137)Cs. Solution samples were taken after set periods of time and analyzed by inductively coupled plasma mass spectroscopy. Depending on the initial cesium concentration, its equilibrium concentration in solution ranged from 0.0069 to 8.837 mg L(-1) while the respective surface concentration on coupons varied from 0.0395 to 22.34 μg cm(-2). Equilibrium test results correlated well with the Freundlich isotherm model for the entire test duration. Test results revealed that an increase in temperature resulted in an increase in adsorption rate and a decrease in equilibrium cesium surface concentration. Among several kinetic models considered, the pseudo-second order reaction model was found to be the best to describe the kinetic test results in the studied range of concentrations. The adsorption activation energy determined from Arrhenius equation was found to be approximately 55.9 kJ mol(-1) suggesting that chemisorption was the prevalent mechanism of interaction between cesium ions and cement mortar. Crown Copyright © 2011. Published by Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Wei, Jie; Wang, Jiecheng; Liu, Xiaochen; Ma, Jian; Liu, Changsheng; Fang, Jing; Wei, Shicheng
2011-06-01
Fluoride substituted apatite cement (fs-AC) was synthesized by using the cement powders of tetracalcium phosphate (TTCP) and sodium fluoride (NaF), and the cement powders were mixed with diluted phosphoric acid (H 3PO 4) as cement liquid to form fs-AC paste. The fs-AC paste could be directly filled into the carious cavities to repair damaged dental enamel. The results indicated that the fs-AC paste was changed into fluorapatite crystals with the atom molar ratio for calcium to phosphorus of 1.66 and the F ion amount of 3 wt% after self-hardening for 2 days. The solubility of fs-AC in Tris-HCl solution (pH 6) was slightly lower than hydroxyapatite cement (HAC) that was similar to the apatite in enamel, indicating the fs-AC was much insensitive to the weakly acidic solution than the apatite in enamel. The fs-AC was tightly combined with the enamel surface because of the chemical reaction between the fs-AC and the apatite in enamel after the caries cavities was filled with fs-AC. The extracts of fs-AC caused no cytotoxicity on L929 cells, which satisfied the relevant criterion on dental biomaterials, revealing good cytocompatibility. The fs-AC had potential prospect for the reconstitution of carious lesion of dental enamel.
On morphology of methane-derived authigenic carbonates
NASA Astrophysics Data System (ADS)
Logvina, E.; Matveeva, T.
2009-04-01
Studies of methane-derived carbonates revealed a great variety their morphological types. Although the processes of these carbonates formation is not clearly understood, it has been suggested that in general bacterially mediated processes of hydrocarbon oxidation, coupled with sulphate reduction, produce unusually high levels of alkalinity and dissolved inorganic carbon in the pore fluids that is partitioned between the precipitating carbonate and CO2 rich plumes which emanate into the water column (Aharon, 1994). These carbonates consist by three main CaCO3 polymorphs - calcite, aragonite and dolomite. Carbonates with different petrography cemented from these polymorphs can be classified according to their specific locality mode of formation and biogenic or non-biogenic origin (Greinert et al., 2002). There are classifications for the authigenic carbonates which are based on petrography, morphology, or based on age and origin. In this work we will consider the petrographical and morphological differences of authigenic carbonates. The large structures vary from 10 to 200 m size, named as chemoherm carbonates. Usually they cemented by pure aragonite with minor Mg-calcite admixture. These chemoherms rise up to 50 m above the seafloor. The structures are irregular in shape and have numerous pores and open pathways resulting from plumbing system of fluid expulsion. This type of authigenic carbonates was observed in the NE Black Sea (Michaelis et al., 2002), at the Hydrate Ridge area (Greinert et al., 2001), at Aleutian accretionary margin (Greinert et al., 2002). Diagenetic carbonates - carbonate cemented sediments both growing at the seafloor or within the sediment framework and showing a large variety of shapes (chimneys, crusts, concretions est.), with grey to dark-grey color. Petrographically the carbonate cement represents by Mg-calcite, protodolomite and dolomite. The diagenetic carbonates occur widely in the fluid venting areas. In particular, diagenetic carbonate chimneys were observed in the NE Atlantic, in the Gulf of Cadiz (Diaz del Rio et al., 2003), offshore Morocco (Magalhães et al., 2002), at northern Kattegat (Jensen et al., 1992), in the Pobitite Kamani area, in north-eastern Bulgaria (Botz et al., 1993). Clathrites (gas hydrate carbonates) are formed at the seawater/sediment interface or within the sediment in close contact with gas hydrates and bacterial mats. This type of the authigenic carbonates in direct contact with gas hydrates were identified and described by G. Bohrmann at Hydrate Ridge in 1998. According to (Bohrmann et al., 1998), they characterize by carbonate-cemented breccia composed of angular clasts cementing by Mg-calcite and aragonite. The brecciated structure causes by gas hydrate formation processes. A pure aragonite layers which form in elongated pores formerly occupied by gas hydrate are typical. This pseudomorphism resembles gas hydrate bubble structures. As a whole, clathrites are associated with bacterial mats on the seafloor next to gas hydrates and within the gas hydrate pore structure. References: G. Bohrmann, J. Greinert, E. Suess and M. Torres. Authigenic carbonates from the Cascadia subduction zone and their relation to gas hydrate stability: Geology, 1998, v. 26, pp. 647-650. J. Greinert, G. Bohrmann, and E. Suess. Gas hydrate-associated carbonates and methane-venting at Hydrate Ridge: Classification, distribution, and origin of authigenic lithologies, in Paull, C. and Dillon W.P. ed., Natural gas hydrates: Occurrence, distribution, and detection: Geophysical Monograph 124: 87-98, American Geophysical Union, 2001, pp. 99-113. J. Greinert, G. Bohrmann, and M. Elvert Stromatolitic fabric of authigenic carbonate crusts in 4850 m water depth, Aleutian accretionary margin: Result of anaerobic methane oxidation by Archaea at cold seeps. International Journal of Earth Sciences, 2002, 91, pp. 698-711. P. Aharon. Carbon and oxygen isotope tracers of submarine hydrocarbon emissions: Northern Gulf of Mexico. Israel Journal of earth Sciences, 1994, 43, pp. 157-164. P. Jensen, I. Aagaard, R. A. Burke Jr et al. "Bubbling reefs" in the Kattegat: submarine landscapes of carbonate-cemented rocks support a diverse ecosystem at methane seeps, Mar. Ecol. Prog. Ser., 1992, 83, pp. 103-112. R.W. Botz, V. Georgiev, P. Stoffers, et al. Stable isotope study of carbonate-cemented rocks from the Pobitite Kamani area, north-eastern Bulgaria. Geologische Rundschau, 1993, 82, pp. 663- 666. V. Diaz del Rio, L. Somoza, J. Martinez-Frias, et al. Vast field of hydrocarbon-derived carbonate chimneys related to the accretionary wedge/olistostrome of the Gulf of Cadiz. Marine Geology, 2003, 195, pp.177-200. V. Magalhães, C. Vasconcelos, L. Gaspar et al. Methane related aythigenic carbonates, chimneys and crusts from the Gulf of Cadiz, Geophysical Research Abstracts, 2002, Vol. 5, 12842. W. Michaelis, R. Seifert, K. Nauhaus, T. et al. Microbial Reefs in the Black Sea Fueled by Anaerobic Oxidation of Methane. Science, 2002, 297, pp. 1013-1015.
Keller, Margaret A.; Macquaker, Joe H.S.; Taylor, Kevin G.; Polya, David
2014-01-01
Diagenesis significantly impacts mudstone lithofacies. Processes operating to control diagenetic pathways in mudstones are poorly known compared to analogous processes occurring in other sedimentary rocks. Selected organic-carbon-rich mudstones, from the Kimmeridge Clay and Monterey Formations, have been investigated to determine how varying starting compositions influence diagenesis.The sampled Kimmeridge Clay Formation mudstones are organized into thin homogenous beds, composed mainly of siliciclastic detritus, with some constituents derived from water-column production (e.g., coccoliths, S-depleted type-II kerogen, as much as 52.6% total organic carbon [TOC]) and others from diagenesis (e.g., pyrite, carbonate, and kaolinite). The sampled Monterey Formation mudstones are organized into thin beds that exhibit pelleted wavy lamination, and are predominantly composed of production-derived components including diatoms, coccoliths, and foraminifera, in addition to type-IIS kerogen (as much as 16.5% TOC), and apatite and silica cements.During early burial of the studied Kimmeridge Clay Formation mudstones, the availability of detrital Fe(III) and reactive clay minerals caused carbonate- and silicate-buffering reactions to operate effectively and the pore waters to be Fe(II) rich. These conditions led to pyrite, iron-poor carbonates, and kaolinite cements precipitating, preserved organic carbon being S-depleted, and sweet hydrocarbons being generated. In contrast, during the diagenesis of the sampled Monterey Formation mudstones, sulfide oxidation, coupled with opal dissolution and the reduced availability of both Fe(III) and reactive siliciclastic detritus, meant that the pore waters were poorly buffered and locally acidic. These conditions resulted in local carbonate dissolution, apatite and silica cements precipitation, natural kerogen sulfurization, and sour hydrocarbons generation.Differences in mud composition at deposition significantly influence subsequent diagenesis. These differences impact their source rock attributes and mechanical properties.
Microseismicity Induced by Fluid Pressure Drop (Laboratory Study)
NASA Astrophysics Data System (ADS)
Turuntaev, Sergey; Zenchenko, Evgeny; Melchaeva, Olga
2013-04-01
Pore pressure change in saturated porous rocks may result in its fracturing (Maury et Fourmaintraux, 1993) and corresponding microseismic event occurrences. Microseismicity due to fluid injection is considered in numerous papers (Maxwell, 2010, Shapiro et al., 2005). Another type of the porous medium fracturing is related with rapid pore pressure drop at some boundary. The mechanism of such fracturing was considered by (Khristianovich, 1985) as a model of sudden coal blowing and by (Alidibirov, Panov, 1998) as a model of volcano eruptions. If the porous saturated medium has a boundary where it directly contacted with fluid under the high pressure (in a hydraulic fracture or in a borehole), and the pressure at that boundary is dropped, the conditions for tensile cracks can be achieved at some distance from the boundary. In the paper, the results of experimental study of saturated porous sample fracturing due to pore pressure rapid drop are discussed. The samples (82 mm high, ∅60 mm) were made of quartz sand, which was cemented by "liquid glass" glue with mass fraction 1%. The sample (porosity 35%, uniaxial unconfined compression strength 2.5 MPa) was placed in a mould and saturated by oil. The upper end of the sample contacted with the mould upper lid, the lower end contacted with fluid. The fluid pressure was increased to 10 MPa and then discharged through the bottom nipple. The pressure increases/drops were repeated 30-50 times. Pore pressure and acoustic emission (AE) were registered by transducers mounted into upper and bottom lids of the mould. It was found, that AE sources (corresponded to microfracturing) were spreading from the open end to the closed end of the sample, and that maximal number of AE events was registered at some distance from the opened end. The number of AE pulses increased with every next pressure drop, meanwhile the number of pulses with high amplitudes diminished. It was found that AE maximal rate corresponded to the fluid pressure gradient maximal values. The model of AE relation with the pore pressure gradient was considered based on the following assumptions: AE event occurred when the pore pressure gradient reaches some critical value; the critical value varies and can be described by Weibull distribution. Permeability variation during the fluid pressure drop was estimated by means of fluid pressure data and pore-elastic equation solution for small time intervals (0.01 sec). The study showed possibility to solve both a direct problem of microseismicity variation relation with fluid pressure changes and an inverse problem of defining permeability by registering microseismic activity variation in particular volume of porous medium alongside with pore pressure measurements at some point.
Grangeon, Sylvain; De Nolf, Wout; Harker, Nicholas; Boulahya, Faiza; Bourbon, Xavier
2018-01-01
To understand the main properties of cement, a ubiquitous material, a sound description of its chemistry and mineralogy, including its reactivity in aggressive environments and its mechanical properties, is vital. In particular, the porosity distribution and associated sample carbonation, both of which affect cement’s properties and durability, should be quantified accurately, and their kinetics and mechanisms of formation known both in detail and in situ. However, traditional methods of cement mineralogy analysis (e.g. chemical mapping) involve sample preparation (e.g. slicing) that can be destructive and/or expose cement to the atmosphere, leading to preparation artefacts (e.g. dehydration). In addition, the kinetics of mineralogical development during hydration, and associated porosity development, cannot be examined. To circumvent these issues, X-ray diffraction computed tomography (XRD-CT) has been used. This allowed the mineralogy of ternary blended cement composed of clinker, fly ash and blast furnace slag to be deciphered. Consistent with previous results obtained for both powdered samples and dilute systems, it was possible, using a consolidated cement paste (with a water-to-solid ratio akin to that used in civil engineering), to determine that the mineralogy consists of alite (only detected in the in situ hydration experiment), calcite, calcium silicate hydrates (C-S-H), ettringite, mullite, portlandite, and an amorphous fraction of unreacted slag and fly ash. Mineralogical evolution during the first hydration steps indicated fast ferrite reactivity. Insights were also gained into how the cement porosity evolves over time and into associated spatially and time-resolved carbonation mechanisms. It was observed that macroporosity developed in less than 30 h of hydration, with pore sizes reaching about 100–150 µm in width. Carbonation was not observed for this time scale, but was found to affect the first 100 µm of cement located around macropores in a sample cured for six months. Regarding this carbonation, the only mineral detected was calcite. PMID:29765604
Injectable Foams for Regenerative Medicine
Prieto, Edna M.; Page, Jonathan M.; Harmata, Andrew J.
2013-01-01
The design of injectable biomaterials has attracted considerable attention in recent years. Many injectable biomaterials, such as hydrogels and calcium phosphate cements, have nanoscale pores that limit the rate of cellular migration and proliferation. While introduction of macroporosity has been suggested to increase cellular infiltration and tissue healing, many conventional methods for generating macropores often require harsh processing conditions that preclude their use in injectable foams. In recent years, processes such as porogen leaching, gas foaming, and emulsion-templating have been adapted to generate macroporosity in injectable calcium phosphate cements, hydrogels, and hydrophobic polymers. While some of the more mature injectable foam technologies have been evaluated in clinical trials, there are challenges remaining to be addressed, such as the biocompatibility and ultimate fate of the sacrificial phase used to generate pores within the foam after it sets in situ. Furthermore, while implantable scaffolds can be washed extensively to remove undesirable impurities, all of the components required to synthesize injectable foams must be injected into the defect. Thus, every compound in the foam must be biocompatible and non-cytotoxic at the concentrations utilized. As future research addresses these critical challenges, injectable macroporous foams are anticipated to have an increasingly significant impact on improving patient outcomes for a number of clinical procedures. PMID:24127230
The effect of plasma on shear bond strength between resin cement and colored zirconia
2017-01-01
PURPOSE To investigate the effect of non-thermal atmospheric pressure plasma (NTAPP) treatment on shear bond strength (SBS) between resin cement and colored zirconia made with metal chlorides. MATERIALS AND METHODS 60 zirconia specimens were divided into 3 groups using coloring liquid. Each group was divided again into 2 sub-groups using plasma treatment; the experimental group was treated with plasma, and the control group was untreated. The sub-groups were: N (non-colored), C (0.1 wt% aqueous chromium chloride solution), M (0.1 wt% aqueous molybdenum chloride solution), NP (non-colored with plasma), CP (0.1 wt% aqueous chromium chloride solution with plasma), and MP (0.1 wt% aqueous molybdenum chloride solution with plasma). Composite resin cylinders were bonded to zirconia specimens with MDP-based resin cement, and SBS was measured using a universal testing machine. All data was analyzed statistically using a 2-way ANOVA test and a Tukey test. RESULTS SBS significantly increased when specimens were treated with NTAPP regardless of coloring (P<.001). Colored zirconia containing molybdenum showed the highest value of SBS, regardless of NTAPP. The molybdenum group showed the highest SBS, whereas the chromium group showed the lowest. CONCLUSION NTAPP may increase the SBS of colored zirconia and resin cement. The NTAPP effect on SBS is not influenced by the presence of zirconia coloring. PMID:28435621
Factors affecting hazardous waste solidification/stabilization: a review.
Malviya, Rachana; Chaudhary, Rubina
2006-09-01
Solidification/stabilization is accepted as a well-established disposal technique for hazardous waste. As a result many different types of hazardous wastes are treated with different binders. The S/S products have different property from waste and binders individually. The effectiveness of S/S process is studied by physical, chemical and microstructural methods. This paper summarizes the effect of different waste stream such as heavy metals bearing sludge, filter cake, fly ash, and slag on the properties of cement and other binders. The factors affecting strength development is studied using mix designs, including metal bearing waste alters the hydration and setting time of binders. Pore structure depends on relative quantity of the constituents, cement hydration products and their reaction products with admixtures. Carbonation and additives can lead to strength improvement in waste-binder matrix.
Building materials. VOC emissions, diffusion behaviour and implications from their use.
Katsoyiannis, Athanasios; Leva, Paolo; Barrero-Moreno, Josefa; Kotzias, Dimitrios
2012-10-01
Five cement- and five lime-based building materials were examined in an environmental chamber for their emissions of Volatile Organic Compounds (VOCs). Typical VOCs were below detection limits, whereas not routinely analysed VOCs, like neopentyl glycol (NPG), dominated the cement-based products emissions, where, after 72 h, it was found to occur, in levels as high as 1400 μg m(-3), accounting for up to 93% of total VOCs. The concentrations of NPG were not considerably changed between the 24 and 72 h of sampling. The permeability of building materials was assessed through experiments with a dual environmental chamber; it was shown that building materials facilitate the diffusion of chemicals through their pores, reaching equilibrium relatively fast (6 h). Copyright © 2012 Elsevier Ltd. All rights reserved.
Unosson, Johanna; Montufar, Edgar B; Engqvist, Håkan; Ginebra, Maria-Pau; Persson, Cecilia
2016-01-01
Resorbable calcium phosphate based bone void fillers should work as temporary templates for new bone formation. The incorporation of macropores with sizes of 100 -300 µm has been shown to increase the resorption rate of the implant and speed up bone ingrowth. In this work, macroporous brushite cements were fabricated through foaming of the cement paste, using two different synthetic surfactants, Tween® 80 and Pluronic® F-127. The macropores formed in the Pluronic samples were both smaller and less homogeneously distributed compared with the pores formed in the Tween samples. The porosity and compressive strength (CS) were comparable to previously developed hydroxyapatite foams. The cement foam containing Tween, 0.5M citric acid in the liquid, 1 mass% of disodium dihydrogen pyrophosphate mixed in the powder and a liquid to powder ratio of 0.43 mL/g, showed the highest porosity values (76% total and 56% macroporosity), while the CS was >1 MPa, that is, the hardened cement could be handled without rupture of the foamed structure. The investigated brushite foams show potential for future clinical use, both as bone void fillers and as scaffolds for in vitro bone regeneration. © 2015 The Authors. Journal of Biomedical Materials Research Part B: Applied Biomaterials Published by Wiley Periodicals, Inc.
[A study on alpha-tricalcium phosphate bone cement carbon fiber-reinforced].
Wu, Wenjin; Yang, Weizhong; Zhou, Dali; Ma, Jiang; Xiao, Bin
2006-06-01
In order to improve the mechanical properties of alpha-tricalcium phosphate (alpha-TCP), we prepared surface-modified carbon fibers (CF) reinforced alpha-TCP composite bone cement. Bone cement was soaked in Ringer's body solution to test its capacity of fast formation of hydroxyapatite crystals and self-solidification. Scan electronic microscope (SEM) observation and compressive strength measurement were taken to analyze the mechanical properties and the micro- morphological structure of CF reinforced alpha-TCP bone cement. The results showed that the bone cement was transferred into hydroxyapatite plates after being soaked in Ringer's simulated body fluid for 5 days. Suitable amount of carbon fibers could well spread in and bond with the matrix of the bone cement. The mechanical properties of the bone cement have been improved by CF reinforcing; the compressive strength reaches 46.7 MPa when the amount of carbon fibers is 0.5% in weight percent, which is 22% higher than that of the non-reinforced alpha-TCP bone cement.
Role of calcium on chloride binding in hydrated Portland cement–metakaolin–limestone blends
DOE Office of Scientific and Technical Information (OSTI.GOV)
Shi, Zhenguo; Geiker, Mette Rica; De Weerdt, Klaartje
Chloride binding is investigated for Portland cement–metakaolin–limestone pastes exposed to CaCl{sub 2} and NaCl solutions. The phase assemblages and the amount of Friedel's salt are evaluated using TGA, XRD and thermodynamic modeling. A larger amount of Friedel's salt is observed in the metakaolin blends compared to the pure Portland cement. A higher total chloride binding is observed for the pastes exposed to the CaCl{sub 2} solution relative to those in the NaCl solution. This is reflected by the fact that calcium increases the quantity of Friedel's salt in the metakaolin blends by promoting the transformation of strätlingite and/or monocarbonate tomore » Friedel's salt. Calcium increases also the amount of chloride in the diffuse layer of the C-S-H for the pure cement. A linear correlation between the total bound chloride and the uptake of calcium from the CaCl{sub 2} solution is obtained and found to be independent on the type of cement blend.« less
Lommatzsch, Marco; Exner, Ulrike; Gier, Susanne; Grasemann, Bernhard
2015-01-01
The present study examines deformation bands in calcareous arkosic sands. The investigated units can be considered as an equivalent to the Matzen field in the Vienna Basin (Austria), which is one of the most productive oil reservoirs in central Europe. The outcrop exposes carbonate-free and carbonatic sediments of Badenian age separated by a normal fault. Carbonatic sediments in the hanging wall of the normal fault develop dilation bands with minor shear displacements (< 2 mm), whereas carbonate-free sediments in the footwall develop cataclastic shear bands with up to 70 cm displacement. The cataclastic shear bands show a permeability reduction up to 3 orders of magnitude and strong baffling effects in the vadose zone. Carbonatic dilation bands show a permeability reduction of 1-2 orders of magnitude and no baffling structures. We distinguished two types of deformation bands in the carbonatic units, which differ in deformation mechanisms, distribution and composition. Full-cemented bands form as dilation bands with an intense syn-kinematic calcite cementation, whereas the younger loose-cemented bands are dilatant shear bands cemented by patchy calcite and clay minerals. All analyzed bands are characterized by a porosity and permeability reduction caused by grain fracturing and cementation. The changed petrophysical properties and especially the porosity evolution are closely related to diagenetic processes driven by varying pore fluids in different diagenetic environments. The deformation band evolution and sealing capacity is controlled by the initial host rock composition. PMID:26300577
Experimental study of the caprock / cement interface under CO2 geological storage conditions
NASA Astrophysics Data System (ADS)
Jobard, Emmanuel; Sterpenich, Jérôme; Pironon, Jacques; Randi, Aurélien; Caumon, Marie-Camille
2013-04-01
In the framework of CO2 geological storage, one of the critical point leading to possible massive CO2 leakages is the behavior of the interfaces crossed by the injection well. The lack of relevant data on the behavior of these interfaces (rock/well materials) in the presence of CO2 under high pressure and temperature conditions led to the development of a new experimental model called "Sandwich". These batch experiments consisted in putting a caprock (Callovo-Oxfordian claystone of the Paris Basin) in contact with cement (Portland class G) in the presence of supercritical CO2 with or without aqueous solution. The new experimental device was designed in order to follow the evolution of a clayey caprock, a Portland cement and their interface submitted to the acidic attack of carbonic acid through a study of the initial and final states. This model should help to document the behavior of interfaces in the proximal zone at the injection site. After one month of ageing at 80° C under 100 bar of CO2 pressure, the caprock, the cement and the interface between caprock and cement are investigated thanks to SEM, cathodoluminescence and Raman spectrometry. The main results reveal i) the influence of the presence of an aqueous solution since the carbonation mechanisms are quite different under dry and wet atmospheres, ii) the good cohesion of the different interfaces despite the carbonation of the cement, iii) the precipitation of different carbonate phases, which relates the changes in the chemistry of the solution to time, iv) the enrichment of silica in the cement phase submitted to the action of CO2 putting into evidence new mechanisms of in situ silica re-condensation, v) the very good behavior of the caprock despite the alkaline flux from cement and the acidic attack from the dissolved CO2. These experimental results will be compared to those obtained by geochemical simulations performed with PHREEQC. This study was financially supported by the French agency ANR (ANR-08-PCO2-006).
Urrutia, Oscar; Erro, Javier; Zabini, Andre; Hoshiba, Kent; Blandin, Anne F; Baigorri, Roberto; Martín-Pastor, Manuel; Alis, Yves; Yvin, Jean C; García-Mina, José M
2018-05-16
This study describes the efficiency of a new coating material for preparing granulated potassium-fertilizers with a potassium release to the soil solution sensitive to rainfall intensity. The composite is prepared by reaction of an alkyd-resin with cement in the absence of water. The complementary use of diverse analytical techniques showed that the presence of the cement fraction induced alkyd resin reticulation and gradual cement-resin hardening. Scanning electron microscopy revealed the formation of micro and nanopores within cement-clusters, whose water permeability is affected by the resin reticulation and amphiphilic character. Potassium release was evaluated in water, soil-columns, and in soil-plant trials in pots and open-field. Agronomic results were consistent with potassium release rates obtained in water solution and soil columns. The composite-coated potassium fertilizer was more efficient than the noncoated one in providing plant available potassium, with this effect being dependent on water presence in soil.
A new approximation for pore pressure accumulation in marine sediment due to water waves
NASA Astrophysics Data System (ADS)
Jeng, D.-S.; Seymour, B. R.; Li, J.
2007-01-01
The residual mechanism of wave-induced pore water pressure accumulation in marine sediments is re-examined. An analytical approximation is derived using a linear relation for pore pressure generation in cyclic loading, and mistakes in previous solutions (Int. J. Numer. Anal. Methods Geomech. 2001; 25:885-907; J. Offshore Mech. Arctic Eng. (ASME) 1989; 111(1):1-11) are corrected. A numerical scheme is then employed to solve the case with a non-linear relation for pore pressure generation. Both analytical and numerical solutions are verified with experimental data (Laboratory and field investigation of wave-sediment interaction. Joseph H. Defrees Hydraulics Laboratory, School of Civil and Environmental Engineering, Cornell University, Ithaca, NY, 1983), and provide a better prediction of pore pressure accumulation than the previous solution (J. Offshore Mech. Arctic Eng. (ASME) 1989; 111(1):1-11). The parametric study concludes that the pore pressure accumulation and use of full non-linear relation of pore pressure become more important under the following conditions: (1) large wave amplitude, (2) longer wave period, (3) shallow water, (4) shallow soil and (5) softer soils with a low consolidation coefficient. Copyright
Experimental study on mix proportion of fiber reinforced cementitious composites
NASA Astrophysics Data System (ADS)
Jia, Yi; Zhao, Renda; Liao, Ping; Li, Fuhai; Yuan, Yuan; Zhou, Shuang
2017-10-01
To study the mechanical property of fiber reinforced cementations composites influenced by the fiber length, quartz sand diameter, matrix of water cement ratio, volume fraction of fiber and magnesium acrylate solution. Several 40×40×160 mm standard test specimens, "8" specimens and long "8" specimens and 21 groups of fiber concrete specimens were fabricated. The flexural, compressive and uniaxial tensile strength were tested by using the bending resistance, compression resistance and electronic universal testing machine. The results show that flexural and compressive strength of fiber reinforced cementations composites increases along with the increase of quartz sand diameter, with the growth of the PVA fiber length increases; When the water-binder ratio is 0.25 and powder-binder ratio is 0.3, the PVA fiber content is 1.5% of the mass of cementations materials, there is a phenomenon of strain hardening; The addition of magnesium acrylate solution reduces the tensile strength of PVA fiber reinforced cementations composites, the tensile strength of the specimens in the curing age of 7d is decreased by about 21% and the specimens in curing age of 28d is decreased by more than 50%.
A Study on the Properties of Carbon Black Mortar Using Granulated Blast Furnace Slag and Polymer.
Jang, Hong-Seok; Jeon, Ui-Hyeon; So, Seung-Young
2015-11-01
White Portland Cement (WPC) and inorganic pigment have been used in colored concrete, but there are some physical problems such as increases in efflorescence, and poor workability and low economics. The aim of this study was to investigate the effects of GBFS and polymer (methyl cellulose) on the physical properties of carbon black mortar. For this purpose, a flow test, compressive strength test and color evaluation and was carried out on cement mortar mixed with polymer by changing the proportion of cement and ratio of GBFS. The results show that the addition of polymer influences significantly the color value efficiency in colored mortar. This is due to the reduction of overall amount of micro pore. This polymer films prevent the transport of soluble calcium towards the surface, and decreases efflorescence. And the flow of colored mortar was increased in proportion to the addition rate of the GBFS. In addition the strength of colored mortars with GBFS at the long-term aged (after 28 days) was higher than that of the general WPC mortar, although its strength was developed slowly at the early ages.
The cement solidification systems at LANL
DOE Office of Scientific and Technical Information (OSTI.GOV)
Veazey, G.W.
1990-01-01
There are two major cement solidification systems at Los Alamos National Laboratory. Both are focused primarily around treating waste from the evaporator at TA-55, the Plutonium Processing Facility. The evaporator receives the liquid waste stream from TA-55's nitric acid-based, aqueous-processing operations and concentrates the majority of the radionuclides in the evaporator bottoms solution. This is sent to the TA-55 cementation system. The evaporator distillate is sent to the TA-50 facility, where the radionuclides are precipitated and then cemented. Both systems treat TRU-level waste, and so are operated according to the criteria for WIPP-destined waste, but they differ in both cementmore » type and mixing method. The TA-55 systems uses Envirostone, a gypsum-based cement and in-drum prop mixing; the TA-50 systems uses Portland cement and drum tumbling for mixing.« less
Pore Structure Characterization in Concrete Prepared with Carbonated Fly Ash
NASA Astrophysics Data System (ADS)
Sahoo, Sanjukta
2018-03-01
Carbon dioxide capture and storage (CCS) is a technique to address the global concern of continuously rising CO2 level in the atmosphere. Fly ash is considered as a suitable medium for CCS due to presence of metal oxides. The fly ash which has already sequestered carbon dioxide is referred to as carbonated fly ash. Recent research reveals better durability of concretes using carbonated fly ash as part replacement of cement. In the present research pore structure characterization of the carbonated fly ash concrete has been carried out. Mercury Intrusion porosimetry test has been conducted on control concrete and concrete specimens using fly ash and carbonated fly ash at replacement levels of 25% and 40%. The specimens have been water cured for 28 days and 90 days. It is observed that porosity reduction rate is more pronounced in carbonated fly ash concrete compared to control concrete at higher water curing age. Correlation analysis is also carried out which indicates moderately linear relationship between porosity % and pore distribution with particle size and water curing.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Chen, Cheng-Gang; Sun, Chang-Jung, E-mail: sun.3409@hotmail.com; Gau, Sue-Huai
2013-04-15
Highlights: ► Milling extracted MSWI fly ash. ► Increasing specific surface area, destruction of the crystalline texture, and increasing the amount of amorphous materials. ► Increasing heavy metal stability. ► Inducing pozzolanic reactions and increasing the early and later strength of the cement paste. - Abstract: A water extraction process can remove the soluble salts present in municipal solid waste incinerator (MSWI) fly ash, which will help to increase the stability of the synthetic materials produced from the MSWI fly ash. A milling process can be used to stabilize the heavy metals found in the extracted MSWI fly ash (EA)more » leading to the formation of a non-hazardous material. This milled extracted MSWI fly ash (MEA) was added to an ordinary Portland cement (OPC) paste to induce pozzolanic reactions. The experimental parameters included the milling time (96 h), water to binder ratios (0.38, 0.45, and 0.55), and curing time (1, 3, 7 and 28 days). The analysis procedures included inductively coupled plasma atomic emission spectroscopy (ICP/AES), BET, mercury intrusion porosimetry (MIP), X-ray diffraction (XRD), and nuclear magnetic resonance (NMR) imaging. The results of the analyses indicate that the milling process helped to stabilize the heavy metals in the MEA, with an increase in the specific surface area of about 50 times over that of OPC. The addition of the MEA to the OPC paste decreased the amount of Ca(OH){sub 2} and led to the generation of calcium–silicate–hydrates (C–S–H) which in turned increased the amount of gel pores and middle sized pores in the cement. Furthermore, a comparison shows an increase in the early and later strength over that of OPC paste without the addition of the milled extracted ash. In other words, the milling process could stabilize the heavy metals in the MEA and had an activating effect on the MEA, allowing it to partly substitute OPC in OPC paste.« less
NASA Astrophysics Data System (ADS)
Ping, Jinglei; Johnson, A. T. Charlie; A. T. Charlie Johnson Team
Conventional electrical methods for detecting charge transfer through protein pores perturb the electrostatic condition of the solution and chemical reactivity of the pore, and are not suitable to be used for complex biofluids. We developed a non-perturbative methodology ( fW input power) for quantifying trans-pore electrical current and detecting the pore status (i.e., open vs. closes) via graphene microelectrodes. Ferritin was used as a model protein featuring a large interior compartment, well-separated from the exterior solution with discrete pores as charge commuting channels. The charge flowing through the ferritin pores transfers into the graphene microelectrode and is recorded by an electrometer. In this example, our methodology enables the quantification of an inorganic nanoparticle-protein nanopore interaction in complex biofluids. The authors acknowledge the support from the Defense Advanced Research Projects Agency (DARPA) and the U.S. Army Research Office under Grant Number W911NF1010093.
NASA Astrophysics Data System (ADS)
Tittarelli, Francesca; Mobili, Alessandra; Vicerè, Anna Maria; Roventi, Gabriella; Bellezze, Tiziano
2017-10-01
The effect of a new passivation treatment, obtained by immersion of the galvanized reinforcements in a trivalent chromium salts based solution, on the chlorides induced corrosion has been investigated. To investigate also the effect of cement alkalinity on corrosion behaviour of reinforcements, concretes manufactured with three different European cements were compared. The obtained results show that the alternative treatment based on hexavalent chromium-free baths forms effective protection layers on the galvanized rebar surfaces. The higher corrosion rates of zinc coating in concrete manufactured with Portland cement compared to those recorded for bars in concrete manufactured with pozzolanic cement depends strongly on the higher chloride content at the steel concrete interface.
Burbank, Brant D; Slater, Michael; Kava, Alyssa; Doyle, James; McHale, William A; Latta, Mark A; Gross, Stephen M
2016-02-01
Dental materials capable of releasing calcium, phosphate and fluoride are of great interest for remineralization. Microencapsulated aqueous solutions of these ions in orthodontic cement demonstrate slow, sustained release by passive diffusion through a permeable membrane without the need for dissolution or etching of fillers. The potential to charge a dental material formulated with microencapsulated water with fluoride by toothbrushing with over the counter toothpaste and the effect of microcapsules on cement adhesion to enamel was determined. Orthodontic cements that contained microcapsules with water and controls without microcapsules were brushed with over-the-counter toothpaste and fluoride release was measured. Adhesion measurements were performed loading orthodontic brackets to failure. Cements that contained microencapsulated solutions of 5.0M Ca(NO3)2, 0.8M NaF, 6.0MK2HPO4 or a mixture of all three were prepared. Ion release profiles were measured as a function of time. A greater fluoride charge and re-release from toothbrushing was demonstrated compared to a control with no microcapsules. Adhesion of an orthodontic cement that contained microencapsulated remineralizing agents was 8.5±2.5MPa compared to the control without microcapsules which was of 8.3±1.7MPa. Sustained release of fluoride, calcium and phosphate ions from cement formulated with microencapsulated remineralizing agents was demonstrated. Orthodontic cements with microcapsules show a release of bioavailable fluoride, calcium, and phosphate ions near the tooth surface while having the ability to charge with fluoride and not effect the adhesion of the material to enamel. Incorporation of microcapsules in dental materials is promising for promoting remineralization. Copyright © 2015 Elsevier Ltd. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kirchheim,, A. P.; Dal Molin, D.C.; Emwas, Abdul-Hamid
2010-12-01
This study details the differences in real-time hydration between pure tricalcium aluminate (cubic C{sub 3}A or 3CaO {center_dot} Al{sub 2}O{sub 3}) and Na-doped tricalcium aluminate (orthorhombic C{sub 3}A or Na{sub 2}Ca{sub 8}Al{sub 6}O{sub 18}), in aqueous solutions containing sulfate ions. Pure phases were synthesized in the laboratory to develop an independent benchmark for the reactions, meaning that their reactions during hydration in a simulated early age cement pore solution (saturated with respect to gypsum and lime) were able to be isolated. Because the rate of this reaction is extremely rapid, most microscopy methods are not adequate to study the earlymore » phases of the reactions in the early stages. Here, a high-resolution full-field soft X-ray imaging technique operating in the X-ray water window, combined with solution analysis by {sup 27}Al nuclear magnetic resonance (NMR) spectroscopy, was used to capture information regarding the mechanism of C{sub 3}A hydration during the early stages. There are differences in the hydration mechanism between the two types of C{sub 3}A, which are also dependent on the concentration of sulfate ions in the solution. The reactions with cubic C{sub 3}A (pure) seem to be more influenced by higher concentrations of sulfate ions, forming smaller ettringite needles at a slower pace than the orthorhombic C{sub 3}A (Na-doped) sample. The rate of release of aluminate species into the solution phase is also accelerated by Na doping.« less
Hydroxyapatite clay for gap filling and adequate bone ingrowth.
Maruyama, M; Terayama, K; Ito, M; Takei, T; Kitagawa, E
1995-03-01
In uncemented total hip arthroplasty, a complete filling of the gap between femoral prosthesis and the host bone is difficult and defects would remain, because the anatomy of the reamed intramedullary canal cannot fit the prosthesis. Therefore, it seems practical to fill the gap with a clay containing hydroxyapatite (HA), which has an osteoconductive character. The clay (HA clay) is made by mixing HA granules (size 0.1 mm or more) having a homogeneous pore distribution and a porosity of 35-48 vol%, and a viscous substance such as a saline solution of sodium alginate (SSSA). In the first experiment, the ratio of HA granules and sodium alginate in SSSA is set for the same handling properties of HA clay and polymethylmethacrylate bone cement (standard viscosity) before hardening. As a result, the ratio is set for 55 wt% of HA in the clay and 12.5 wt% of sodium alginate in SSSA (i.e., HA:sodium alginate:saline solution = 9.8:1:7). In the second study, the gap between the femoral stem and bone model is completely filled with HA clay. However, the gap is not filled only with HA granules or HA granules mixed with saline solution. In the third animal experiment, using an unloaded model, histology shows that HA clay has an osteoconductive property bridging the gap between the implant and the cortical bone without any adverse reaction. HA clay is considered a useful biomaterial to fill the gap with adequate bone ingrowth.
He, Fupo; Chen, Yan; Li, Jiyan; Lin, Bomiao; Ouyang, Yi; Yu, Bo; Xia, Yuanyou; Yu, Bo; Ye, Jiandong
2015-04-01
In this study, a platelet-rich plasma poly(lactic-co-glycolic acid) (PRP-PLGA)/calcium phosphate cement (CPC) composite scaffold was prepared by incorporating PRP into PLGA/CPC scaffold with unidirectional pore structure, which was fabricated by the unidirectional freeze casting of CPC slurry and the following infiltration of PLGA. The results from in vitro cell experiments and in vivo implantation in femoral defects manifested that incorporation of PRP into PLGA/CPC scaffold improved in vitro cell response (cell attachment, proliferation, and differentiation), and markedly boosted bone formation, angiogenesis and material degradation. The incorporation of PRP into scaffold showed more outstanding improvement in osteogenesis as the scaffolds were used to repair the segmental radial defects, especially at the early stage. The new bone tissues grew along the unidirectional lamellar pores of scaffold. At 12 weeks postimplantation, the segmental radial defects treated with PRP-PLGA/CPC scaffold had almost recuperated, whereas treated with the scaffold without PRP was far from healed. Taken together, the PRP-PLGA/CPC scaffold with unidirectional pore structure is a promising candidate to repair bone defects at various sites. © 2014 Wiley Periodicals, Inc.
NASA Astrophysics Data System (ADS)
Zhang, Xiaoxian; Crawford, John W.; Flavel, Richard J.; Young, Iain M.
2016-10-01
The Lattice Boltzmann (LB) model and X-ray computed tomography (CT) have been increasingly used in combination over the past decade to simulate water flow and chemical transport at pore scale in porous materials. Because of its limitation in resolution and the hierarchical structure of most natural soils, the X-ray CT tomography can only identify pores that are greater than its resolution and treats other pores as solid. As a result, the so-called solid phase in X-ray images may in reality be a grey phase, containing substantial connected pores capable of conducing fluids and solute. Although modified LB models have been developed to simulate fluid flow in such media, models for solute transport are relatively limited. In this paper, we propose a LB model for simulating solute transport in binary soil images containing permeable solid phase. The model is based on the single-relaxation time approach and uses a modified partial bounce-back method to describe the resistance caused by the permeable solid phase to chemical transport. We derive the relationship between the diffusion coefficient and the parameter introduced in the partial bounce-back method, and test the model against analytical solution for movement of a pulse of tracer. We also validate it against classical finite volume method for solute diffusion in a simple 2D image, and then apply the model to a soil image acquired using X-ray tomography at resolution of 30 μm in attempts to analyse how the ability of the solid phase to diffuse solute at micron-scale affects the behaviour of the solute at macro-scale after a volumetric average. Based on the simulated results, we discuss briefly the danger in interpreting experimental results using the continuum model without fully understanding the pore-scale processes, as well as the potential of using pore-scale modelling and tomography to help improve the continuum models.
Glass-ionomer cement formulations. II. The synthesis of novel polycarobxylic acids.
Crisp, S; Kent, B E; Lewis, B G; Ferner, A J; Wilson, A D
1980-06-01
The synthesis of many polycarboxylic acids is reported. An account is given of their stability in aqueous solution and the properties of cements formed by their reaction with ion-leachable glasses. A copolymer of acrylic and itaconic acids was found to combine several favorable characteristics.
Innovative solutions to buried Portland concrete cement roadways : construction report.
DOT National Transportation Integrated Search
1999-01-01
Maine has hundreds of miles of highway that were constructed of Portland Concrete Cement : (PCC) roughly 6 to 6.1 meters (18 to 20 feet) wide forty or more years ago. Since that time these : same highways have been paved and widened to 6.7 or 7 meter...
Innovative solutions to buried portland cement concrete roadways : first interim report.
DOT National Transportation Integrated Search
2000-05-01
Maine has hundreds of miles of highway that were constructed of Portland Cement : Concrete (PCC) roughly 6 to 6.1 meters (18 to 20 feet) wide forty or more years ago. Since that : time these same highways have been paved and widened to 6.7 or 7 meter...
Relating salt marsh pore water geochemistry patterns to vegetation zones and hydrologic influences
NASA Astrophysics Data System (ADS)
Moffett, Kevan B.; Gorelick, Steven M.
2016-03-01
Physical, chemical, and biological factors influence vegetation zonation in salt marshes and other wetlands, but connections among these factors could be better understood. If salt marsh vegetation and marsh pore water geochemistry coorganize, e.g., via continuous plant water uptake and persistently unsaturated sediments controlling vegetation zone-specific pore water geochemistry, this could complement known physical mechanisms of marsh self-organization. A high-resolution survey of pore water geochemistry was conducted among five salt marsh vegetation zones at the same intertidal elevation. Sampling transects were arrayed both parallel and perpendicular to tidal channels. Pore water geochemistry patterns were both horizontally differentiated, corresponding to vegetation zonation, and vertically differentiated, relating to root influences. The geochemical patterns across the site were less broadly related to marsh hydrology than to vegetation zonation. Mechanisms contributing to geochemical differentiation included: root-induced oxidation and nutrient (P) depletion, surface and creek-bank sediment flushing by rainfall or tides, evapotranspiration creating aerated pore space for partial sediment flushing in some areas while persistently saturated conditions hindered pore water renewal in others, and evapoconcentration of pore water solutes overall. The concentrated pore waters draining to the tidal creeks accounted for 41% of ebb tide solutes (median of 14 elements), including being a potentially toxic source of Ni but a slight sink for Zn, at least during the short, winter study period in southern San Francisco Bay. Heterogeneous vegetation effects on pore water geochemistry are not only significant locally within the marsh but may broadly influence marsh-estuary solute exchange and ecology.
Magnesium-phosphate-glass cements with ceramic-type properties
Sugama, T.; Kukacka, L.E.
1982-09-23
Rapid setting magnesium phosphate (Mg glass) cementitious materials consisting of magnesium phosphate cement paste, polyborax and water-saturated aggregate, exhibits rapid setting and high early strength characteristics. The magnesium glass cement is prepared from a cation-leachable powder and a bivalent metallic ion-accepting liquid such as an aqueous solution of diammonium phosphate and ammonium polyphosphate. The cation-leachable powder includes a mixture of two different magnesium oxide powders processed and sized differently which when mixed with the bivalent metallic ion-accepting liquid provides the magnesium glass cement consisting primarily of magnesium ortho phosphate tetrahydrate, with magnesium hydroxide and magnesium ammonium phosphate hexahydrate also present. The polyborax serves as a set-retarder. The resulting magnesium mono- and polyphosphate cements are particularly suitable for use as a cementing matrix in rapid repair systems for deteriorated concrete structures as well as construction materials and surface coatings for fireproof structures.
Peculiarities of the processes of hydration of binding substances in the arbolite mixture
NASA Astrophysics Data System (ADS)
Innokentieva, L. S.; Egorova, A. D.; Emelianova, Z. V.
2017-09-01
Cement and sand solution is traditionally used for production of wood concrete. But it is known that impact of water-soluble substances of wood on the hardening cement is shown in the stabilizing effect. The "Cement poisons" consisting generally of the HOCH carbohydrate groups, sedimented on a surface of particles of minerals of cement 3CaO.SiO2 (three-calcic silicate) and 3CaO.Al2O3 (three-calcic aluminate) form the thinnest covers which complicate the course of processes of hydration of cement. Plaster in comparison with cement is less sensitive to extractive substances of wood therefore their combination to wood (including waste of logging and a woodworking) both coniferous and deciduous species is allowed. Composite plaster binding with hongurin as active mineral additive agent are applied at selection of composition of arbolite, at the same time dependences of their physicomechanical properties on characteristics of filler are received.
Magnesium phosphate glass cements with ceramic-type properties
Sugama, Toshifumi; Kukacka, Lawrence E.
1984-03-13
Rapid setting magnesium phosphate (Mg glass) cementitious materials consisting of magnesium phosphate cement paste, polyborax and water-saturated aggregate exhibiting rapid setting and high early strength characteristics. The magnesium glass cement is prepared from a cation-leachable powder and a bivalent metallic ion-accepting liquid such as an aqueous solution of diammonium phosphate and ammonium polyphosphate. The cation-leachable powder includes a mixture of two different magnesium oxide powders processed and sized differently which when mixed with the bivalent metallic ion-accepting liquid provides the magnesium glass cement consisting primarily of magnesium ortho phosphate tetrahydrate, with magnesium hydroxide and magnesium ammonium phosphate hexahydrate also present. The polyborax serves as a set-retarder. The resulting magnesium mono- and polyphosphate cements are particularly suitable for use as a cementing matrix in rapid repair systems for deteriorated concrete structures as well as construction materials and surface coatings for fireproof structures.
NASA Astrophysics Data System (ADS)
de Vries, Enno T.; Raoof, Amir; van Genuchten, Martinus Th.
2017-07-01
Many environmental and agricultural applications involve the transport of water and dissolved constituents through aggregated soil profiles, or porous media that are structured, fractured or macroporous in other ways. During the past several decades, various process-based macroscopic models have been used to simulate contaminant transport in such media. Many of these models consider advective-dispersive transport through relatively large inter-aggregate pore domains, while exchange with the smaller intra-aggregate pores is assumed to be controlled by diffusion. Exchange of solute between the two domains is often represented using a first-order mass transfer coefficient, which is commonly obtained by fitting to observed data. This study aims to understand and quantify the solute exchange term by applying a dual-porosity pore-scale network model to relatively large domains, and analysing the pore-scale results in terms of the classical dual-porosity (mobile-immobile) transport formulation. We examined the effects of key parameters (notably aggregate porosity and aggregate permeability) on the main dual-porosity model parameters, i.e., the mobile water fraction (ϕm) and the mass transfer coefficient (α). Results were obtained for a wide range of aggregate porosities (between 0.082 and 0.700). The effect of aggregate permeability was explored by varying pore throat sizes within the aggregates. Solute breakthrough curves (BTCs) obtained with the pore-scale network model at several locations along the domain were analysed using analytical solutions of the dual-porosity model to obtain estimates of ϕm and α. An increase in aggregate porosity was found to decrease ϕm and increase α, leading to considerable tailing in the BTCs. Changes in the aggregate pore throat size affected the relative flow velocity between the intra- and inter-aggregate domains. Higher flow velocities within the aggregates caused a change in the transport regime from diffusion dominated to more advection dominated. This change increased the exchange rate of solutes between the mobile and immobile domains, with a related increase in the value of the mass transfer coefficient and less tailing in the BTCs.
Attar, Hanaa El; Elhiny, Omnia; Salem, Ghada; Abdelrahman, Ahmed; Attia, Mazen
2016-12-15
To test the solubility of dual cure resin modified resin cement in a food simulating solution and the shear bond strength compared to conventional Glass ionomer cement. The materials tested were self-adhesive dual cure resin modified cement and Glass Ionomer (GIC). Twenty Teflon moulds were divided into two groups of tens. The first group was injected and packed with the modified resin cement, the second group was packed with GIC. To test the solubility, each mould was weighed before and after being placed in an analytical reagent for 30 days. The solubility was measured as the difference between the initial and final drying mass. To measure the Shear bond strength, 20 freshly extracted wisdom teeth were equally divided into two groups and embedded in self-cure acrylic resin. Four mm sections of stainless steel bands were cemented to the exposed buccal surfaces of teeth under a constant load of 500 g. Shear bond strength was measured using a computer controlled materials testing machine and the load required to deband the samples was recorded in Newtons. GIC showed significantly higher mean weight loss and an insignificant lower Shear bond strength, compared to dual cure resin Cement. It was found that dual cure resin modified cement was less soluble than glass ionomer cement and of comparable bond strength rendering it more useful clinically for orthodontic band cementation.
Research of cost aspects of cement pavements construction
NASA Astrophysics Data System (ADS)
Bezuglyi, Artem; Illiash, Sergii; Tymoshchuk, Oleksandr
2017-09-01
The tendency to increasing traffic volume on public roads and to increased axle loads of vehicles makes the road scientists to develop scientifically justified methods for preserving the existing and developing the new transport network of Ukraine. One of the options for solving such issues is the construction of roads with rigid (cement concrete) pavement. However, any solution must be justified considering technical and economic components. This paper presents the results of the research of cost aspects of cement pavements construction.
Parris, T.M.; Burruss, R.C.; O'Sullivan, P. B.
2003-01-01
Along the southeast border of the 1002 Assessment Area in the Arctic National Wildlife Refuge, Alaska, an explicit link between gas generation and deformation in the Brooks Range fold and thrust belt is provided through petrographic, fluid inclusion, and stable isotope analyses of fracture cements integrated with zircon fission-track data. Predominantly quartz-cemented fractures, collected from thrusted Triassic and Jurassic rocks, contain crack-seal textures, healed microcracks, and curved crystals and fluid inclusion populations, which suggest that cement growth occurred before, during, and after deformation. Fluid inclusion homogenization temperatures (175-250??C) and temperature trends in fracture samples suggest that cements grew at 7-10 km depth during the transition from burial to uplift and during early uplift. CH4-rich (dry gas) inclusions in the Shublik Formation and Kingak Shale are consistent with inclusion entrapment at high thermal maturity for these source rocks. Pressure modeling of these CH4-rich inclusions suggests that pore fluids were overpressured during fracture cementation. Zircon fission-track data in the area record postdeposition denudation associated with early Brooks Range deformation at 64 ?? 3 Ma. With a closure temperature of 225-240??C, the zircon fission-track data overlap homogenization temperatures of coeval aqueous inclusions and inclusions containing dry gas in Kingak and Shublik fracture cements. This critical time-temperature relationship suggests that fracture cementation occurred during early Brooks Range deformation. Dry gas inclusions suggest that Shublik and Kingak source rocks had exceeded peak oil and gas generation temperatures at the time structural traps formed during early Brooks Range deformation. The timing of hydrocarbon generation with respect to deformation therefore represents an important exploration risk for gas exploration in this part of the Brooks Range fold and thrust belt. The persistence of gas high at thermal maturity levels suggests, however, that significant volumes of gas may have been generated.
Immediate impact on the rim zone of cement based materials due to chemical attack
DOE Office of Scientific and Technical Information (OSTI.GOV)
Schwotzer, M., E-mail: matthias.schwotzer@kit.edu; Scherer, T.; Gerdes, A.
2015-01-15
Cement based materials are in their widespread application fields exposed to various aqueous environments. This can lead to serious chemical changes affecting the durability of the materials. In particular in the context of service life prediction a detailed knowledge of the reaction mechanisms is a necessary base for the evaluation of the aggressivity of an aqueous medium and this is deduced commonly from long term investigations. However, these processes start immediately at the material/water-interface, when a cementitious system comes into contact with an aqueous solution, altering here the chemical composition and microstructure. This rim zone represents the first hurdle thatmore » has to be overcome by an attacking aqueous solution. Therefore, the properties of the surface near area should be closely associated with the further course of deterioration processes by reactive transport. In this context short term exposure experiments with hardened cement paste over 4 and 48 h have been carried out with demineralized water, hard tap water and different sulfate solutions. In order to investigate immediate changes in the near-surface region, depth profile cuts have been performed on the cement paste samples by means of focused ion beam preparation techniques. A scanning beam of Gallium ions is applied to cut a sharp edge in the cement paste surface, providing insights into the composition and microstructure of the upper ten to hundred microns. Electron microscopic investigations on such a section of the rim zone, together with surface sensitive X-ray diffraction accompanied by a detailed characterization of the bulk composition confirm that the properties of the material/water interface are of relevance for the durability of cement based systems in contact with aqueous solutions. In this manner, focused ion beam investigations constitute auspicious tools to contribute to a more sophisticated understanding of the reaction mechanisms. - Highlights: • The chemical stability is related to the properties of material/water interface. • Properties of the rim zone readjust quickly, triggered by hydrochemical conditions. • Durability research can be improved by combining FIB techniques and common analytics.« less
Leaching and mechanical behaviour of concrete manufactured with recycled aggregates.
Sani, D; Moriconi, G; Fava, G; Corinaldesi, V
2005-01-01
The reuse of debris from building demolition is of increasing public interest because it decreases the volume of material to be disposed to landfill. This research is focused on the evaluation of the possibility of reusing recycled aggregate from construction or demolition waste (C&D) as a substitute for natural aggregate in concrete production. In most applications, cement based materials are used for building construction due to their cost effectiveness and performance; however their impact on the surrounding environment should be monitored. The interstitial pore fluid in contact with hydrated cementitious materials is characterized by persistent alkaline pH values buffered by the presence of hydrate calcium silicate, portlandite and alkaline ions. An experimental plan was carried out to investigate concrete structural properties in relation to alkali release in aqueous solution. Results indicate that the presence of recycled aggregate increases the leachability of unreactive ions (Na, K, Cl), while for calcium the substitution resulted in a lower net leaching. In spite of the lower mechanical resistance (40% less), such a waste concrete may be suggested as more environmentally sustainable.
Study on small-strain behaviours of methane hydrate sandy sediments using discrete element method
DOE Office of Scientific and Technical Information (OSTI.GOV)
Yu Yanxin; Cheng Yipik; Xu Xiaomin
Methane hydrate bearing soil has attracted increasing interest as a potential energy resource where methane gas can be extracted from dissociating hydrate-bearing sediments. Seismic testing techniques have been applied extensively and in various ways, to detect the presence of hydrates, due to the fact that hydrates increase the stiffness of hydrate-bearing sediments. With the recognition of the limitations of laboratory and field tests, wave propagation modelling using Discrete Element Method (DEM) was conducted in this study in order to provide some particle-scale insights on the hydrate-bearing sandy sediment models with pore-filling and cementation hydrate distributions. The relationship between shear wavemore » velocity and hydrate saturation was established by both DEM simulations and analytical solutions. Obvious differences were observed in the dependence of wave velocity on hydrate saturation for these two cases. From the shear wave velocity measurement and particle-scale analysis, it was found that the small-strain mechanical properties of hydrate-bearing sandy sediments are governed by both the hydrate distribution patterns and hydrate saturation.« less
Kwon, Yang-Hee; Kang, Sung-Hoon; Hong, Sung-Gul; Moon, Juhyuk
2017-02-24
Without using strong alkaline solution or ordinary Portland cement, a new structural binder consisting of fly ash and hydrated lime was hardened through an intensified pozzolanic reaction. The main experimental variables are the addition of silica fume and initial thermal treatment (60 °C for 3 days). A series of experiments consisting of mechanical testing (compressive and flexural strength, modulus of elasticity), X-ray diffraction, and measurements of the heat of hydration, pore structure, and shrinkage were conducted. These tests show that this new fly ash-based mortar has a compressive strength of 15 MPa at 91 days without any silica fume addition or initial thermal treatment. The strength increased to over 50 MPa based on the acceleration of the intensified pozzolanic reaction from the silica fume addition and initial thermal treatment. This is explained by a significant synergistic effect induced by the silica fume. It intensifies the pozzolanic reaction under thermal treatment and provides a space filling effect. This improved material performance can open a new pathway to utilize the industrial by-product of fly ash in cementless construction materials.
NASA Astrophysics Data System (ADS)
Radonjic, M.
2015-12-01
Recent focus on carbon emission from cement industry inspired researchers to improve CSH properties by reducing Ca/Si ratio at the nanoscale, and lower porosity (permeability) of hydrated cement at micro scale. If implemented in wellbore cement technology, both of these efforts could provide advanced properties for wellbore infrastructure. These advancements would further reduce the issue of leaky wellbores in fluid injections, hydraulic fracturing and subsurface storage for existing operating wells. Numerous inadequately abandoned wells, however, pose more complex engineering problems, primarily due to the difficulty in locating fluid flow pathways along the wellbore structure. In order to appreciate the difficulty of this problem, we need to remind ourselves that: a typical 30,000-ft. wellbore with an average production casing of 8 inches in diameter can be presented in scale by a 6-m long human hair of 150 μm these structures are placed in the subsurface, often not just vertical in geometry but deviated close to 90° tangent where monitoring and remediation becomes demanding and if we consider that wellbore cement is not continuously placed along the wellbore and it is approximately 1/10 of a wellbore diameter, we can see that the properties of these materials demand application of nano-science and a different scale phenomena than perhaps previously acknowledged. The key concept behind Ca/Si reduction associated with improved mechanical properties is traditionally achieved chemically, by addition of supplemental cementitious materials. In our study we have tried to evaluate CSH alterations due to mechanically induced phase transformation. The data suggest that confined compression-extrusion of hydrated wellbore cement and the consequent propagation of pore water can change cement composition by dissolving and removing Ca, therefore reducing Ca/Si of cement phases. The advantage of this approach is that the process is less impacted by pressure/temperature oscillations found in subsurface conditions. In addition, we have proved experimentally, that even cement samples stored in corrosive environment for two years can successfully be treated and healed by confined compression of tubular expansion for purpose of microannular gas flow remediation.
DOT National Transportation Integrated Search
1998-06-01
We used a simulated concrete pore water solution to evaluate the corrosion protection performance of concrete corrosion-inhibiting admixtures and epoxy-coated reinforcing bars (ECR). We evaluated three commercial corrosion inhibitors, ECR from three ...
Permeability-porosity relationships in sedimentary rocks
Nelson, Philip H.
1994-01-01
In many consolidated sandstone and carbonate formations, plots of core data show that the logarithm of permeability (k) is often linearly proportional to porosity (??). The slope, intercept, and degree of scatter of these log(k)-?? trends vary from formation to formation, and these variations are attributed to differences in initial grain size and sorting, diagenetic history, and compaction history. In unconsolidated sands, better sorting systematically increases both permeability and porosity. In sands and sandstones, an increase in gravel and coarse grain size content causes k to increase even while decreasing ??. Diagenetic minerals in the pore space of sandstones, such as cement and some clay types, tend to decrease log(k) proportionately as ?? decreases. Models to predict permeability from porosity and other measurable rock parameters fall into three classes based on either grain, surface area, or pore dimension considerations. (Models that directly incorporate well log measurements but have no particular theoretical underpinnings from a fourth class.) Grain-based models show permeability proportional to the square of grain size times porosity raised to (roughly) the fifth power, with grain sorting as an additional parameter. Surface-area models show permeability proportional to the inverse square of pore surface area times porosity raised to (roughly) the fourth power; measures of surface area include irreducible water saturation and nuclear magnetic resonance. Pore-dimension models show permeability proportional to the square of a pore dimension times porosity raised to a power of (roughly) two and produce curves of constant pore size that transgress the linear data trends on a log(k)-?? plot. The pore dimension is obtained from mercury injection measurements and is interpreted as the pore opening size of some interconnected fraction of the pore system. The linear log(k)-?? data trends cut the curves of constant pore size from the pore-dimension models, which shows that porosity reduction is always accompanied by a reduction in characteristic pore size. The high powers of porosity of the grain-based and surface-area models are required to compensate for the inclusion of the small end of the pore size spectrum.
The physical properties of accelerated Portland cement for endodontic use.
Camilleri, J
2008-02-01
To investigate the physical properties of a novel accelerated Portland cement. The setting time, compressive strength, pH and solubility of white Portland cement (Lafarge Asland; CEM 1, 52.5 N) and accelerated Portland cement (Proto A) produced by excluding gypsum from the manufacturing process (Aalborg White) and a modified version with 4 : 1 addition of bismuth oxide (Proto B) were evaluated. Proto A set in 8 min. The compressive strength of Proto A was comparable with that of Portland cement at all testing periods (P > 0.05). Additions of bismuth oxide extended the setting time and reduced the compressive strength (P < 0.05). Both cements and storage solution were alkaline. All cements tested increased by >12% of their original weight after immersion in water for 1 day with no further absorption after 28 days. Addition of bismuth oxide increased the water uptake of the novel cement (P < 0.05). The setting time of Portland cement can be reduced by excluding the gypsum during the last stage of the manufacturing process without affecting its other properties. Addition of bismuth oxide affected the properties of the novel cement. Further investigation on the effect that bismuth oxide has on the properties of mineral trioxide aggregate is thus warranted.
BiOBr@SiO2 flower-like nanospheres chemically-bonded on cement-based materials for photocatalysis
NASA Astrophysics Data System (ADS)
Wang, Dan; Hou, Pengkun; Yang, Ping; Cheng, Xin
2018-02-01
Endowment of photocatalytic property on the surface of concrete structure can contribute to the self-cleaning of the structure and purification of the polluted environment. We developed a nano-structured BiOBr@SiO2 photocatalyst and innovatively used for surface-treatment of cement-based materials with the hope of attaining the photocatalytic property in visible-light region and surface modification/densification performances. The SiO2 layer on the flower-like BiOBr@SiO2 helps to maintain a stable distribution of the photocatalyst, as well as achieving a chemical bonding between the coating and the cement matrix. Results showed that the color fading rate of during the degradation of Rhodamine B dye of the BiOBr-cem sample is 2 times higher compared with the commonly studied C, N-TiO2-cem sample. The photo-degradation rates of samples BiOBr-cem and BiOBr@SiO2-cem are 93 and 81% within 150 min, respectively, while sample BiOBr@SiO2-cem reveals a denser and smoother surface after curing for 28 days and pore-filling effect at size within 0.01-0.2 μm when compared with untreated samples. Moreover, additional C-S-H gel can be formed due to the pozzolanic reaction between BiOBr@SiO2 and the hardened cement matrix. Both advantages of the BiOBr@SiO2 favor its application for surface-treatment of hardened cement-based material to acquire an improved surface quality, as well as durable photocatalytic functionality.
Composite Material from By-products and Its Properties
NASA Astrophysics Data System (ADS)
Šeps, K.; Broukalová, I.; Vodička, J.
2017-09-01
The paper shows an example of utilization of specific textile admixture - fluffs of torn textiles from waste cars in production of composite with aggregate consisting entirely of unsorted recycled concrete. The admixture in the mixture of recycled concrete and cement binder fills the pores and voids in composite. The elaborated composite has working title STEREDconcrete. In the article, basic mechanical-physical properties of the composite are presented also the fire resistance of STEREDconcrete, which was determined in tests.
Conservation of ornamental stone by Myxococcus xanthus-induced carbonate biomineralization.
Rodriguez-Navarro, Carlos; Rodriguez-Gallego, Manuel; Ben Chekroun, Koutar; Gonzalez-Muñoz, Maria Teresa
2003-04-01
Increasing environmental pollution in urban areas has been endangering the survival of carbonate stones in monuments and statuary for many decades. Numerous conservation treatments have been applied for the protection and consolidation of these works of art. Most of them, however, either release dangerous gases during curing or show very little efficacy. Bacterially induced carbonate mineralization has been proposed as a novel and environmentally friendly strategy for the conservation of deteriorated ornamental stone. However, the method appeared to display insufficient consolidation and plugging of pores. Here we report that Myxococcus xanthus-induced calcium carbonate precipitation efficiently protects and consolidates porous ornamental limestone. The newly formed carbonate cements calcite grains by depositing on the walls of the pores without plugging them. Sonication tests demonstrate that these new carbonate crystals are strongly attached to the substratum, mostly due to epitaxial growth on preexisting calcite grains. The new crystals are more stress resistant than the calcite grains of the original stone because they are organic-inorganic composites. Variations in the phosphate concentrations of the culture medium lead to changes in local pH and bacterial productivity. These affect the structure of the new cement and the type of precipitated CaCO(3) polymorph (vaterite or calcite). The manipulation of culture medium composition creates new ways of controlling bacterial biomineralization that in the future could be applied to the conservation of ornamental stone.
Conservation of Ornamental Stone by Myxococcus xanthus-Induced Carbonate Biomineralization
Rodriguez-Navarro, Carlos; Rodriguez-Gallego, Manuel; Ben Chekroun, Koutar; Gonzalez-Muñoz, Maria Teresa
2003-01-01
Increasing environmental pollution in urban areas has been endangering the survival of carbonate stones in monuments and statuary for many decades. Numerous conservation treatments have been applied for the protection and consolidation of these works of art. Most of them, however, either release dangerous gases during curing or show very little efficacy. Bacterially induced carbonate mineralization has been proposed as a novel and environmentally friendly strategy for the conservation of deteriorated ornamental stone. However, the method appeared to display insufficient consolidation and plugging of pores. Here we report that Myxococcus xanthus-induced calcium carbonate precipitation efficiently protects and consolidates porous ornamental limestone. The newly formed carbonate cements calcite grains by depositing on the walls of the pores without plugging them. Sonication tests demonstrate that these new carbonate crystals are strongly attached to the substratum, mostly due to epitaxial growth on preexisting calcite grains. The new crystals are more stress resistant than the calcite grains of the original stone because they are organic-inorganic composites. Variations in the phosphate concentrations of the culture medium lead to changes in local pH and bacterial productivity. These affect the structure of the new cement and the type of precipitated CaCO3 polymorph (vaterite or calcite). The manipulation of culture medium composition creates new ways of controlling bacterial biomineralization that in the future could be applied to the conservation of ornamental stone. PMID:12676699
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hansley, P.L.; Nuccio, V.F.
Comparison of the petrology of shallow and deep oil reservoirs in the Upper Cretaceous Shannon Sandstone Beds of the Steele Member of the Cody Shale strongly suggests that organic acids have had a more significant impact on the diagenetic alteration of aluminosilicate grains and carbonate cements in the deep reservoirs than in the shallow reservoirs. In shallow reservoirs, detrital grains exhibit minor dissolution, sparse and small overgrowths, and secondary porosity created by dissolution of early calcite cement. However, deeper sandstones are characterized by extensive dissolution of detrital K-feldspar and detrital glauconite grains, and precipitation of abundant, large quartz and feldsparmore » overgrowths. Throughout the Shannon and Steele, dissolution of glauconite and degradation of kerogen were probably aided by clay mineral/organic catalysis, which caused simultaneous reduction of iron and oxidation of kerogen. This process resulted in release of ferrous iron and organic acids and was promoted in the deep reservoirs by higher formation temperatures accounting for more extensive dissolution of aluminosilicate grains. Carbonic acid produced from the dissolution of early calcite cement, decarboxylation of organic matter, and influx of meteoric water after Laramide uplift produced additional dissolution of cements and grains. Dissolution by organic acids and complexing by organic acid anions, however, best explain the intensity of diagenesis and absence of dissolution products in secondary pores and on etched surfaces of framework grains in deep reservoirs.« less
Diesen, Veronica; Forsberg, Kerstin; Jonsson, Mats
2017-10-15
The deep repository for low and intermediate level radioactive waste SFR in Sweden will contain large amounts of cellulosic waste materials contaminated with radionuclides. Over time the repository will be filled with water and alkaline conditions will prevail. In the present study degradation of cellulosic materials and the ability of cellulosic degradation products to solubilize and thereby mobilise Eu(III) under repository conditions has been investigated. Further, the possible immobilization of Eu(III) by sorption onto cement in the presence of degradation products has been investigated. The cellulosic material has been degraded under anaerobic and aerobic conditions in alkaline media (pH: 12.5) at ambient temperature. The degradation was followed by measuring the total organic carbon (TOC) content in the aqueous phase as a function of time. After 173days of degradation the TOC content is highest in the anaerobic artificial cement pore water (1547mg/L). The degradation products are capable of solubilising Eu(III) and the total europium concentration in the aqueous phase was 900μmol/L after 498h contact time under anaerobic conditions. Further it is shown that Eu(III) is adsorbed to the hydrated cement to a low extent (<9μmol Eu/g of cement) in the presence of degradation products. Copyright © 2017 Elsevier B.V. All rights reserved.
Long, Wu-Jian; Wei, Jing-Jie; Ma, Hongyan; Xing, Feng
2017-11-24
This paper presents an experimental investigation on the effect of uniformly dispersed graphene oxide (GO) nanosheets on dynamic mechanical properties of cement based composites prepared with recycled fine aggregate (RFA). Three different amounts of GO, 0.05%, 0.10%, and 0.20% in mass of cement, were used in the experiments. The visual inspections of GO nanosheets were also carried out after ultrasonication by transmission electron microscope (TEM) atomic force microscope (AFM), and Raman to characterize the dispersion effect of graphite oxide. Dynamic mechanical analyzer test showed that the maximum increased amount of loss factor and storage modulus, energy absorption was 125%, 53%, and 200% when compared to the control sample, respectively. The flexural and compressive strengths of GO-mortar increased up to 22% to 41.3% and 16.2% to 16.4% with 0.20 wt % GO at 14 and 28 days, respectively. However the workability decreased by 7.5% to 18.8% with 0.05% and 0.2% GO addition. Microstructural analysis with environmental scanning electron microscopy (ESEM)/backscattered mode (BSEM) showed that the GO-cement composites had a much denser structure and better crystallized hydration products, meanwhile mercury intrusion porosimetry (MIP) testing and image analysis demonstrated that the incorporation of GO in the composites can help in refining capillary pore structure and reducing the air voids content.
Wei, Jing-Jie; Xing, Feng
2017-01-01
This paper presents an experimental investigation on the effect of uniformly dispersed graphene oxide (GO) nanosheets on dynamic mechanical properties of cement based composites prepared with recycled fine aggregate (RFA). Three different amounts of GO, 0.05%, 0.10%, and 0.20% in mass of cement, were used in the experiments. The visual inspections of GO nanosheets were also carried out after ultrasonication by transmission electron microscope (TEM) atomic force microscope (AFM), and Raman to characterize the dispersion effect of graphite oxide. Dynamic mechanical analyzer test showed that the maximum increased amount of loss factor and storage modulus, energy absorption was 125%, 53%, and 200% when compared to the control sample, respectively. The flexural and compressive strengths of GO-mortar increased up to 22% to 41.3% and 16.2% to 16.4% with 0.20 wt % GO at 14 and 28 days, respectively. However the workability decreased by 7.5% to 18.8% with 0.05% and 0.2% GO addition. Microstructural analysis with environmental scanning electron microscopy (ESEM)/backscattered mode (BSEM) showed that the GO-cement composites had a much denser structure and better crystallized hydration products, meanwhile mercury intrusion porosimetry (MIP) testing and image analysis demonstrated that the incorporation of GO in the composites can help in refining capillary pore structure and reducing the air voids content. PMID:29186810
High temperature ion channels and pores
NASA Technical Reports Server (NTRS)
Cheley, Stephen (Inventor); Gu, Li Qun (Inventor); Bayley, Hagan (Inventor); Kang, Xiaofeng (Inventor)
2011-01-01
The present invention includes an apparatus, system and method for stochastic sensing of an analyte to a protein pore. The protein pore may be an engineer protein pore, such as an ion channel at temperatures above 55.degree. C. and even as high as near 100.degree. C. The analyte may be any reactive analyte, including chemical weapons, environmental toxins and pharmaceuticals. The analyte covalently bonds to the sensor element to produce a detectable electrical current signal. Possible signals include change in electrical current. Detection of the signal allows identification of the analyte and determination of its concentration in a sample solution. Multiple analytes present in the same solution may also be detected.
Daniele Tonina; Alberto Bellin
2008-01-01
Pore-scale dispersion (PSD), aquifer heterogeneity, sampling volume, and source size influence solute concentrations of conservative tracers transported in heterogeneous porous formations. In this work, we developed a new set of analytical solutions for the concentration ensemble mean, variance, and coefficient of variation (CV), which consider the effects of all these...
Innovative solutions to buried portland cement concrete roadways.
DOT National Transportation Integrated Search
2005-03-01
Forty or more years ago hundreds of miles of Maine highways were constructed of Portland Cement : Concrete (PCC) to a width of 5.5 to 6.0 m (18 to 20 ft). Since that time these same highways have been : paved and widened to 6.7 or 7.3 m (22 or 24 ft)...
Innovative solutions to buried portland cement concrete roadways : second interim.
DOT National Transportation Integrated Search
2001-04-01
Maine has hundreds of miles of highway that were constructed of : Portland Cement Concrete (PCC) roughly 6 to 6.1 m (18 to 20 ft) wide forty : or more years ago. Since that time these same highways have been paved : and widened to 6.7 or 7 m (22 or 2...
Characterization and analyses of acid-extractable and leached trace elements in dental cements.
Camilleri, J; Kralj, P; Veber, M; Sinagra, E
2012-08-01
Determination of the elemental constitution and investigation of the total and leachable arsenic, chromium and lead in Portland cement, pure tricalcium silicate, Biodentine, Bioaggregate and mineral trioxide aggregate (MTA) Angelus. The chemical composition of Portland cement, MTA Angelus, tricalcium silicate cement, Biodentine and Bioaggregate was determined using X-ray fluorescence (XRF). Measurements of arsenic, lead and chromium were taken with inductively coupled plasma-mass spectrometry (ICP-MS), following acid digestion on the hydrated material and on leachates of cements soaked in Hank's balanced salt solution (HBSS). All the cements investigated had a similar oxide composition with the main oxide being calcium and silicon oxide. Both the Portland cement and MTA Angelus had an additional aluminium oxide. The dental cements included a radiopacifying material. All the materials tested had higher acid-extractable arsenic content than the level set by ISO 9917-1 (2007) and an acceptable level of lead. Regardless these high levels of trace elements present in the materials, the leaching in HBSS was minimal for all the dental material tested in contrast to the high levels displayed by Portland cement. Dental materials based on tricalcium silicate cement and MTA Angelus release minimal quantities of trace elements when in contact with simulated body fluids. The results of acid extraction could be affected by nonspecific matrix effects by the cement. © 2012 International Endodontic Journal.
NASA Astrophysics Data System (ADS)
Falcon-Suarez, I.; North, L. J.; Best, A. I.
2017-12-01
To date, the most promising mitigation strategy for reducing global carbon emissions is Carbon Capture and Storage (CCS). The storage technology (i.e., CO2 geosequestration, CGS) consists of injecting CO2 into deep geological formations, specifically selected for such massive-scale storage. To guarantee the mechanical stability of the reservoir during and after injection, it is crucial to improve existing monitoring techniques for controlling CGS activities. We developed a comprehensive experimental program to investigate the integrity of the Sleipner CO2 storage site in the North Sea - the first commercial CCS project in history where 1 Mtn/y of CO2 has been injected since 1996. We assessed hydro-mechanical effects and the related geophysical signatures of three synthetic sandstones and samples from the Utsira Sand formation (main reservoir at Sleipner), at realistic pressure-temperature (PT) conditions and fluid compositions. Our experimental approach consists of brine-CO2 flow-through tests simulating variable inflation/depletion scenarios, performed in the CGS-rig (Fig. 1; Falcon-Suarez et al., 2017) at the National Oceanography Centre (NOC) in Southampton. The rig is designed for simultaneous monitoring of ultrasonic P- and S-wave velocities and attenuations, electrical resistivity, axial and radial strains, pore pressure and flow, during the co-injection of up to two fluids under controlled PT conditions. Our results show velocity-resistivity and seismic-geomechanical relations of practical importance for the distinction between pore pressure and pore fluid distribution during CGS activities. By combining geophysical and thermo-hydro-mechano-chemical coupled information, we can provide laboratory datasets that complement in situ seismic, geomechanical and electrical survey information, useful for the CO2 plume monitoring in Sleipner site and other shallow weakly-cemented sand CCS reservoirs. Falcon-Suarez, I., Marín-Moreno, H., Browning, F., Lichtschlag, A., Robert, K., North, L.J., Best, A.I., 2017. Experimental assessment of pore fluid distribution and geomechanical changes in saline sandstone reservoirs during and after CO2 injection. International Journal of Greenhouse Gas Control 63, 356-369.
Porosimetric, Thermal and Strength Tests of Aerated and Nonaerated Concretes
NASA Astrophysics Data System (ADS)
Strzałkowski, Jarosław; Garbalińska, Halina
2017-10-01
The paper presents the results of porosimetry tests of lightweight concretes, obtained with three research methods. Impact of different porosity structures on the basic thermal and strength properties was also evaluated. Tests were performed, using the pressure gauge method on fresh concrete mixes, as well as using the mercury porosimetry test and optic RapidAir method on specimens prepared from mature composites. The study was conducted on lightweight concretes, based on expanded clay aggregate and fly ash aggregate, in two variants: with non-aerated and aerated cement matrix. In addition, two reference concretes, based on normal aggregate, were prepared, also in two variants of matrix aeration. Changes in thermal conductivity λ and volumetric specific heat cv throughout the first three months of curing of the concretes were examined. Additionally, tests for compressive strength on cubic samples were performed during the first three months of curing. It was found that the pressure gauge method, performed on a fresh mix, gave lowered values of porosity, compared to the other methods. The mercury porosity tests showed high sensitivity in evaluation of pores smaller than 30μm. Unfortunately, this technique is not suitable for analysing pores greater than 300μm. On the other hand, the optical method proves good in evaluation of large pores, greater than 300μm. The paper also presents results of correlation of individual methods of porosity testing. A consolidated graph of the pore structure, derived from both mercury and optical methods, was presented, too. For the all of six tested concretes, differential graphs of porosity, prepared with both methods, show a very broad convergence. The thermal test results indicate usefulness of aeration of the cement matrix of the composites based on lightweight aggregates for the further reduction of the thermal conductivity coefficient λ of the materials. The lowest values of the λ coefficient were obtained for the aerated concretes based of fly ash aggregate. A diminishing influence of aeration on the volumetric heat capacity cv is clearly seen. Simultaneous aeration of the matrix and use of lightweight aggregates brought about also a significant decrease in the average compressive strength fcm of the tested composites.
Page, W J; Huyer, G; Huyer, M; Worobec, E A
1989-01-01
The major outer membrane protein was extracted from Campylobacter coli by Triton X-100/EDTA fractionation of cell envelopes. This heat-modifiable protein was shown to have pore-forming activity in black lipid bilayers. The C. coli porin formed a relatively small cation-selective pore with a mean single-channel conductance of 0.53 +/- 0.16 nS in 1.0 M KCl. There was no evidence of oligomer formation, which suggested that each protein monomer formed a pore. Pore-forming activity of the C. coli porin and similarly prepared Campylobacter jejuni porin was also measured in liposome-swelling assays. These results confirmed the cation selectivity of both pores. The C. coli porin formed a small pore, which hindered the penetration of solutes with a molecular weight of 262, and a larger pore, which hindered the penetration of solutes with a molecular weight of 340, in a protein-concentration-dependent manner. C. jejuni formed one size of pore that was slightly larger than the C. coli pore and just permitted the passage of solutes, with a molecular weight of 340. A review of the literature concerning in vitro screening of antimicrobial agents tended to confirm the low permeability of the C. jejuni outer membrane to hydrophilic antimicrobial agents except when the molecules had molecular weights of less than 360. The porins of C. jejuni and C. coli may contribute to intrinsic resistance to antimicrobial agents, whereas alternative (nonporin) routes of antimicrobial agent uptake may be more important determinants of susceptibility to antimicrobial agents. Images PMID:2543277
Page, W J; Huyer, G; Huyer, M; Worobec, E A
1989-03-01
The major outer membrane protein was extracted from Campylobacter coli by Triton X-100/EDTA fractionation of cell envelopes. This heat-modifiable protein was shown to have pore-forming activity in black lipid bilayers. The C. coli porin formed a relatively small cation-selective pore with a mean single-channel conductance of 0.53 +/- 0.16 nS in 1.0 M KCl. There was no evidence of oligomer formation, which suggested that each protein monomer formed a pore. Pore-forming activity of the C. coli porin and similarly prepared Campylobacter jejuni porin was also measured in liposome-swelling assays. These results confirmed the cation selectivity of both pores. The C. coli porin formed a small pore, which hindered the penetration of solutes with a molecular weight of 262, and a larger pore, which hindered the penetration of solutes with a molecular weight of 340, in a protein-concentration-dependent manner. C. jejuni formed one size of pore that was slightly larger than the C. coli pore and just permitted the passage of solutes, with a molecular weight of 340. A review of the literature concerning in vitro screening of antimicrobial agents tended to confirm the low permeability of the C. jejuni outer membrane to hydrophilic antimicrobial agents except when the molecules had molecular weights of less than 360. The porins of C. jejuni and C. coli may contribute to intrinsic resistance to antimicrobial agents, whereas alternative (nonporin) routes of antimicrobial agent uptake may be more important determinants of susceptibility to antimicrobial agents.
Silicon-based Porous Ceramics via Freeze Casting of Preceramic Polymers
NASA Astrophysics Data System (ADS)
Naviroj, Maninpat
Freeze casting is a technique for processing porous materials that has drawn significant attention for its effectiveness in producing a variety of tailorable pore structures for ceramics, metals, and polymers. With freeze casting, pores are generated based on a solidification process where ice crystals act as a sacrificial template which can eventually be sublimated to create pores. While the majority of freeze-casting studies have been performed using conventional ceramic suspensions, this work explores an alternative processing route by freeze casting with preceramic polymer solutions. Significant differences exist between freeze casting of a particulate suspension and a polymeric solution. These changes affect the processing method, solidification behavior, and pore structure, thereby introducing new challenges and possibilities for the freeze-casting technique. The first part of this study explored the processing requirements involved with freeze casting of preceramic polymers, along with methods to control the resulting pore structure. Solvent choice, freezing front velocity, and polymer concentration were used as processing variables to manipulate the pore structures. A total of seven organic solvents were freeze cast with a polymethylsiloxane preceramic polymer to produce ceramics with isotropic, dendritic, prismatic, and lamellar pore morphologies. Changes in freezing front velocity and polymer concentration were shown to influence pore size, shape, and connectivity. Differences between suspension- and solution-based samples freeze cast under equivalent conditions were also investigated. Certain solidification microstructures were strongly affected by the presence of suspended particles, creating differences between pore structures generated from the same solvents. Additionally, processing of solution-based samples were found to be the more facile technique. Compressive strength and water permeability of dendritic and lamellar structures were analyzed to determine functional differences between the pore structures. Results show that dendritic structures were up to 30 times stronger, while lamellar structures provided higher permeability constants. A change in freezing front velocity was shown to significantly affect permeability but not compressive strength. Finally, improved pore alignment along the freezing direction was achieved by controlling the nucleation and growth of solvent crystals through the use of a grain-selection template. Dendritic samples freeze cast with a template showed substantial increase in pore alignment, as determined by image analysis and permeability tests, with the permeability constant increasing by up to 6-fold when compared to a control sample.
Compaction and Permeability Reduction of Castlegate Sandstone under Pore Pressure Cycling
NASA Astrophysics Data System (ADS)
Bauer, S. J.
2014-12-01
We investigate time-dependent compaction and permeability changes by cycling pore pressure with application to compressed air energy storage (CAES) in a reservoir. Preliminary experiments capture the impacts of hydrostatic stress, pore water pressure, pore pressure cycling, chemical, and time-dependent considerations near a borehole in a CAES reservoir analog. CAES involves creating an air bubble in a reservoir. The high pressure bubble serves as a mechanical battery to store potential energy. When there is excess grid energy, bubble pressure is increased by air compression, and when there is energy needed on the grid, stored air pressure is released through turbines to generate electricity. The analog conditions considered are depth ~1 km, overburden stress ~20 MPa and a pore pressure ~10MPa. Pore pressure is cycled daily or more frequently between ~10 MPa and 6 MPa, consistent with operations of a CAES facility at this depth and may continue for operational lifetime (25 years). The rock can vary from initially fully-to-partially saturated. Pore pressure cycling changes the effective stress.Jacketed, room temperature tap water-saturated samples of Castlegate Sandstone are hydrostatically confined (20 MPa) and subjected to a pore pressure resulting in an effective pressure of ~10 MPa. Pore pressure is cycled between 6 to 10 MPa. Sample displacement measurements yielded determinations of volumetric strain and from water flow measurements permeability was determined. Experiments ran for two to four weeks, with 2 to 3 pore pressure cycles per day. The Castlegate is a fluvial high porosity (>20%) primarily quartz sandstone, loosely calcite cemented, containing a small amount of clay.Pore pressure cycling induces compaction (~.1%) and permeability decreases (~20%). The results imply that time-dependent compactive processes are operative. The load path, of increasing and decreasing pore pressure, may facilitate local loosening and grain readjustments that results in the compaction and permeability decreases observed. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Dept. of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.SAND2014-16586A
Attar, Hanaa El; Elhiny, Omnia; Salem, Ghada; Abdelrahman, Ahmed; Attia, Mazen
2016-01-01
AIM: To test the solubility of dual cure resin modified resin cement in a food simulating solution and the shear bond strength compared to conventional Glass ionomer cement. MATERIALS AND METHOD: The materials tested were self-adhesive dual cure resin modified cement and Glass Ionomer (GIC). Twenty Teflon moulds were divided into two groups of tens. The first group was injected and packed with the modified resin cement, the second group was packed with GIC. To test the solubility, each mould was weighed before and after being placed in an analytical reagent for 30 days. The solubility was measured as the difference between the initial and final drying mass. To measure the Shear bond strength, 20 freshly extracted wisdom teeth were equally divided into two groups and embedded in self-cure acrylic resin. Four mm sections of stainless steel bands were cemented to the exposed buccal surfaces of teeth under a constant load of 500 g. Shear bond strength was measured using a computer controlled materials testing machine and the load required to deband the samples was recorded in Newtons. RESULTS: GIC showed significantly higher mean weight loss and an insignificant lower Shear bond strength, compared to dual cure resin Cement. CONCLUSION: It was found that dual cure resin modified cement was less soluble than glass ionomer cement and of comparable bond strength rendering it more useful clinically for orthodontic band cementation. PMID:28028417
Role of Substrate on Quartz Cementation in Quartz Aggregates
NASA Astrophysics Data System (ADS)
Farver, J. R.; Winslow, D.; Onasch, C.
2010-12-01
Quartz cementation in quartz aggregates has been experimentally investigated. The starting material was disaggregated detrital quartz grains from the well-sorted, mature St. Peter Sandstone. The ‘as-is’ grains have patches of iron oxide coatings and some have euhedral overgrowths that contain iron oxide dust rims. In addition a set of experiments was run using grains that were cleaned by soaking in sodium hydrosulfite and sodium bisulfate solutions to remove exposed iron oxide coatings. Experimental charges consisted of amorphous silica powder (≈30 mg) to provide a source of silica for the quartz cement, AlCl3 powder (≈3 mg) to provide a tracer for Cathodoluminescence (CL) identification of cement formed during the experiment, 25 wt% NaCl brine solution (≈25 mg) to increase the silica solubility and to better mimic oil field brines, and the natural quartz grains (100-130 mg). The charges were weld-sealed in Au capsules and run in cold-seal pressure vessels at 250°C to 450°C at 150 MPa confining pressure for up to 8 weeks. After the experiments, the samples were vacuum impregnated with a low viscosity epoxy containing a blue dye. After curing, the sample charge was sawn in half along its long axis and one half was polished (to 1 micron diamond paste) for analysis. The nature and amount of quartz cement in the samples were determined by a combination of CL, light microscopy, and scanning electron microscopy. Photomosaics of the samples were created and the amount of cement, porosity, and average grain sizes were determined by point-counting. The cement formed during the experiment was easily recognized from the quartz grains (and previous overgrowths) by the difference in luminescence. The results indicate the amorphous silica powder provides a ready source for silica for quartz cementation due to its greater solubility than the quartz. The cementation rates are rapid (>14% cement formed in 2 weeks at 450°C and >7% in 8 weeks at 250°C). Compared to experiments using crushed fragments of synthetic quartz (Pepple, 2007), the amount of cement in these natural samples was greater. Cementation followed a common pattern in all samples. Microfractures, which formed during pressurization of the charges, healed very rapidly followed by overgrowths on the quartz grains. Cementation began closest to the amorphous silica, then progressed away. There was no measurable difference in the amount of quartz cement formed in samples of the as-is and cleaned St. Peter Sandstone indicating that iron played no role in the rate of cementation. Although the amount of cement formed increased with increasing temperature and duration of the experiments, the rate of cementation decreased dramatically in longer duration (8 weeks) experiments suggesting a change in the precipitation mechanism/rate. This apparent change in precipitation rate may reflect a decrease in available surfaces for nucleation and/or a decrease in growth rate as euhedral faces develop as proposed by Lander et al (2008).
Fabrication and cytocompatibility of spherical magnesium ammonium phosphate granules.
Christel, Theresa; Geffers, Martha; Klammert, Uwe; Nies, Berthold; Höß, Andreas; Groll, Jürgen; Kübler, Alexander C; Gbureck, Uwe
2014-09-01
Magnesium phosphate compounds, as for example struvite (MgNH4PO4·6H2O), have comparable characteristics to calcium phosphate bone substitutes, but degrade faster under physiological conditions. In the present work, we used a struvite forming calcium doped magnesium phosphate cement with the formulation Ca0.75Mg2.25(PO4)2 and an ammonium phosphate containing aqueous solution to produce round-shaped granules. For the fabrication of spherical granules, the cement paste was dispersed in a lipophilic liquid and stabilized by surfactants. The granules were characterized with respect to morphology, size distribution, phase composition, compressive strength, biocompatibility and solubility. In general, it was seen that small granules can hardly be produced by means of emulsification, when the raw material is a hydraulic paste, because long setting times promote coalescence of initially small unhardened cement droplets. Here, this problem was solved by using an aqueous solution containing both the secondary (NH4)2HPO4 and primary ammonium phosphates NH4H2PO4 to accelerate the setting reaction. This resulted in granules with 97 wt.% having a size in the range between 200 and 1,000 μm. The novel solution composition doubled the compressive strength of the cement to 37 ± 5 MPa without affecting either the conversion to struvite or the cytocompatibility using human fetal osteoblasts. Copyright © 2014 Elsevier B.V. All rights reserved.
Method of fabrication of supported liquid membranes
Luebke, David R.; Hong, Lei; Myers, Christina R.
2015-11-17
Method for the fabrication of a supported liquid membrane having a dense layer in contact with a porous layer, and a membrane liquid layer within the interconnected pores of the porous layer. The dense layer is comprised of a solidified material having an average pore size less than or equal to about 0.1 nanometer, while the porous layer is comprised of a plurality of interconnected pores and has an average pore size greater than 10 nanometers. The supported liquid membrane is fabricated through the preparation of a casting solution of a membrane liquid and a volatile solvent. A pressure difference is established across the dense layer and porous layer, the casting solution is applied to the porous layer, and the low viscosity casting solution is drawn toward the dense layer. The volatile solvent is evaporated and the membrane liquid precipitates, generating a membrane liquid layer in close proximity to the dense layer.
NASA Astrophysics Data System (ADS)
Laleian, A.; Valocchi, A. J.; Werth, C. J.
2017-12-01
Multiscale models of reactive transport in porous media are capable of capturing complex pore-scale processes while leveraging the efficiency of continuum-scale models. In particular, porosity changes caused by biofilm development yield complex feedbacks between transport and reaction that are difficult to quantify at the continuum scale. Pore-scale models, needed to accurately resolve these dynamics, are often impractical for applications due to their computational cost. To address this challenge, we are developing a multiscale model of biofilm growth in which non-overlapping regions at pore and continuum spatial scales are coupled with a mortar method providing continuity at interfaces. We explore two decompositions of coupled pore-scale and continuum-scale regions to study biofilm growth in a transverse mixing zone. In the first decomposition, all reaction is confined to a pore-scale region extending the transverse mixing zone length. Only solute transport occurs in the surrounding continuum-scale regions. Relative to a fully pore-scale result, we find the multiscale model with this decomposition has a reduced run time and consistent result in terms of biofilm growth and solute utilization. In the second decomposition, reaction occurs in both an up-gradient pore-scale region and a down-gradient continuum-scale region. To quantify clogging, the continuum-scale model implements empirical relations between porosity and continuum-scale parameters, such as permeability and the transverse dispersion coefficient. Solutes are sufficiently mixed at the end of the pore-scale region, such that the initial reaction rate is accurately computed using averaged concentrations in the continuum-scale region. Relative to a fully pore-scale result, we find accuracy of biomass growth in the multiscale model with this decomposition improves as the interface between pore-scale and continuum-scale regions moves downgradient where transverse mixing is more fully developed. Also, this decomposition poses additional challenges with respect to mortar coupling. We explore these challenges and potential solutions. While recent work has demonstrated growing interest in multiscale models, further development is needed for their application to field-scale subsurface contaminant transport and remediation.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ahmed, K.; Tonks, M.; Zhang, Y.
A detailed phase field model for the effect of pore drag on grain growth kinetics was implemented in MARMOT. The model takes into consideration both the curvature-driven grain boundary motion and pore migration by surface diffusion. As such, the model accounts for the interaction between pore and grain boundary kinetics, which tends to retard the grain growth process. Our 2D and 3D simulations demonstrate that the model capture all possible pore-grain boundary interactions proposed in theoretical models. For high enough surface mobility, the pores move along with the migrating boundary as a quasi-rigid-body, albeit hindering its migration rate compared tomore » the pore-free case. For less mobile pores, the migrating boundary can separate from the pores. For the pore-controlled grain growth kinetics, the model predicts a strong dependence of the growth rate on the number of pores, pore size, and surface diffusivity in agreement with theroretical models. An evolution equation for the grain size that includes these parameters was derived and showed to agree well with numerical solution. It shows a smooth transition from boundary-controlled kinetics to pore-controlled kinetics as the surface diffusivity decreases or the number of pores or their size increases. This equation can be utilized in BISON to give accurate estimate for the grain size evolution. This will be accomplished in the near future. The effect of solute drag and anisotropy of grain boundary on grain growth will be investigated in future studies.« less
Ait Ouarabi, Mohand; Antonaci, Paola; Boubenider, Fouad; Gliozzi, Antonio S; Scalerandi, Marco
2017-01-07
Alkaline solutions, such as sodium, potassium or lithium silicates, appear to be very promising as healing agents for the development of encapsulated self-healing concretes. However, the evolution of their mechanical and acoustic properties in time has not yet been completely clarified, especially regarding their behavior and related kinetics when they are used in the form of a thin layer in contact with a hardened cement matrix. This study aims to monitor, using linear and nonlinear ultrasonic methods, the evolution of a sodium silicate solution interacting with a cement matrix in the presence of localized cracks. The ultrasonic inspection via linear methods revealed that an almost complete recovery of the elastic and acoustic properties occurred within a few days of healing. The nonlinear ultrasonic measurements contributed to provide further insight into the kinetics of the recovery due to the presence of the healing agent. A good regain of mechanical performance was ascertained through flexural tests at the end of the healing process, confirming the suitability of sodium silicate as a healing agent for self-healing cementitious systems.
The impact of sulphate and magnesium on chloride binding in Portland cement paste
DOE Office of Scientific and Technical Information (OSTI.GOV)
De Weerdt, K., E-mail: klaartje.d.weerdt@ntnu.no; SINTEF Building and Infrastructure, Trondheim; Orsáková, D.
2014-11-15
The effect of magnesium and sulphate present in sea water on chloride binding in Portland cement paste was investigated. Ground well hydrated cement paste was exposed to MgCl{sub 2}, NaCl, NaCl + MgCl{sub 2}, MgSO{sub 4} + MgCl{sub 2} and artificial sea water solutions with a range of concentrations at 20 °C. Chloride binding isotherms are determined and pH of the solutions were measured. A selection of samples was examined by SEM-EDS to identify phase changes upon exposure. The experimental data were compared with calculations of a thermodynamic model. Chloride binding from sea water was similar to chloride binding formore » NaCl solutions. The magnesium content in the sea water lead to a slight decrease in pH, but this did not result in a notable increase in chloride binding. The sulphate present in sea water reduces both chloride binding in C–S–H and AFm phases, as the C–S–H incorporates more sulphates instead of chlorides, and part of the AFm phases converts to ettringite.« less
Accumulation of Colloidal Particles in Flow Junctions Induced by Fluid Flow and Diffusiophoresis
NASA Astrophysics Data System (ADS)
Shin, Sangwoo; Ault, Jesse T.; Warren, Patrick B.; Stone, Howard A.
2017-10-01
The flow of solutions containing solutes and colloidal particles in porous media is widely found in systems including underground aquifers, hydraulic fractures, estuarine or coastal habitats, water filtration systems, etc. In such systems, solute gradients occur when there is a local change in the solute concentration. While the effects of solute gradients have been found to be important for many applications, we observe an unexpected colloidal behavior in porous media driven by the combination of solute gradients and the fluid flow. When two flows with different solute concentrations are in contact near a junction, a sharp solute gradient is formed at the interface, which may allow strong diffusiophoresis of the particles directed against the flow. Consequently, the particles accumulate near the pore entrance, rapidly approaching the packing limit. These colloidal dynamics have important implications for the clogging of a porous medium, where particles that are orders of magnitude smaller than the pore width can accumulate and block the pores within a short period of time. We also show that this effect can be exploited as a useful tool for preconcentrating biomolecules for rapid bioassays.
NASA Astrophysics Data System (ADS)
Schaffhauser, Maria; Krainer, Karl; Sanders, Diethard Gerald; Spötl, Christoph
2010-05-01
The Trogkofel massif in the Carnic Alps, Austria/Italy, consists of a succession up to 400 m thick of limestones deposited along a platform margin (Trogkofel Limestone; Artinskian). The top of the Trogkofel Limestone is erosively overlain by the Tarvis Breccia. Up-section, the Trogkofel Limestone consists of well-bedded shallow-water bioclastic limestones with intercalated mud mounds, overlain by thick-bedded to unbedded limestones (bioclastic grainstones, packstones, rudstones) and cementstone mounds rich in phylloid algae, Tubiphytes, bryozoans and Archaeolithoporella. In the cementstone mounds, bioclasts are coated by thick fringes and botryoids of fibrous calcite, and of calcite spar that probably represents calcitized aragonite. Primary and intrinsic pores are filled by microbialite, and/or by mudstone to bioclastic wackestone. Shallow-water bioclastic grainstones are cemented by isopachous fringes of fibrous calcite, or by sparry calcite. Throughout the succession, evidence for meteoric-vadose dissolution is present. The Trogkofel Limestone is riddled by palaeokarstic dykes and caverns filled by (a) isopachous cement fringes up to a few decimetres thick, and/or (b) by red, geopetally-laminated lime mudstone to bio-lithoclastic wackestone; geopetal laminasets locally display convolute bedding. Small dissolution cavities are filled by grey internal sediment, or by crystal silt. Brecciated internal sediments overlain by unbrecciated, geopetally-laminated infillings record deformation during or after deposition of the Trogkofel Limestone. Polyphase fractures cemented by calcite may cross-cut both internal sediments and host rock. In the Trogkofel Limestone, local dolomitization is common. Replacement dolomites show a wide range of shapes and fabrics, including: (a) fine-crystalline anhedral xenotopic fabric, (b) coarse-crystalline subhedral to euhedral, hypidiotopic to idiotopic fabric of turbid or optically zoned crystals, and (c) saddle dolomite as replacement and filling of fractures. Closely below the erosional surface at the top of the Trogkofel Limestone, the dolomite is characterized by vuggy porosity. The Tarvis Breccia, which represents coarse alluvial fan deposits, in turn, is thick-bedded, poorly sorted, typically clast-supported, and consists of angular lithoclasts embedded in a matrix of former lime mudstone. Both, matrix as well as lithoclasts, are dolomitized. Various types of cement (isopachous, botryoidal, microbialite, calcite spar), karstic cavity fills (isopachous cements, internal sediments), and replacement dolomites of the Trogkofel section, as well as of the Tarvis Breccia were analysed for their stable isotopic composition. δ18O and δ13C data produced so far allow to differentiate between replacement dolomites and saddle dolomite of the Trogkofel Limestone and the Tarvis Breccia. Saddle dolomite shows the most depleted oxygen isotope values, suggesting formation during relatively high temperatures. Carbon isotope values are invariably positive in all dolomite types indicating lacking influence of organic diagenesis on the alkalinity of the deep-burial pore water. Matrix dolomite from the Tarvis Breccia shows slightly positive δ18O values. Calcite cements show a wide range in δ18O values (ca. -1 to -7 permil VPDB), which overlaps the composition of unaltered brachiopod shells (ca. -3 permil VPDB). Oxygen isotope values of calcite cements reveal a trend towards depleted δ18O values. This trend is reflecting most likely increasing temperature.
NASA Astrophysics Data System (ADS)
Mancio, Mauricio
In reinforced concrete, a passive layer forms because of the alkaline conditions in the pores of the cement paste, where large concentrations of hydroxides create a solution with pH typically between 12 and 14. The corrosion resistance of the material depends on the characteristics and integrity of the passive film; however, currently very limited information is available about the passive films formed on carbon steel under such conditions. This work presents an electrochemical and in-situ Surface-Enhanced Raman Spectroscopic (SERS) study of passive films formed on low-carbon steel in highly alkaline environments. More specifically, the study focuses on the characterization of the films formed on ASTM A36 steel reinforcing bar exposed to aqueous solutions that aim to reproduce the chemistry of the environment typically found within the cement paste. Electrochemical techniques such as cyclic potentiodynamic polarization curves, galvanostatic cathodic polarization and linear polarization resistance were employed, in addition to in-situ Surface Enhanced Raman Spectroscopy (SERS). The experimental setup was built in a way that SERS experiments could be performed simultaneously with potentiodynamic polarization curves, enabling a detailed analysis of the formation and reduction of the surface films as a function of applied potential. Three solutions with different pH levels were used for the polarization and SERS experiments, namely 0.55M KOH + 0.16M NaOH ([OH-]=0.71), 0.08M KOH + 0.02M NaOH ([OH-]=0.10) and 0.008M KOH + 0.002M NaOH ([OH-]=0.01). Additional NaOH solutions in which the pH was varied from 13 to 9 and the ionic strength from 10 -5 to 10-1 were prepared for a pilot study using linear polarization resistance. Results show that the features observed in the cyclic potentiodynamic polarization curves correlated well with the potential arrests observed in the GCP plots as well as with the changes observed in the SERS spectra, providing valuable information about the formation of passive films on carbon steel in each of the environments studied in this research. Although there are key differences among the films formed in the different solutions tested---particularly regarding their thickness and protectiveness---once the film-formation processes had been completed, generally the films were characterized by an inner layer of Fe(II) and an outer layer of Fe(III). A Fe(OH)2-like species appears consistently as dominating the inner Fe(II) layer, while the outer typically composed mostly by gamma-Fe2O3 and/or gamma-FeOOH. Film thickness varied from about 22 nm to 266 nm depending on the pH of the solution, and decreased as pH was reduced.
Investigation of fatigue crack growth in acrylic bone cement using the acoustic emission technique.
Roques, A; Browne, M; Thompson, J; Rowland, C; Taylor, A
2004-02-01
Failure of the bone cement mantle has been implicated in the loosening process of cemented hip stems. Current methods of investigating degradation of the cement mantle in vitro often require sectioning of the sample to confirm failure paths. The present research investigates acoustic emission as a passive experimental method for the assessment of bone cement failure. Damage in bone cement was monitored during four point bending fatigue tests through an analysis of the peak amplitude, duration, rise time (RT) and energy of the events emitted from the damage sections. A difference in AE trends was observed during failure for specimens aged and tested in (i) air and (ii) Ringer's solution at 37 degrees C. It was noted that the acoustic behaviour varied according to applied load level; events of higher duration and RT were emitted during fatigue at lower stresses. A good correlation was observed between crack location and source of acoustic emission, and the nature of the acoustic parameters that were most suited to bone cement failure characterisation was identified. The methodology employed in this study could potentially be used as a pre-clinical assessment tool for the integrity of cemented load bearing implants.
Durability of Waste Glass Flax Fiber Reinforced Mortar
NASA Astrophysics Data System (ADS)
Aly, M.; Hashmi, M. S. J.; Olabi, A. G.; Messeiry, M.
2011-01-01
The main concern for natural fibre reinforced mortar composites is the durability of the fibres in the alkaline environment of cement. The composites may undergo a reduction in strength as a result of weakening of the fibres by a combination of alkali attack and fibre mineralisation. In order to enhance the durability of natural fiber reinforced cement composites several approaches have been studied including fiber impregnation, sealing of the matrix pore system and reduction of matrix alkalinity through the use of pozzolanic materials. In this study waste glass powder was used as a pozzolanic additive to improve the durability performance of flax fiber reinforced mortar (FFRM). The durability of the FFRM was studied by determining the effects of ageing in water and exposure to wetting and drying cycles; on the microstructures and flexural behaviour of the composites. The mortar tests demonstrated that the waste glass powder has significant effect on improving the durability of FFRM.
Du, Yan-Jun; Jiang, Ning-Jun; Shen, Shui-Long; Jin, Fei
2012-07-30
Remediation of contaminated lands in China urban areas is of great concern. Degradation of construction facilities caused by acid rain is a serious environmental pollution issue in China. This paper presents an investigation of the effects of acid rain on leaching and hydraulic properties of cement-based solidified/stabilized lead contaminated soil. Laboratory tests including infiltration test and soaking test are conducted. It is found that the soil hydraulic conductivity decreases with increase in the pore volume of flow of permeant liquids (acid rain and distilled water). The decreasing rate in the case of the acid rain is lower than that in the case of the distilled water. The soaking test results show that pH and the presence of sulfate ions of acid rain have considerable influence on the leached concentrations and leaching rate of calcium. Copyright © 2012 Elsevier B.V. All rights reserved.
Ductile flow of methane hydrate
Durham, W.B.; Stern, L.A.; Kirby, S.H.
2003-01-01
Compressional creep tests (i.e., constant applied stress) conducted on pure, polycrystalline methane hydrate over the temperature range 260-287 K and confining pressures of 50-100 MPa show this material to be extraordinarily strong compared to other icy compounds. The contrast with hexagonal water ice, sometimes used as a proxy for gas hydrate properties, is impressive: over the thermal range where both are solid, methane hydrate is as much as 40 times stronger than ice at a given strain rate. The specific mechanical response of naturally occurring methane hydrate in sediments to environmental changes is expected to be dependent on the distribution of the hydrate phase within the formation - whether arranged structurally between and (or) cementing sediments grains versus passively in pore space within a sediment framework. If hydrate is in the former mode, the very high strength of methane hydrate implies a significantly greater strain-energy release upon decomposition and subsequent failure of hydrate-cemented formations than previously expected.
Stefanoni, Matteo; Angst, Ueli M; Elsener, Bernhard
2018-05-09
Corrosion in carbonated concrete is an example of corrosion in dense porous media of tremendous socio-economic and scientific relevance. The widespread research endeavors to develop novel, environmentally friendly cements raise questions regarding their ability to protect the embedded steel from corrosion. Here, we propose a fundamentally new approach to explain the scientific mechanism of corrosion kinetics in dense porous media. The main strength of our model lies in its simplicity and in combining the capillary condensation theory with electrochemistry. This reveals that capillary condensation in the pore structure defines the electrochemically active steel surface, whose variability upon changes in exposure relative humidity is accountable for the wide variability in measured corrosion rates. We performed experiments that quantify this effect and find good agreement with the theory. Our findings are essential to devise predictive models for the corrosion performance, needed to guarantee the safety and sustainability of traditional and future cements.
[An experimental study on the adaptation of three kinds of porcelain fused-to-metal restorations].
Pei, Yan-Ping; Chen, Ji-Hua; Chang, Qing; Lin, Song-Shan; Zhang, He
2009-04-01
To compare the adaptation of porcelain fused-to-metal (PFM) restorations made from Ni-Cr alloy, precious alloy and galvanized forming copings after cementation and to provide a theory guidance for their application. Three kinds of crowns (Ni-Cr alloy, precious alloy and galvanized forming) were manufactured and cleaned by ultrasonic vibrate with alcoholic solution for 5 minutes, and cemented on their dies as their order. All the crowns were cemented by polycarboxylate zinc-cement and maintained 10 minutes. After coated in the center of methyl acrylic resins, all the samples were cut vertically along buccolingual direction. The cement thickness of PFM was measured by scanning electron microscope and the data were analyzed by multivariate ANOVA. No significant difference was found between the cement thickness of precious alloy crown and galvanized forming crown (P>0.05), while both of these two kinds of crown had significant differences in cement thickness with Ni-Cr crown (P<0.05). The adaptation of precious alloy crown and galvanized forming crown are superior to Ni-Cr crown.
Influence of Carbon Nanotube Clustering on Mechanical and Electrical Properties of Cement Pastes
Jang, Sung-Hwan; Kawashima, Shiho; Yin, Huiming
2016-01-01
Given the continued challenge of dispersion, for practical purposes, it is of interest to evaluate the impact of multi-walled carbon nanotubes (MWCNTs) at different states of clustering on the eventual performance properties of cement paste. This study evaluated the clustering of MWCNTs and the resultant effect on the mechanical and electrical properties when incorporated into cement paste. Cement pastes containing different concentrations of MWCNTs (up to 0.5% by mass of cement) with/without surfactant were characterized. MWCNT clustering was assessed qualitatively in an aqueous solution through visual observation, and quantitatively in cement matrices using a scanning electron microscopy technique. Additionally, the corresponding 28-day compressive strength, tensile strength, and electrical conductivity were measured. Results showed that the use of surfactant led to a downward shift in the MWCNT clustering size distribution in the matrices of MWCNT/cement paste, indicating improved dispersion of MWCNTs. The compressive strength, tensile strength, and electrical conductivity of the composites with surfactant increased with MWCNT concentration and were higher than those without surfactant at all concentrations. PMID:28773348
Efficiency of fly ash belite cement and zeolite matrices for immobilizing cesium.
Goñi, S; Guerrero, A; Lorenzo, M P
2006-10-11
The efficiency of innovative matrices for immobilizing cesium is presented in this work. The matrix formulation included the use of fly ash belite cement (FABC-2-W) and gismondine-type Na-P1 zeolite, both of which are synthesized from fly ash of coal combustion. The efficiency for immobilizing cesium is evaluated from the leaching test ANSI/ANS 16.1-1986 at the temperature of 40 degrees C, from which the apparent diffusion coefficient of cesium is obtained. Matrices with 100% of FABC-2-W are used as a reference. The integrity of matrices is evaluated by porosity and pore-size distribution from mercury intrusion porosimetry, X-ray diffraction and nitrogen adsorption analyses. Both matrices can be classified as good solidify systems for cesium, specially the FABC-2-W/zeolite matrix in which the replacement of 50% of belite cement by the gismondine-type Na-P1 zeolite caused a decrease of two orders of magnitude of cesium mean Effective Diffusion Coefficient (D(e)) (2.8e-09 cm(2)/s versus 2.2e-07 cm(2)/s, for FABC-2-W/zeolite and FABC-2-W matrices, respectively).
Yokoyama, Atsuro; Yamamoto, Satoru; Kawasaki, Takao; Kohgo, Takao; Nakasu, Masanori
2002-02-01
We developed a calcium phosphate cement that could be molded into any desired shape due to its chewing-gum-like consistency after mixing. The powder component of the cement consists of alpha-tricalcium phosphate and tetracalcium phosphate, which were made by decomposition of hydroxyapatite ceramic blocks. The liquid component consists of citric acid, chitosan and glucose solution. In this study, we used 20% citric acid (group 20) and 45% citric acid (group 45). The mechanical properties and biocompatibility of this new cement were investigated. The setting times of cements were 5.5 min, in group 20 and 6.4 min, in group 45. When incubated in physiological saline, the cements were transformed to hydroxyapatite at 3, and 6 weeks, the compressive strengths were 15.6 and 20.7 MPa, in group 45 and group 20, respectively. The inflammatory response around the cement implanted on the bone and in the subcutaneous tissue in rats was more prominent in group 45 than in group 20 at 1 week after surgery. After 4 weeks, the inflammation disappeared and the cement had bound to bone in both groups. These results indicate that this new calcium phosphate cement is a suitable bone substitute material and that the concentration of citric acid in the liquid component affects its mechanical properties and biocompatibility.
Maruo, Yukinori; Nishigawa, Goro; Yoshihara, Kumiko; Minagi, Shogo; Matsumoto, Takuya; Irie, Masao
2017-03-01
Dental ceramic surfaces are modified with silane coupling agents, such as γ-methacryloxypropyl trimethoxy silane (γ-MPTS), to improve bond strength. For bonding between lithium disilicate glass ceramic and resin cement, the objective was to investigate if 8-methacryloxyoctyl trimethoxy silane (8-MOTS) could yield a similar performance as the widely used γ-MPTS. One hundred and ten lithium disilicate glass ceramic specimens were randomly divided into 11 groups (n=10) according to pretreatment regime. All specimens were pretreated with a different solution composed of one or a combination of these agents: 10 or 20wt% silane coupling agent of γ-MPTS or 8-MOTS, followed by a hydrolysis solution of acetic acid or 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP). Each pretreated surface was luted to a stainless steel rod of 3.6mm diameter and 2.0mm height with resin cement. Shear bond strength between ceramic and cement was measured after 24-h storage in 37°C distilled water. 8-MOTS produced the same bonding performance as γ-MPTS. Both silane coupling agents significantly increased the bond strength of resin cement, depending on their concentration. When activated by 10-MDP hydrolysis solution, 20wt% concentration produced the highest values (γ-MPTS: 24.9±5.1MPa; 8-MOTS: 24.6±7.4MPa). Hydrolysis with acetic acid produced lower bond strengths than with 10-MDP. Silane coupling pretreatment with 8-MOTS increased the initial bond strength between lithium disilicate glass ceramic and resin cement, rendering the same bonding effect as the conventional γ-MPTS. Copyright © 2016 The Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Deuerling, Kelly M.; Martin, Jonathan B.; Martin, Ellen E.; Scribner, Cecilia A.
2018-01-01
The exchange of proglacial river water with active layer pore water could alter water chemical compositions in glacial outwash plains and oceanic solute fluxes. To evaluate effects of this exchange, we sampled Watson River and adjacent pore water during the 2013 melt season at two sandurs in western Greenland; one in Sandflugtdalen and the other near the confluence with Søndre Strømfjord. We measured temperature, specific conductivity, and head gradients between the river and bank over a week-long period at Sandflugtdalen, as well as sediment hydraulic conductivity and chemical compositions of waters from both sites. Specific conductivity of pore water is four to ten times greater than river water as solutes are concentrated from weathering reactions, cryoconcentration, and evaporation. Pore water compositions are predominantly altered by carbonate dissolution and sulfide mineral oxidation. High concentrations of HCO3 and SO4 result from solute recycling and dissolution of secondary Ca-Mg carbonate/sulfate salts initially formed by near-surface evaporation in the summer and at depth by freeze-in of the active layer and cryoconcentration in the winter. High hydraulic conductivity (10-5 to 10-4 m/s) and diurnal fluctuations of river stage during our study caused exchange of river and pore water immediately adjacent to the river channel, with a net loss of river water to the bank. Pore water >6 m from the river continuously flowed away from the river. Approximately 1-8% of the river discharge through the Sandflugtdalen was lost to the river bank during our 6.75 day study based on calculations using Darcy's Law. Although not sampled, some of this water should discharge to the river during low river stage early and late in the melt season. Elevated pore water solute concentrations in sandurs and water exchange at diurnal and seasonal frequency should impact fluxes of solutes to the ocean, although understanding the magnitude of this effect will require long-term evaluation throughout the melt season.
Hu, Yuan; Sinha, Sudipta Kumar
2015-01-01
Cell-penetrating and antimicrobial peptides show remarkable ability to translocate across physiological membranes. Along with factors such as electric potential induced-perturbations of membrane structure and surface tension effects, experiments invoke pore-like membrane configurations during the solute transfer process into vesicles and cells. The initiation and formation of pores are associated with a non-trivial free energy cost, thus necessitating consideration of the factors associated with pore formation and attendant free energetics. Due to experimental and modeling challenges related to the long timescales of the translocation process, we use umbrella-sampling molecular dynamics simulations with a lipid-density based order parameter to investigate membrane pore-formation free energy employing Martini coarse-grained models. We investigate structure and thermodynamic features of the pore in 18 lipids spanning a range of head-groups, charge states, acyl chain lengths and saturation. We probe the dependence of pore-formation barriers on area per lipid, lipid bilayer thickness, membrane bending rigidities in three different lipid classes. The pore formation free energy in pure bilayers and peptide translocating scenarios are significantly coupled with bilayer thickness. Thicker bilayers require more reversible work to create pores. Pore formation free energy is higher in peptide-lipid systems relative to the peptide-free lipid systems due to penalties to maintain solvation of charged hydrophilic solutes within the membrane environment. PMID:25614183
Numerical Simulation of the Freeze-Thaw Behavior of Mortar Containing Deicing Salt Solution
Esmaeeli, Hadi S.; Farnam, Yaghoob; Bentz, Dale P.; Zavattieri, Pablo D.; Weiss, Jason
2016-01-01
This paper presents a one-dimensional finite difference model that is developed to describe the freeze-thaw behavior of an air-entrained mortar containing deicing salt solution. A phenomenological model is used to predict the temperature and the heat flow for mortar specimens during cooling and heating. Phase transformations associated with the freezing/melting of water/ice or transition of the eutectic solution from liquid to solid are included in this phenomenological model. The lever rule is used to calculate the quantity of solution that undergoes the phase transformation, thereby simulating the energy released/absorbed during phase transformation. Undercooling and pore size effects are considered in the numerical model. To investigate the effect of pore size distribution, this distribution is considered using the Gibbs-Thomson equation in a saturated mortar specimen. For an air-entrained mortar, the impact of considering pore size (and curvature) on freezing was relatively insignificant; however the impact of pore size is much more significant during melting. The fluid inside pores smaller than 5 nm (i.e., gel pores) has a relatively small contribution in the macroscopic freeze-thaw behavior of mortar specimens within the temperature range used in this study (i.e., +24 °C to −35 °C), and can therefore be neglected for the macroscopic freeze-thaw simulations. A heat sink term is utilized to simulate the heat dissipation during phase transformations. Data from experiments performed using a low-temperature longitudinal guarded comparative calorimeter (LGCC) on mortar specimens fully saturated with various concentration NaCl solutions or partially saturated with water is compared to the numerical results and a promising agreement is generally obtained. PMID:28082830
Numerical Simulation of the Freeze-Thaw Behavior of Mortar Containing Deicing Salt Solution.
Esmaeeli, Hadi S; Farnam, Yaghoob; Bentz, Dale P; Zavattieri, Pablo D; Weiss, Jason
2017-02-01
This paper presents a one-dimensional finite difference model that is developed to describe the freeze-thaw behavior of an air-entrained mortar containing deicing salt solution. A phenomenological model is used to predict the temperature and the heat flow for mortar specimens during cooling and heating. Phase transformations associated with the freezing/melting of water/ice or transition of the eutectic solution from liquid to solid are included in this phenomenological model. The lever rule is used to calculate the quantity of solution that undergoes the phase transformation, thereby simulating the energy released/absorbed during phase transformation. Undercooling and pore size effects are considered in the numerical model. To investigate the effect of pore size distribution, this distribution is considered using the Gibbs-Thomson equation in a saturated mortar specimen. For an air-entrained mortar, the impact of considering pore size (and curvature) on freezing was relatively insignificant; however the impact of pore size is much more significant during melting. The fluid inside pores smaller than 5 nm (i.e., gel pores) has a relatively small contribution in the macroscopic freeze-thaw behavior of mortar specimens within the temperature range used in this study (i.e., +24 °C to -35 °C), and can therefore be neglected for the macroscopic freeze-thaw simulations. A heat sink term is utilized to simulate the heat dissipation during phase transformations. Data from experiments performed using a low-temperature longitudinal guarded comparative calorimeter (LGCC) on mortar specimens fully saturated with various concentration NaCl solutions or partially saturated with water is compared to the numerical results and a promising agreement is generally obtained.
Duff, J.H.; Murphy, F.; Fuller, C.C.; Triska, F.J.
1998-01-01
A new method for collecting pore-water samples in sand and gravel streambeds is presented. We developed a mini drivepoint solution sampling (MINIPOINT) technique to collect pore-water samples at 2.5-cm vertical resolution. The sampler consisted of six small-diameter stainless steel drivepoints arranged in a 10-cm-diameter circular array. In a simple procedure, the sampler was installed in the streambed to preset drivepoint depths of 2.5, 5.0, 7.5, 10.0, 12.5, and 15.0 cm. Sampler performance was evaluated in the Shingobee River, Minnesota, and Pinal Creek, Arizona, by measuring the vertical gradient of chloride concentration in pore water beneath the streambed that was established by the uninterrupted injection to the stream for 3 d. Pore-water samples were withdrawn from all drivepoints simultaneously. In the first evaluation, the vertical chloride gradient was unchanged at withdrawal rates between 0.3 and 4.0 ml min-1 but was disturbed at higher rates. In the second evaluation, up to 70 ml of pore water was withdrawn from each drivepoint at a withdrawal rate of 2.5 ml min-1 without disturbing the vertical chloride gradient. Background concentrations of other solutes were also determined with MINIPOINT sampling. Steep vertical gradients were present for biologically reactive solutes such as DO, NH4/+, NO3/-, and dissolved organic C in the top 20 cm of the streambed. These detailed solute profiles in the hyporheic zone could not have been determined without a method for close interval vertical sampling that does not disturb natural hydrologic mixing between stream water and groundwater.
Reactions in glass-ionomer cements: IV. Effect of chelating comonomers on setting behavior.
Wilson, A D; Crisp, S; Ferner, A J
1976-01-01
The oscillating rheometer is a valuable instrument for studying the effects of additives on the setting behavior of a cement system. Using this instrument, it was found that certain chelating comonomers, the hydroxycarboxylic acids, could improve the setting characteristics of the glass-ionomer cement system when added to the PAA solution. The acid chelates probably assign the extraction of metal ions from the glass and also tend to hold them in solution, preventing premature ion binding of the polyanion chains. The effect is to increase the rate of hardening without reducing the working time, which may indeed by slightly increased. Tartaric acid, the most effective of the comonomers, can form a chelate bridge between aluminum atoms, and this metal complex probably acts as a flexible bridge structure linking polyanion chains. This mechanism offers some steric advantages over a simple salt bridge.
Testing Mercury Porosimetry with 3D Printed Porosity Models
NASA Astrophysics Data System (ADS)
Hasiuk, F.; Ewing, R. P.; Hu, Q.
2014-12-01
Mercury intrusion porosimetry is one of the most widely used techniques to study the porous nature of a geological and man-made materials. In the geosciences, it is commonly used to describe petroleum reservoir and seal rocks as well as to grade aggregates for the design of asphalt and portland cement concretes. It's wide utility stems from its ability to characterize a wide range of pore throat sizes (from nanometers to around a millimeter). The fundamental physical model underlying mercury intrusion porosimetry, the Washburn Equation, is based on the assumption that rock porosity can be described as a bundle of cylindrical tubes. 3D printing technology, also known as rapid prototyping, allows the construction of intricate and accurate models, exactly what is required to build models of rock porosity. We evaluate the applicability of the Washburn Equation by comparing properties (like porosity, pore and pore throat size distribution, and surface area) computed on digital porosity models (built from CT data, CAD designs, or periodic geometries) to properties measured via mercury intrusion porosimetry on 3D printed versions of the same digital porosity models.
Sharp Permeability Transitions due to Shallow Diagenesis of Subduction Zone Sediments
NASA Astrophysics Data System (ADS)
James, S.; Screaton, E.
2013-12-01
The permeability of hemipelagic sediments is an important factor in fluid flow in subduction zones and can be affected by porosity changes and cementation-dissolution processes acting during diagenesis. Anomalously high porosities have been observed in cores from the Shikoku Basin sediments approaching the Nankai Trough subduction zone. These high porosities have been attributed to the presence of minor amounts of amorphous silica cement that strengthen the sediment and inhibit consolidation. The porosity rapidly drops from 66-68% to 54-56% at a diagenetic boundary where the amorphous silica cement dissolves. Although the anomalous porosity profiles at Nankai have received attention, the magnitude of the corresponding permeability change has not been addressed. In this study, permeability profiles were constructed using permeability-porosity relationships from previous studies, to estimate the magnitude and rate of permeability changes with depth. The predicted permeability profiles for the Nankai Trough sediment cores indicate that permeability drops by almost one order of magnitude across the diagenetic boundary. This abrupt drop in permeability has the potential to facilitate significant changes in pore fluid pressures and thus to influence the deformation of the sediment onto the accretionary prism. At the Costa Rica subduction zone, results vary with location. Site U1414 offshore the Osa Peninsula shows porosities stable at 69% above 145 mbsf and then decrease to 54% over a 40 m interval. A porosity drop of that magnitude is predicted to correlate to an order of magnitude permeability decrease. In contrast, porosity profiles from Site 1039 offshore the Nicoya Peninsula and Site U1381 offshore the Osa Peninsula show anomalously high porosities but no sharp drop. It is likely that sediments do not cross the diagenetic boundary due to the extremely low (<10°C/km) thermal gradient at Site 1039 and the thin (<100 m) sediment cover at Site U1381. At these locations, the porosity loss and permeability reduction may occur after the sediment is subducted and contribute to high pore pressures at the plate boundary.
NASA Astrophysics Data System (ADS)
Sample, J. C.
2006-12-01
Deformation bands occur in an outcrop of a petroleum-bearing, sandstone-rich unit of the Monterey Formation along the active Newport-Inglewood fault zone (NIFZ), near Corona del Mar, California. The deformation bands likely developed in a damage zone associated with a strand of the NIFZ. The bands appear to have formed in poorly lithified sandstone. They are relatively oil-free whereas the matrix sandstone contains oil in pore space. The deformation bands acted as baffles to flow, but continuing deformation likely breached permeability barriers over time. Thus the bands did not completely isolate compartments from oil migration, but similar structures in the subsurface would likely slow the rate of production in reservoirs. The network of bands at Corona del Mar forms a mesh with band intersection lines lying parallel to the trend of the NIFZ (northwest). This geometry formed as continuing deformation in the NIFZ rotated early bands into unfavorable orientations for continuing deformation, and new bands formed at high angles to the first set. Permeability in this setting is likely to have been anisotropic, higher parallel to strike of the NIFZ and lower vertically and perpendicular to the strike of the fault zone. One unique type of deformation band found here formed by dilation and early oil migration along fractures, and consequent carbonate cementation along fracture margins. These are thin, planar zones of oil 1 - 2 mm thick sandwiched between parallel, carbonate-cemented, positively weathering ribs. These bands appear to represent early oil migration by hydrofracture. Based on crosscutting relationships between structures and cements, there are three distinct phases of oil migration: early migration along discrete hydrofractures; dominant pore migration associated with periodic breaching of deformation bands; and late migration along open fractures, some several centimeters in width. This sequence may be representative of migration histories along the NIFZ in the Los Angeles basin.
Leaching of heavy metals from solidified waste using Portland cement and zeolite as a binder.
Napia, Chuwit; Sinsiri, Theerawat; Jaturapitakkul, Chai; Chindaprasirt, Prinya
2012-07-01
This study investigated the properties of solidified waste using ordinary Portland cement (OPC) containing synthesized zeolite (SZ) and natural zeolite (NZ) as a binder. Natural and synthesized zeolites were used to partially replace the OPC at rates of 0%, 20%, and 40% by weight of the binder. Plating sludge was used as contaminated waste to replace the binder at rates of 40%, 50% and 60% by weight. A water to binder (w/b) ratio of 0.40 was used for all of the mixtures. The setting time and compressive strength of the solidified waste were investigated, while the leachability of the heavy metals was determined by TCLP. Additionally, XRD, XRF, and SEM were performed to investigate the fracture surface, while the pore size distribution was analyzed with MIP. The results indicated that the setting time of the binders marginally increased as the amount of SZ and NZ increased in the mix. The compressive strengths of the pastes containing 20 and 40wt.% of NZ were higher than those containing SZ. The compressive strengths at 28 days of the SZ solidified waste mixes were 1.2-31.1MPa and those of NZ solidified waste mixes were 26.0-62.4MPa as compared to 72.9MPa of the control mix at the same age. The quality of the solidified waste containing zeolites was better than that with OPC alone in terms of the effectiveness in reducing the leachability. The concentrations of heavy metals in the leachates were within the limits specified by the US EPA. SEM and MIP revealed that the replacement of Portland cement by zeolites increased the total porosity but decreased the average pore size and resulted in the better containment of heavy ions from the solidified waste. Copyright © 2012 Elsevier Ltd. All rights reserved.
Solute location in a nanoconfined liquid depends on charge distribution
DOE Office of Scientific and Technical Information (OSTI.GOV)
Harvey, Jacob A.; Thompson, Ward H., E-mail: wthompson@ku.edu
2015-07-28
Nanostructured materials that can confine liquids have attracted increasing attention for their diverse properties and potential applications. Yet, significant gaps remain in our fundamental understanding of such nanoconfined liquids. Using replica exchange molecular dynamics simulations of a nanoscale, hydroxyl-terminated silica pore system, we determine how the locations explored by a coumarin 153 (C153) solute in ethanol depend on its charge distribution, which can be changed through a charge transfer electronic excitation. The solute position change is driven by the internal energy, which favors C153 at the pore surface compared to the pore interior, but less so for the more polar,more » excited-state molecule. This is attributed to more favorable non-specific solvation of the large dipole moment excited-state C153 by ethanol at the expense of hydrogen-bonding with the pore. It is shown that a change in molecule location resulting from shifts in the charge distribution is a general result, though how the solute position changes will depend upon the specific system. This has important implications for interpreting measurements and designing applications of mesoporous materials.« less
Characterization of Biogenic Gas and Mineral Formation Process by Denitrification in Porous Media
NASA Astrophysics Data System (ADS)
Hall, C. A.; Kim, D.; Mahabadi, N.; van Paassen, L. A.
2017-12-01
Biologically mediated processes have been regarded and developed as an alternative approach to traditional ground improvement techniques. Denitrification has been investigated as a potential ground improvement process towards liquefaction hazard mitigation. During denitrification, microorganisms reduce nitrate to dinitrogen gas and facilitate calcium carbonate precipitation as a by-product under adequate environmental conditions. The formation of dinitrogen gas desaturates soils and allows for potential pore pressure dampening during earthquake events. While, precipitation of calcium carbonate can improve the mechanical properties by filling the voids and cementing soil particles. As a result of small changes in gas and mineral phases, the mechanical properties of soils can be significantly affected. Prior research has primarily focused on quantitative analysis of overall residual calcium carbonate mineral and biogenic gas products in lab-scale porous media. However, the distribution of these products at the pore-scale has not been well-investigated. In this research, denitrification is activated in a microfluidic chip simulating a homogenous pore structure. The denitrification process is monitored by sequential image capture, where gas and mineral phase changes are evaluated by image processing. Analysis of these images correspond with previous findings, which demonstrate that biogenic gas behaviour at the pore scale is affected by the balance between reaction, diffusion, and convection rates.
Anovitz, Lawrence M.; Freiburg, Jared T.; Wasbrough, Matthew; ...
2017-11-06
To examine the effects of burial diagenesis on heirarchical pore structures in sandstone and compare those with the effects of overgrowth formation, we obtained samples of St. Peter Sandstone from drill cores obtained in the Illinois and Michigan Basins. The multiscale pore structure of rocks in sedimentary reservoirs and the mineralogy associated with those pores are critical factors for estimating reservoir properties, including fluid mass in place, permeability, and capillary pressures, as well as geochemical interactions between the rock and the fluid. The combination of small- and ultra-small-angle neutron scattering with backscattered electron or X ray-computed tomographic imaging, or both,more » provided a means by which pore structures were quantified at scales ranging from aproximately 1 nm to 1 cm—seven orders of magnitude. Larger scale (>10 µm) porosity showed the expected logarithmic decrease in porosity with depth, although there was significant variation in each sample group. However, small- and ultra-small-angle neutron scattering data showed that the proportion of small-scale porosity increased with depth. Porosity distributions were not continuous, but consisted of a series of log normal-like distributions at several distinct scales within these rocks. Fractal dimensions at larger scales decreased (surfaces smoothed) with increasing depth, and those at smaller scales increased (surfaces roughened) and pores become more isolated (higher lacunarity). Furthermore, data suggest that changes in pore-size distributions are controlled by both physical (compaction) and chemical effects (precipitation, cementation, dissolution).« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Anovitz, Lawrence M.; Freiburg, Jared T.; Wasbrough, Matthew
To examine the effects of burial diagenesis on heirarchical pore structures in sandstone and compare those with the effects of overgrowth formation, we obtained samples of St. Peter Sandstone from drill cores obtained in the Illinois and Michigan Basins. The multiscale pore structure of rocks in sedimentary reservoirs and the mineralogy associated with those pores are critical factors for estimating reservoir properties, including fluid mass in place, permeability, and capillary pressures, as well as geochemical interactions between the rock and the fluid. The combination of small- and ultra-small-angle neutron scattering with backscattered electron or X ray-computed tomographic imaging, or both,more » provided a means by which pore structures were quantified at scales ranging from aproximately 1 nm to 1 cm—seven orders of magnitude. Larger scale (>10 µm) porosity showed the expected logarithmic decrease in porosity with depth, although there was significant variation in each sample group. However, small- and ultra-small-angle neutron scattering data showed that the proportion of small-scale porosity increased with depth. Porosity distributions were not continuous, but consisted of a series of log normal-like distributions at several distinct scales within these rocks. Fractal dimensions at larger scales decreased (surfaces smoothed) with increasing depth, and those at smaller scales increased (surfaces roughened) and pores become more isolated (higher lacunarity). Furthermore, data suggest that changes in pore-size distributions are controlled by both physical (compaction) and chemical effects (precipitation, cementation, dissolution).« less
Piemjai, Morakot; Nakabayashi, Nobuo
2015-01-01
A dentin-cement-prosthesis complex restored with either all-porcelain, cured resin-composite, or cast base metal alloy and cemented with either of the different resin cements was trimmed into a mini-dumbbell shape for tensile testing. The fractured surfaces and characterization of the dentin-cement interface of bonded specimens were investigated using a Scanning Electron Microscope. A significantly higher tensile strength of all-porcelain (12.5 ± 2.2 MPa) than that of cast metal (9.2 ± 3.5 MPa) restorations was revealed with cohesive failure in the cement and failure at the prosthesis-cement interface in Super-Bond C&B group. No significant difference in tensile strength was found among the types of restorations using the other three cements with adhesive failure on the dentin side and cohesive failure in the cured resin. SEM micrographs demonstrated the consistent hybridized dentin in Super-Bond C&B specimens that could resist degradation when immersed in hydrochloric acid followed by NaOCl solutions whereas a detached and degraded interfacial layer was found for the other cements. The results suggest that when complete hybridization of resin into dentin occurs tensile strength at the dentin-cement is higher than at the cement-prosthesis interfaces. The impermeable hybridized dentin can protect the underlying dentin and pulp from acid demineralization, even if detachment of the prosthesis has occurred. PMID:26539520
Pathways of fluid transport and reabsorption across the peritoneal membrane.
Asghar, R B; Davies, S J
2008-05-01
The three-pore model of peritoneal fluid transport predicts that once the osmotic gradient has dissipated, fluid reabsorption will be due to a combination of small-pore reabsorption driven by the intravascular oncotic pressure, and an underlying disappearance of fluid from the cavity by lymphatic drainage. Our study measured fluid transport by these pathways in the presence and absence of an osmotic gradient. Paired hypertonic and standard glucose-dwell studies were performed using radio-iodinated serum albumin as an intraperitoneal volume marker and changes in intraperitoneal sodium mass to determine small-pore versus transcellular fluid transport. Disappearance of iodinated albumin was considered to indicate lymphatic drainage. Variability in transcellular ultrafiltration was largely explained by the rate of small-solute transport across the membrane. In the absence of an osmotic gradient, fluid reabsorption occurred via the small-pore pathway, the rate being proportional to the small-solute transport characteristics of the membrane. In most cases, fluid removal from the peritoneal cavity by this pathway was faster than by lymphatic drainage. Our study shows that the three-pore model describes the pathways of peritoneal fluid transport well. In the presence of high solute transport, poor transcellular ultrafiltration was due to loss of the osmotic gradient and an enhanced small-pore reabsorption rate after this gradient dissipated.
Lee, Jian-Yuan; Wang, Yining; Tang, Chuyang Y; Huo, Fengwei
2015-11-23
The efficiency of forward osmosis (FO) process is generally limited by the internal concentration polarization (ICP) of solutes inside its porous substrate. In this study, mesoporous silica gel (SG) with nominal pore size ranging from 4-30 nm was used as fillers to prepare SG-based mixed matrix substrates. The resulting mixed matrix membranes had significantly reduced structural parameter and enhanced membrane water permeability as a result of the improved surface porosity of the substrates. An optimal filler pore size of ~9 nm was observed. This is in direct contrast to the case of thin film nanocomposite membranes, where microporous nanoparticle fillers are loaded to the membrane rejection layer and are designed in such a way that these fillers are able to retain solutes while allowing water to permeate through them. In the current study, the mesoporous fillers are designed as channels to both water and solute molecules. FO performance was enhanced at increasing filler pore size up to 9 nm due to the lower hydraulic resistance of the fillers. Nevertheless, further increasing filler pore size to 30 nm was accompanied with reduced FO efficiency, which can be attributed to the intrusion of polymer dope into the filler pores.
Lee, Jian-Yuan; Wang, Yining; Tang, Chuyang Y.; Huo, Fengwei
2015-01-01
The efficiency of forward osmosis (FO) process is generally limited by the internal concentration polarization (ICP) of solutes inside its porous substrate. In this study, mesoporous silica gel (SG) with nominal pore size ranging from 4–30 nm was used as fillers to prepare SG-based mixed matrix substrates. The resulting mixed matrix membranes had significantly reduced structural parameter and enhanced membrane water permeability as a result of the improved surface porosity of the substrates. An optimal filler pore size of ~9 nm was observed. This is in direct contrast to the case of thin film nanocomposite membranes, where microporous nanoparticle fillers are loaded to the membrane rejection layer and are designed in such a way that these fillers are able to retain solutes while allowing water to permeate through them. In the current study, the mesoporous fillers are designed as channels to both water and solute molecules. FO performance was enhanced at increasing filler pore size up to 9 nm due to the lower hydraulic resistance of the fillers. Nevertheless, further increasing filler pore size to 30 nm was accompanied with reduced FO efficiency, which can be attributed to the intrusion of polymer dope into the filler pores. PMID:26592565
Perspectives and limits for cement kilns as a destination for RDF.
Genon, G; Brizio, E
2008-11-01
RDF, the high calorific value fraction of MSW obtained by conventional separation systems, can be employed in technological plants (mainly cement kilns) in order to obtain a useful energy recovery. It is interesting and important to evaluate this possibility within the general framework of waste-to-energy solutions. The solution must be assessed on the basis of different aspects, namely: technological features and clinker characteristics; local atmospheric pollution; the effects of RDF used in cement kilns on the generation of greenhouse gases; the economics of conventional solid fuels substitution and planning perspectives, from the point of view of the destination of RDF and optimal cement kiln policy. The different experiences of this issue throughout Europe are reviewed, and some applications within Italy are also been considered. The main findings of the study are that the use of RDF in cement kilns instead of coal or coke offers environmental benefits in terms of greenhouse gases, while the formation of conventional gaseous pollutants is not a critical aspect. Indeed, the generation of nitrogen oxides can probably be lower because of lower flame temperatures or lower air excess. The presence of chlorinated micro-pollutants is not influenced by the presence of RDF in fuel, whereas depending on the quality of the RDF, some problems could arise compared to the substituted fuel as far as heavy metals are concerned, chiefly the more volatile ones.
Perspectives and limits for cement kilns as a destination for RDF
DOE Office of Scientific and Technical Information (OSTI.GOV)
Genon, G.; Brizio, E.
2008-11-15
RDF, the high calorific value fraction of MSW obtained by conventional separation systems, can be employed in technological plants (mainly cement kilns) in order to obtain a useful energy recovery. It is interesting and important to evaluate this possibility within the general framework of waste-to-energy solutions. The solution must be assessed on the basis of different aspects, namely: technological features and clinker characteristics; local atmospheric pollution; the effects of RDF used in cement kilns on the generation of greenhouse gases; the economics of conventional solid fuels substitution and planning perspectives, from the point of view of the destination of RDFmore » and optimal cement kiln policy. The different experiences of this issue throughout Europe are reviewed, and some applications within Italy are also been considered. The main findings of the study are that the use of RDF in cement kilns instead of coal or coke offers environmental benefits in terms of greenhouse gases, while the formation of conventional gaseous pollutants is not a critical aspect. Indeed, the generation of nitrogen oxides can probably be lower because of lower flame temperatures or lower air excess. The presence of chlorinated micro-pollutants is not influenced by the presence of RDF in fuel, whereas depending on the quality of the RDF, some problems could arise compared to the substituted fuel as far as heavy metals are concerned, chiefly the more volatile ones.« less
Factors affecting plant growth in membrane nutrient delivery
NASA Technical Reports Server (NTRS)
Dreschel, T. W.; Wheeler, R. M.; Sager, J. C.; Knott, W. M.
1990-01-01
The development of the tubular membrane plant growth unit for the delivery of water and nutrients to roots in microgravity has recently focused on measuring the effects of changes in physical variables controlling solution availability to the plants. Significant effects of membrane pore size and the negative pressure used to contain the solution were demonstrated. Generally, wheat grew better in units with a larger pore size but equal negative pressure and in units with the same pore size but less negative pressure. Lettuce also exhibited better plant growth at less negative pressure.
Biotribological properties at the stem-cement interface lubricated with different media.
Zhang, H Y; Luo, J B; Zhou, M; Zhang, Y; Huang, Y L
2013-04-01
Debonding of the stem-cement interface occurs inevitably in-vivo under physiological loading, and pseudo-synovial fluid is subsequently pumped into this interface, serving as the lubricant. However, the influence of protein adsorption onto the femoral stem surface has not been well taken into consideration in previous in vitro studies. The biotribological properties at the stem-cement interface were investigated through a series of fretting frictional tests using polished stainless steel 316L stem and smooth bone cement, lubricated by three different media at body temperature, i.e. 100% calf serum, 25% calf serum, and 0.9% saline solution. The surface characterization of the femoral stem was evaluated sequentially using optical microscope, optical interferometer, scanning electron microscope, and Raman spectroscopy. The friction coefficient generally kept stable during the test, and the minimum value (0.254) was obtained when 100% calf serum was used as the lubricant. Slight scratches were detected within the contact area for the stainless steel 316L stems lubricated by 100% calf serum and 25% calf serum, which was further surrounded by the adsorbed protein film with alveolate feature. Additionally, a wear scar was present within the contact area when 0.9% saline solution was used as the lubricant. Protein adsorption onto the stainless steel 316L stem surface affected the biotribological properties at the stem-cement interface under oscillatory fretting mechanism. Generation of wear debris at the stem-cement interface may be postponed by modification of physicochemical properties of the femoral stem to promote protein adsorption. Copyright © 2013 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Sokol, E. V.; Gaskova, O. L.; Kozmenko, O. A.; Kokh, S. N.; Vapnik, E. A.; Novikova, S. A.; Nigmatulina, E. N.
2014-11-01
This study shows that the mineral assemblages from clastic dikes in areas adjacent to the Dead Sea graben may be considered as natural analogues of alkaline concretes. The main infilling material of the clastic dikes is composed of well-sorted and well-rounded quartz sand. The cement of these hard rocks contains hydroxylapophyllite, tacharanite, calcium silicate hydrates, opal, calcite, and zeolite-like phases, which is indicative of a similarity of the natural cementation processes and industrial alkaline concrete production from quartz sands and industrial alkaline cements. The quartz grains exhibit a variety of reaction textures reflecting the interaction with alkaline solutions (opal and calcium hydrosilicate overgrowths; full replacement with apophyllite or thomsonite + apophyllite). The physicochemical analysis and reconstruction of the chemical composition of peralkaline Ca, Na, and K solutions that formed these assemblages reveal that the solutions evolved toward a more stable composition of zeolite-like phases, which are more resistant to long-term chemical weathering and atmospheric corrosion. The 40Ar/39Ar age of 6.2 ± 0.7 Ma obtained for apophyllite provides conclusive evidence for the high corrosion resistance of the assemblages consisting of apophyllite and zeolite-like phases.
A speciation solver for cement paste modeling and the semismooth Newton method
DOE Office of Scientific and Technical Information (OSTI.GOV)
Georget, Fabien, E-mail: fabieng@princeton.edu; Prévost, Jean H., E-mail: prevost@princeton.edu; Vanderbei, Robert J., E-mail: rvdb@princeton.edu
2015-02-15
The mineral assemblage of a cement paste may vary considerably with its environment. In addition, the water content of a cement paste is relatively low and the ionic strength of the interstitial solution is often high. These conditions are extreme conditions with respect to the common assumptions made in speciation problem. Furthermore the common trial and error algorithm to find the phase assemblage does not provide any guarantee of convergence. We propose a speciation solver based on a semismooth Newton method adapted to the thermodynamic modeling of cement paste. The strong theoretical properties associated with these methods offer practical advantages.more » Results of numerical experiments indicate that the algorithm is reliable, robust, and efficient.« less
Modelling the leaching of Pb, Cd, As, and Cr from cementitious waste using PHREEQC.
Halim, Cheryl E; Short, Stephen A; Scott, Jason A; Amal, Rose; Low, Gary
2005-10-17
A leaching model was developed using the United States Geological Survey public domain PHREEQC geochemical package to simulate the leaching of Pb, Cd, As, and Cr from cementitious wastes. The model utilises both kinetic terms and equilibrium thermodynamics of key compounds and provides information on leachate and precipitate speciation. The model was able to predict the leaching of Pb, Cd, As, and Cr from cement in the presence of both simple (0.1 and 0.6M acetic acid) and complex municipal landfill leachates. Heavy metal complexation by the municipal landfill leachate was accounted for by the introduction of a monoprotic organic species into the model. The model indicated Pb and As were predominantly incorporated within the calcium silicate hydrate matrix while a greater portion of Cd was seen to exist as discrete particles in the cement pores and Cr (VI) existed mostly as free CrO4(2-) ions. Precipitation was found to be the dominant mechanism controlling heavy metal solubility with carbonate and silicate species governing the solubility of Pb and carbonate, silicate and hydroxide species governing the solubility of Cd. In the presence of acetic acid, at low pH values Pb and Cd acetate complexes were predominant whereas, at high pH values, hydroxide species dominated. At high pH values, the concentration of As in the leachate was governed by the solubility of Ca3(AsO4)2 with the presence of carbonate alkalinity competing with arsenate for Ca ions. In the presence of municipal landfill leachate, Pb and Cd organic complexes dominated the heavy metal species in solution. The reduction of As and Cr in municipal landfill leachate was crucial for determining aqueous speciation, with typical municipal landfill conditions providing the reduced forms of As and Cr.
Cement Distribution and Diagenetic Pathway of the Miocene Sediments on Kardiva Platform, Maldives.
NASA Astrophysics Data System (ADS)
Laya, J. C.; Prince, K.; Betzler, C.; Eberli, G. P.; Blättler, C. L.; Swart, P. K.; Reolid, J.; Alvarez Zarikian, C. A.; Reijmer, J.
2017-12-01
The Maldives archipelago is an ideal example for understanding the dynamics of isolated carbonate platforms. While previous sedimentological studies have focused on oceanographic and climatic controls on deposition, there have been limited studies on the diagenetic evolution of the Maldives archipelago. This project seeks to establish a relationship between the facies, cement distribution, and diagenetic evolution of the Kardiva Platform and associated diagenetic fluids. Samples from cores of IODP Expedition 359 at Sites U1645, U1469, and U1470 were analyzed for stable isotope geochemistry and detailed petrography including SEM, confocal and CL microscopy to investigate variations in facies, cements, porosity and diagenetic products. The facies analyzed consist mainly of planktonic and benthic foraminifers, red coralline algae, echinoderm, coral and skeletal fragments. The main facies include foraminifera grain/packstone, red algae rich grain/packstone, algal floatstone and coral floatstone. Those facies present a cyclic and general shallowing upwards trend. These facies are interpreted as shallow platform deposits on proximal areas to the margin associated with the oligophotic zone. Cement volume varies between 5% and 48%, and they have been classified as isopachous, bladed to fibrous (dog tooth), drusy and equant. Equant and drusy show recognizable growth bands with CL and confocal. Evidence of intense dissolution is shown by extensive moldic porosity within phreatic and limited vadose zones. In addition, dolomite appears as a replacement phase associated with red-algae-rich horizons and as cement on pore walls and voids. These deposits experienced a variety of diagenetic processes driven by the evolution of diagenetic fluid chemistry and by the nature of the skeletal components. Those processes can be tied to external controls such as climate (monsoonal effects), sea-level and currents.
In vitro evaluation of microleakage of various types of dental cements.
Medić, Vesna; Obradović-Djuricić, Kosovka; Dodić, Slobodan; Petrović, Renata
2010-01-01
Microleakage is defined as the clinically undetectable seepage of oral fluids containing bacteria and debris between cement layer and tooth restoration. This in vitro study investigated the effect of different dental cements (zinc-phosphate, polycarboxylate, glass-ionomer and resin cement) on microleakage in different ceramic crown systems (metal ceramic crown, metal ceramic crown with a porcelain margin, Empress 2 and in Ceram all-ceramic crowns) fixed on extracted human teeth. One hundred and sixty intact human premolars were randomized to four groups of forty teeth each, according to the different ceramic crown systems. They were prepared in a standardized manner for metal-ceramic and all-ceramic crowns. Crowns were made following a standard laboratory technique, and each group of crowns were divided into four groups according to the different cement agents and cemented on their respective abutments. The specimens were subjected to thermocycling, placed in methylene blue solutions, embedded in resin blocks and vertically cut in the bucco-oral and meso-distal direction. The microleakage in the area of tooth-cement interface was defined as linear penetration of methylene blue and was determined with a microscope to assign microleakage scores using a five-point scale. A significant association was found between a cement type and degree of microleakage (p = 0.001). No statistically significant differences were found among the different ceramic crown systems luted with the same dental cement. The smallest degree of microleakage was observed in specimens luted with resin cement (X = 1.73), followed by glass-ionomer cement (X=2.45) and polycarboxylate cement (X = 3.20). The greatest degree of microleakage was detected in the crowns fixed with zincphosphate cement (X = 3.33). The investigated dental cements revealed different sealing abilities. The use of resin cement resulted in the percentage of 0 microleakage scores. Due to this feature, the resin cement is to be recommended in everyday clinical practice.
NASA Astrophysics Data System (ADS)
Cao, P.; Karpyn, Z.; Li, L.
2013-12-01
CO2-brine has the potential to alter wellbore cement in depleted oil and gas reservoirs under geological CO2 sequestration conditions. A better understanding of CO2-brine-cement-rock interaction is needed to evaluate the seal integrity of candidate sequestration formation in the long run. This work investigates possible alteration of wellbore cement when bonded by different host formation rock upon exposure to CO2-saturated brine. Composite cement-sandstone and cement-limestone core samples were created to perform reactive coreflood experiments. After an eight-day dynamic flow-through period, both cores had a similar extent of porosity increase, while the cement-limestone core experienced a ten-fold higher increase in permeability. With the aid of X-ray Micro-CT imaging and Scanning Electron Microscopy, it is observed that cement underwent greater degradation at the cement-sandstone interface. Degradation of cement-limestone core mainly took place on the host rock matrix. Worm holes were developed and a solution channel was formed in the limestone, creating a dominant flow path that altered both flow and reaction behavior. Limestone buffered the injected acidic brine preventing further deterioration of cement near the core outlet. Changes in fluid chemistry of limestone and sandstone coreflood effluents are compared. Results from this work are aimed at assisting the development and validation of robust reactive transport models through direct measurement of cemented rock core porosity and permeability evolution as well as the effluent aqueous chemistry change. This will subsequently improve predictive capabilities of reactive transport models associated with CO2 sequestration in geologic environments. Permeability Evolution of Cement-Rock Core Sample during Dynamic Flow of CO2-Brine
Effect of different resin luting cements on the marginal fit of lithium disilicate pressed crowns.
Mounajjed, Radek; Salinas, Thomas J; Ingr, Tomas; Azar, Basel
2017-11-15
The vertical marginal discrepancy of restorations can increase upon cementation, and poor marginal fit can lead to cement dissolution, marginal discoloration, microleakage, and secondary caries. The amount of increase is related to the type of luting cement used, but how lithium disilicate pressed crowns are affected by different resin cements is unclear. The purpose of this in vitro study was to compare the effect of using different resin luting cements on the vertical marginal discrepancy of lithium disilicate pressed crowns. A total of 18 intact extracted mandibular third molars were disinfected in a solution of 10% formalin for 7 days and were then prepared to receive a ceramic crown. Impressions were made with polyvinyl siloxane and lithium disilicate pressed crowns made and cemented with 1 of 3 resin luting cements. The marginal discrepancy was measured at 4 points on the finishing line of each tooth, with optical microscopy at ×200 magnification before and after cementation. Statistical analysis was done with the Kruskal-Wallis test to compare the median marginal increase among the 3 groups. The least amount of marginal increase after cementation was with Harvard PremiumFlow cement, with an average marginal increase of 42 ±11 μm. RelyX Ultimate cement increased the margins by an average 45 ±29 μm. The highest marginal increase was found in the Enamel Plus HRi preheated composite resin group (116 ±47 μm). The marginal increase of pressed crowns cemented with preheated composite resin (Enamel Plus HRi) exceeded the clinically acceptable range of marginal discrepancy. Copyright © 2017 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.
Hu, Yuan; Sinha, Sudipta Kumar; Patel, Sandeep
2015-06-23
Cell-penetrating and antimicrobial peptides show a remarkable ability to translocate across physiological membranes. Along with factors such as electric-potential-induced perturbations of membrane structure and surface tension effects, experiments invoke porelike membrane configurations during the solute transfer process into vesicles and cells. The initiation and formation of pores are associated with a nontrivial free-energy cost, thus necessitating a consideration of the factors associated with pore formation and the attendant free energies. Because of experimental and modeling challenges related to the long time scales of the translocation process, we use umbrella sampling molecular dynamics simulations with a lipid-density-based order parameter to investigate membrane-pore-formation free energy employing Martini coarse-grained models. We investigate structure and thermodynamic features of the pore in 18 lipids spanning a range of headgroups, charge states, acyl chain lengths, and saturation. We probe the dependence of pore-formation barriers on the area per lipid, lipid bilayer thickness, and membrane bending rigidities in three different lipid classes. The pore-formation free energy in pure bilayers and peptide translocating scenarios are significantly coupled with bilayer thickness. Thicker bilayers require more reversible work to create pores. The pore-formation free energy is higher in peptide-lipid systems than in peptide-free lipid systems due to penalties to maintain the solvation of charged hydrophilic solutes within the membrane environment.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Yanping Guo; Abhishek Yadav; Tanju Karanfil
Adsorption of trichloroethylene (TCE) and atrazine, two synthetic organic contaminants (SOCs) having different optimum adsorption pore regions, by four activated carbons and an activated carbon fiber (ACF) was examined. Adsorbents included two coconut-shell based granular activated carbons (GACs), two coal-based GACs (F400 and HD4000) and a phenol formaldehyde-based activated carbon fiber. The selected adsorbents had a wide range of pore size distributions but similar surface acidity and hydrophobicity. Single solute and preloading (with a dissolved organic matter (DOM)) isotherms were performed. Single solute adsorption results showed that (i) the adsorbents having higher amounts of pores with sizes about the dimensionsmore » of the adsorbate molecules exhibited higher uptakes, (ii) there were some pore structure characteristics, which were not completely captured by pore size distribution analysis, that also affected the adsorption, and (iii) the BET surface area and total pore volume were not the primary factors controlling the adsorption of SOCs. The preloading isotherm results showed that for TCE adsorbing primarily in pores <10 {angstrom}, the highly microporous ACF and GACs, acting like molecular sieves, exhibited the highest uptakes. For atrazine with an optimum adsorption pore region of 10-20 {angstrom}, which overlaps with the adsorption region of some DOM components, the GACs with a broad pore size distribution and high pore volumes in the 10-20 {angstrom} region had the least impact of DOM on the adsorption. 25 refs., 3 figs., 3 tabs.« less
Experimental Study on Rise Husk Ash & Fly Ash Based Geo-Polymer Concrete Using M-Sand
NASA Astrophysics Data System (ADS)
Nanda Kishore, G.; Gayathri, B.
2017-08-01
Serious environmental problems by means of increasing the production of Ordinary Portland cement (OPC), which is conventionally used as the primary binder to produce cement concrete. An attempt has been made to reduce the use of ordinary Portland cement in cement concrete. There is no standard mix design of geo-polymer concrete, an effort has been made to know the physical, chemical properties and optimum mix of geo-polymer concrete mix design. Concrete cubes of 100 x 100 x 100 mm were prepared and cured under steam curing for about 24 hours at temperature range of 40°C to 60°C. Fly ash is replaced partially with rice husk ash at percentage of 10%, 15% and 25%. Sodium hydroxide and sodium silicate are of used as alkaline activators with 5 Molar and 10 Molar NaOH solutions. Natural sand is replaced with manufacture sand. Test results were compared with controlled concrete mix of grade M30. The results shows that as the percentage of rice husk ash and water content increases, compressive strength will be decreases and as molarity of the alkaline solution increases, strength will be increases.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Drzewiecki, P.A.; Simo, T.; Moline, G.
1991-03-01
The Middle to Late Ordovician St. Peter Sandstone of the Michigan basin is a fine- to medium-grained quartz sandstone. Extensive stylolitization and intergranular pressure solution have been major factors in reducing the porosity of certain horizons within the St. Peter, resulting in pressure compartmentation of the reservoir. Pressure versus depth data for various Michigan basin wells indicate that the basin contains compartments that are overpressured by as much as 500 psi. Horizons bounding these compartments are often affected by intense stylolitization (or intergranular pressure solution) and quartz cementation and have been correlated with zones of low porosity and permeability ({phi}more » = 0-3%, k = <50 {mu}d). These tight zones can be correlated within single gas fields, and some may extend across the Michigan basin. The St. Peter Sandstone has been buried to depths of about 3,500 m in the central part of the basin and 1,500 m at the margins. Intensely stylolitized zones are found at all depths throughout the basin and do not appear to change in abundance or style with depths. Factors that influence the formation, morphology, and abundance of stylolites in the St. Peter include (1) clay intraclasts, (2) intergranular clay, and (3) fine-grained, feldspar-rich sand. Stylolites also occur at contacts between quartz-cemented and carbonate-cemented zones and within well-cemented sands. Intergranular pressure solution and stylolites may be responsible for the formation of a compartment seal. Understanding their genesis can allow prediction of variations in porosity in Michigan basin well cores.« less
Montufar, Edgar B.; Engqvist, Håkan; Ginebra, Maria‐Pau; Persson, Cecilia
2016-01-01
Abstract Resorbable calcium phosphate based bone void fillers should work as temporary templates for new bone formation. The incorporation of macropores with sizes of 100 −300 µm has been shown to increase the resorption rate of the implant and speed up bone ingrowth. In this work, macroporous brushite cements were fabricated through foaming of the cement paste, using two different synthetic surfactants, Tween® 80 and Pluronic® F‐127. The macropores formed in the Pluronic samples were both smaller and less homogeneously distributed compared with the pores formed in the Tween samples. The porosity and compressive strength (CS) were comparable to previously developed hydroxyapatite foams. The cement foam containing Tween, 0.5M citric acid in the liquid, 1 mass% of disodium dihydrogen pyrophosphate mixed in the powder and a liquid to powder ratio of 0.43 mL/g, showed the highest porosity values (76% total and 56% macroporosity), while the CS was >1 MPa, that is, the hardened cement could be handled without rupture of the foamed structure. The investigated brushite foams show potential for future clinical use, both as bone void fillers and as scaffolds for in vitro bone regeneration. © 2015 The Authors. Journal of Biomedical Materials Research Part B: Applied Biomaterials Published by Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 67–77, 2016. PMID:25615405
NASA Astrophysics Data System (ADS)
Nader, Fadi H.; Champenois, France; Barbier, Mickaël; Adelinet, Mathilde; Rosenberg, Elisabeth; Houel, Pascal; Delmas, Jocelyne; Swennen, Rudy
2016-11-01
The impact of compaction diagenesis on reservoir properties is addressed by means of observations made on five boreholes with different burial histories of the Early Callovian ;Dalle Nacrée; Formation in the Paris Basin. Petrographic analyses were carried out in order to investigate the rock-texture, pore space type and volume, micro-fabrics, and cement phases. Based on the acquired data, a chronologically ordered sequence of diagenetic events (paragenesis) for each borehole was reconstructed taking the burial history into account. Point counting and a segmentation algorithm (Matlab) were used to quantify porosity, as well as the amounts of grain constituents and cement phases on scanned images of studied thin sections. In addition, four key samples were analyzed by 3D imaging using microfocus X-ray computer tomography. Basin margin grainstones display a different burial diagenesis when compared to basin centre grainstones and wackestones. The former have been affected by considerable cementation (especially by blocky calcite) prior to effective burial, in contrast to the basin centre lithologies where burial and compaction prevailed with relatively less cementation. Fracturing and bed-parallel stylolitization, observed especially in basinal wackestone facies also invoke higher levels of mechanical and chemical compaction than observed in basin marginal equivalents. Compaction fluids may have migrated at the time of burial from the basin centre towards its margins, affecting hence the reservoir properties of similar rock textures and facies and resulting in cross-basin spatial diagenetic heterogeneities.
Rupture in cemented granular media: application to wheat endosperm
NASA Astrophysics Data System (ADS)
Topin, V.; Delenne, J.-Y.; Radjai, F.
2009-06-01
The mechanical origin of the wheat hardness used to classify wheat flours is an open issue. Wheat endosperm can be considered as a cemented granular material, consisting of densely packed solid particles (the starch granules) and a pore-filling solid matrix (the protein) sticking to the particles. We use the lattice element method to investigate cemented granular materials with a texture close to that of wheat endosperm and with variable matrix volume fraction and particle-matrix adherence. From the shape of the probability density of vertical stresses we distinguish weak, intermediate and strong stresses. The large stresses occur mostly at the contact zones as in noncohesive granular media with a decreasing exponential distribution. The weak forces reflect the arching effect. The intermediate stresses belong mostly to the bulk of the particles and their distribution is well fit to a Gaussian distribution. We also observe that the stress chains are essentially guided by the cementing matrix in tension and by the particulate backbone in compression. Crack formation is analyzed in terms of particle damage as a function of matrix volume fraction and particle-matrix adherence. Our data provide evidence for three regimes of crack propagation depending on the crack path through the material. We find that particle damage scales well with the relative toughness of the particle-matrix interface. The interface toughness appears therefore to be strongly correlated with particle damage and determines transition from soft to hard behavior in wheat endosperm.
Pérez-Nicolás, María; Alvarez, José Ignacio
2017-01-01
Mortars with two different binders (Portland cement (PC) and high alumina cement (HAC)) were modified upon the bulk incorporation of nano-structured photocatalytic additives (bare TiO2, and TiO2 doped with either iron (Fe-TiO2) or vanadium (V-TiO2)). Plastic and hardened state properties of these mortars were assessed in order to study the influence of these nano-additives. Water demand was increased, slightly by bare TiO2 and Fe-TiO2, and strongly by V-TiO2, in agreement with the reduction of the particle size and the tendency to agglomerate. Isothermal calorimetry showed that hydration of the cementitious matrices was accelerated due to additional nucleation sites offered by the nano-additives. TiO2 and doped TiO2 did not show pozzolanic reactivity in the binding systems. Changes in the pore size distribution, mainly the filler effect of the nano-additives, accounted for the increase in compressive strengths measured for HAC mortars. A complex microstructure was seen in calcium aluminate cement mortars, strongly dependent on the curing conditions. Fe-TiO2 was found to be homogeneously distributed whereas the tendency of V-TiO2 to agglomerate was evidenced by elemental distribution maps. Water absorption capacity was not affected by the nano-additive incorporation in HAC mortars, which is a favourable feature for the application of these mortars. PMID:29036917
Adsorption of polypropylene from dilute solutions on a zeolite column packing.
Macko, Tibor; Pasch, Harald; Denayer, Joeri F
2005-01-01
Faujasite type zeolite CBV-780 was tested as adsorbent for isotactic polypropylene by liquid chromatography. When cyclohexane, cyclohexanol, n-decanol, n-dodecanol, diphenylmethane, or methylcyclohexane was used as mobile phase, polypropylene was fully or partially retained within the column packing. This is the first series of sorbent-solvent systems to show a pronounced retention of isotactic polypropylene. According to the hydrodynamic volumes of polypropylene in solution, macromolecules of polypropylene should be fully excluded from the pore volume of the sorbent. Sizes of polypropylene macromolecules in linear conformations, however, correlate with the pore size of the column packing used. It is presumed that the polypropylene chains partially penetrate into the pores and are retained due to the high adsorption potential in the narrow pores.
Wagner, Brian M.; Schuster, Stephanie A.; Boyes, Barry E.; Shields, Taylor J.; Miles, William L.; Haynes, Mark J.; Moran, Robert E.; Kirkland, Joseph J.; Schure, Mark R.
2017-01-01
To facilitate mass transport and column efficiency, solutes must have free access to particle pores to facilitate interactions with the stationary phase. To ensure this feature, particles should be used for HPLC separations which have pores sufficiently large to accommodate the solute without restricted diffusion. This paper describes the design and properties of superficially porous (also called Fused-Core®, core shell or porous shell) particles with very large (1000 Å) pores specifically developed for separating very large biomolecules and polymers. Separations of DNA fragments, monoclonal antibodies, large proteins and large polystyrene standards are used to illustrate the utility of these particles for efficient, high-resolution applications. PMID:28213987
Wagner, Brian M; Schuster, Stephanie A; Boyes, Barry E; Shields, Taylor J; Miles, William L; Haynes, Mark J; Moran, Robert E; Kirkland, Joseph J; Schure, Mark R
2017-03-17
To facilitate mass transport and column efficiency, solutes must have free access to particle pores to facilitate interactions with the stationary phase. To ensure this feature, particles should be used for HPLC separations which have pores sufficiently large to accommodate the solute without restricted diffusion. This paper describes the design and properties of superficially porous (also called Fused-Core ® , core shell or porous shell) particles with very large (1000Å) pores specifically developed for separating very large biomolecules and polymers. Separations of DNA fragments, monoclonal antibodies, large proteins and large polystyrene standards are used to illustrate the utility of these particles for efficient, high-resolution applications. Copyright © 2017 Elsevier B.V. All rights reserved.
Structure formation control of foam concrete
NASA Astrophysics Data System (ADS)
Steshenko, Aleksei; Kudyakov, Aleksander; Konusheva, Viktoriya; Syrkin, Oleg
2017-01-01
The process of predetermined foam concrete structure formation is considered to be a crucial issue from the point of process control and it is currently understudied thus defining the need for additional research. One of the effective ways of structure formation control in naturally hardening foam concrete is reinforcement with dispersed fibers or introduction of plasticizers. The paper aims at studying the patterns of influence of microreinforcing and plasticizing additives on the structure and performance properties of foam concrete. Preparation of foam concrete mix has been conducted using one-step technology. The structure of modified foam concrete has been studied by means of electron microscopy. The cellular structure of foam concrete samples with the additives is homogeneous; the pores are uniformly distributed over the total volume. It has been revealed that introduction of the Neolas 5.2 plasticizer and microreinforcing fibers in the foam concrete mixture in the amount of 0.4 - 0.1 % by weight of cement leads to reduction of the average pore diameter in the range of 45.3 to 30.2 microns and the standard deviation of the pore average diameter from 23.6 to 9.2 in comparison with the sample without additive. Introduction of modifying additives has stimulated formation of a large number of closed pores. Thus porosity of conditionally closed pores has increased from 16.06 % to 34.48 %, which has lead to increase of frost resistance brand of foam concrete from F15 to F50 and to reduction of its water absorption by weight by 20 %.
NASA Technical Reports Server (NTRS)
Grugel, R.N.; Lee, C.P.; Cox, M.C.; Blandford, B.T.; Anilkumar, A.V.
2008-01-01
Controlled directional solidification experiments were performed in capillary channels, using nitrogen-saturated succinonitrile, to examine the effect of an in-situ stepwise processing pressure increase on an isolated pore evolution. Two experiments were performed using different processing pressure input profiles. The results indicate that a processing pressure increase has a transient effect on pore growth geometry characterized by an initial phase of decreasing pore diameter, followed by a recovery phase of increasing pore diameter. The experimental results also show that processing pressure can be used as a control parameter to either increase or terminate porosity formation. A theoretical model is introduced which indicates that the pore formation process is limited by the diffusion of solute-gas through the melt, and that the observed response toa pressure increase is attributed to the re-equilibration of solute concentration in the melt associated with the increased melt pressure.
Elements of an improved model of debris-flow motion
Iverson, R.M.
2009-01-01
A new depth-averaged model of debris-flow motion describes simultaneous evolution of flow velocity and depth, solid and fluid volume fractions, and pore-fluid pressure. Non-hydrostatic pore-fluid pressure is produced by dilatancy, a state-dependent property that links the depth-averaged shear rate and volumetric strain rate of the granular phase. Pore-pressure changes caused by shearing allow the model to exhibit rate-dependent flow resistance, despite the fact that the basal shear traction involves only rate-independent Coulomb friction. An analytical solution of simplified model equations shows that the onset of downslope motion can be accelerated or retarded by pore-pressure change, contingent on whether dilatancy is positive or negative. A different analytical solution shows that such effects will likely be muted if downslope motion continues long enough, because dilatancy then evolves toward zero, and volume fractions and pore pressure concurrently evolve toward steady states. ?? 2009 American Institute of Physics.
Bian, Xiao-Peng; Yang, Tao; Lin, An-Jun; Jiang, Shao-Yong
2015-01-01
We have developed a technique for the rapid, precise and accurate determination of sulfur isotopes (δ(34)S) by MC-ICP-MS applicable to a range of sulfur-bearing solutions of different sulfur content. The 10 ppm Alfa-S solution (ammonium sulfate solution, working standard of the lab of the authors) was used to bracket other Alfa-S solutions of different concentrations and the measured δ(34)SV-CDT values of Alfa-S solutions deviate from the reference value to varying degrees (concentration effect). The stability of concentration effect has been verified and a correction curve has been constructed based on Alfa-S solutions to correct measured δ(34)SV-CDT values. The curve has been applied to AS solutions (dissolved ammonium sulfate from the lab of the authors) and pore water samples successfully, validating the reliability of our analytical method. This method also enables us to measure the sulfur concentration simultaneously when analyzing the sulfur isotope composition. There is a strong linear correlation (R(2)>0.999) between the sulfur concentrations and the intensity ratios of samples and the standard. We have constructed a regression curve based on Alfa-S solutions and this curve has been successfully used to determine sulfur concentrations of AS solutions and pore water samples. The analytical technique presented here enable rapid, precise and accurate S isotope measurement for a wide range of sulfur-bearing solutions - in particular for pore water samples with complex matrix and varying sulfur concentrations. Also, simultaneous measurement of sulfur concentrations is available. Copyright © 2014 Elsevier B.V. All rights reserved.
Othman, Rahimah; Vladisavljević, Goran T; Simone, Elena; Nagy, Zoltan K; Holdich, Richard G
2017-12-06
Microcrystals of piroxicam (PRX) monohydrate with a narrow size distribution were prepared from acetone/PRX solutions by antisolvent crystallization via metallic membranes with ordered pore arrays. Crystallization was achieved by controlled addition of the feed solution through the membrane pores into a well-stirred antisolvent. A complete transformation of an anhydrous form I into a monohydrate form of PRX was confirmed by Raman spectroscopy and differential scanning calorimetry. The size of the crystals was 7-34 μm and was controlled by the PRX concentration in the feed solution (15-25 g L -1 ), antisolvent/solvent volume ratio (5-30), and type of antisolvent (Milli-Q water or 0.1-0.5 wt % aqueous solutions of hydroxypropyl methyl cellulose (HPMC), poly(vinyl alcohol) or Pluronic P-123). The smallest crystals were obtained by injecting 25 g L -1 PRX solution through a stainless-steel membrane with a pore size of 10 μm into a 0.06 wt % HPMC solution stirred at 1500 rpm using an antisolvent/solvent ratio of 20. HPMC provided better steric stabilization of microcrystals against agglomeration than poly(vinyl alcohol) and Pluronic P-123, due to hydrogen bonding interactions with PRX and water. A continuous production of large PRX monohydrate microcrystals with a volume-weighted mean diameter above 75 μm was achieved in a continuous stirred membrane crystallizer. Rapid pouring of Milli-Q water into the feed solution resulted in a mixture of highly polydispersed prism-shaped and needle-shaped crystals.
Optical coherence tomography investigations of ceramic lumineers
NASA Astrophysics Data System (ADS)
Fernandes, Luana O.; Graça, Natalia D. R. L.; Melo, Luciana S. A.; Silva, Claudio H. V.; Gomes, Anderson S. L.
2016-02-01
Lumineers are veneer laminates used as an alternative for aesthetic dental solutions of the highest quality, but the only current means of its performance assessment is visual inspection. The objective of this study was to use the Optical Coherence Tomography (OCT) technique working in spectral domain to analyze in vivo in a single patient, 14 lumineers 180 days after cementation. It was possible to observe images in various kinds of changes in the cementing line and the laminate. It was concluded that the OCT is an effective and promising method to clinical evaluation of the cementing line in lumineers.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Balhoff, Matthew; Tavassoli, Shayan; Fei Ho, Jostine
The potential leakage of hydrocarbon fluids or CO 2 out of subsurface formations through wells with fractured cement or debonded microannuli is a primary concern in oil and gas production and CO 2 storage. The presence of fractures in a cement annulus with apertures on the order of 10–300 microns can pose a significant leakage danger with effective permeability in the range of 0.1–1 mD (millidarcy). Leakage pathways with small apertures are often difficult to repair using conventional oilfield cement, thus a low-viscosity sealant that can be easily placed into these fractures while providing an effective seal is desired. Themore » development of a novel application using pH-triggered polymeric sealants could potentially be the solution to plugging these fractures and that was the research aim of this study. The application is based on the transport and reaction of a low-pH poly(acrylic acid) polymer through fractures in strongly alkaline cement. The pH-sensitive microgels viscosify upon neutralization with cement to become highly swollen gels with substantial yield stress that can block fluid flow. Experiments in a cement fracture determined the effects of the viscosification and gel deposition via real-time visual observation and measurements of pressure gradient and effluent pH. While the pH-triggered gelling mechanism and rheology measurements of the neutralized polymer gel show promising results, the polymer solution in contact with cement undergoes an undesirable reaction known as polymer syneresis. Syneresis is caused by the release of calcium cation from cement that collapses the polymer network. Syneresis produces an unstable calcium-precipitation byproduct that is detrimental to the strength and stability of the gel in place. As a result, gel-sealed leakage pathways that subjected to various degrees of syneresis often failed to hold back pressures. Several chemicals were studied to inhibit polymer syneresis and tested for pretreatment of cement cores to remove calcium and prevent syneresis during polymer placement. A chelating agent, sodium triphosphate (Na 5P 3O 10), was found to successfully eliminate syneresis without compromising the injectivity of polymer solution during placement. Polymer gel strength is determined by recording the maximum holdback pressure gradients during liquid breakthrough tests after various periods of pretreatment and polymer shut-in time. Cores pretreated with Na 5P 3O 10 successfully held up to an average of 80 psi/ft, which is significantly greater than the expected threshold value of about 0.1-5 psi/ft required to prevent flow in a typical CO 2 leakage scenario. The use of such inexpensive, pH-triggered poly-acrylic acid polymer allows long-term robust seal of leaky wellbores under high pH conditions.« less
Hussein, Esam M A; Agbogun, H M D; Al, Tom A
2015-03-01
A method is presented for interpreting the values of x-ray attenuation coefficients reconstructed in computed tomography of porous media, while overcoming the ambiguity caused by the multichromatic nature of x-rays, dilution by void, and material heterogeneity. The method enables determination of porosity without relying on calibration or image segmentation or thresholding to discriminate pores from solid material. It distinguishes between solution-accessible and inaccessible pores, and provides the spatial and frequency distributions of solid-matrix material in a heterogeneous medium. This is accomplished by matching an image of a sample saturated with a contrast solution with that saturated with a transparent solution. Voxels occupied with solid-material and inaccessible pores are identified by the fact that they maintain the same location and image attributes in both images, with voxels containing inaccessible pores appearing empty in both images. Fully porous and accessible voxels exhibit the maximum contrast, while the rest are porous voxels containing mixtures of pore solutions and solid. This matching process is performed with an image registration computer code, and image processing software that requires only simple subtraction and multiplication (scaling) processes. The process is demonstrated in dolomite (non-uniform void distribution, homogeneous solid matrix) and sandstone (nearly uniform void distribution, heterogeneous solid matrix) samples, and its overall performance is shown to compare favorably with a method based on calibration and thresholding. Copyright © 2014 Elsevier Ltd. All rights reserved.
Pujari-Palmer, Michael; Robo, Celine; Persson, Cecilia; Procter, Philip; Engqvist, Håkan
2018-01-01
Disease and injuries that affect the skeletal system may require surgical intervention and internal fixation, i.e. orthopedic plate and screw insertion, to stabilize the injury and facilitate tissue repair. If the surrounding bone quality is poor the screws may migrate, or the bone may fail, resulting in fixation failure. While numerous studies have shown that cement augmentation of the interface between bone and implant can increase screw pull-out force, the physical properties of cement that influence pull-out force have not been investigated. The present study sought to determine how the physical properties of high strength calcium phosphate cements (hsCPCs, specifically dicalcium phosphate) affected the corresponding orthopedic screw pull-out force in urethane foam models of "healthy" and "osteoporotic" synthetic bone (Sawbones). In the simplest model, where only the bond strength between screw thread and cement (without Sawbone) was tested, the correlation between pull-out force and cement compressive strength (R 2 = 0.79) was weaker than correlation with total cement porosity (R 2 = 0.89). In open pore Sawbone that mimics "healthy" cancellous bone density the stronger cements produced higher pull-out force (50-60% increase). High strength, low porosity cements also produced higher pull-out forces (50-190% increase) in "healthy" Sawbones with cortical fixation if the failure strength of the cortical material was similar to, or greater than (a metal shell), actual cortical bone. This result is of particular clinical relevance where fixation with a metal plate implant is indicated, as the nearby metal can simulate a thicker cortical shell, thereby increasing the pull-out force of screws augmented with stronger cements. The improvement in pull-out force was apparent even at low augmentation volumes of 0.5mL (50% increase), which suggest that in clinical situations where augmentation volume is limited the stronger, lower porosity calcium phosphate cement (CPC) may still produce a significant improvement in screw pull-out force. When the correlation strength of all the tested models were compared both cement porosity and compressive strength accurately predicted pull-out force (R 2 =1.00, R 2 =0.808), though prediction accuracy depended upon the strength of the material surrounding the Sawbone. The correlations strength was low for bone with no, or weak, cortical fixation (R 2 =0.56, 0.36). Higher strength and lower porosity CPCs also produced greater pull-out force (1-1.5kN) than commercial CPC (0.2-0.5kN), but lower pull-out force than PMMA (2-3kN). The results of this study suggest that the likelihood of screw fixation failure may be reduced by selecting calcium phosphate cements with lower porosity and higher compressive strength, in patients with healthy bone mineral density and/or sufficient cortical thickness. This is of particular clinical relevance when fixation with metal plates is indicated, or where the augmentation volume is limited. Copyright © 2017 Elsevier Ltd. All rights reserved.
Accumulation of Colloidal Particles in Flow Junctions Induced by Fluid Flow and Diffusiophoresis
DOE Office of Scientific and Technical Information (OSTI.GOV)
Shin, Sangwoo; Ault, Jesse T.; Warren, Patrick B.
The flow of solutions containing solutes and colloidal particles in porous media is widely found in systems including underground aquifers, hydraulic fractures, estuarine or coastal habitats, water filtration systems, etc. In such systems, solute gradients occur when there is a local change in the solute concentration. While the effects of solute gradients have been found to be important for many applications, we observe an unexpected colloidal behavior in porous media driven by the combination of solute gradients and the fluid flow. When two flows with different solute concentrations are in contact near a junction, a sharp solute gradient is formedmore » at the interface, which may allow strong diffusiophoresis of the particles directed against the flow. Consequently, the particles accumulate near the pore entrance, rapidly approaching the packing limit. These colloidal dynamics have important implications for the clogging of a porous medium, where particles that are orders of magnitude smaller than the pore width can accumulate and block the pores within a short period of time. As a result, we also show that this effect can be exploited as a useful tool for preconcentrating biomolecules for rapid bioassays.« less
Accumulation of Colloidal Particles in Flow Junctions Induced by Fluid Flow and Diffusiophoresis
Shin, Sangwoo; Ault, Jesse T.; Warren, Patrick B.; ...
2017-11-16
The flow of solutions containing solutes and colloidal particles in porous media is widely found in systems including underground aquifers, hydraulic fractures, estuarine or coastal habitats, water filtration systems, etc. In such systems, solute gradients occur when there is a local change in the solute concentration. While the effects of solute gradients have been found to be important for many applications, we observe an unexpected colloidal behavior in porous media driven by the combination of solute gradients and the fluid flow. When two flows with different solute concentrations are in contact near a junction, a sharp solute gradient is formedmore » at the interface, which may allow strong diffusiophoresis of the particles directed against the flow. Consequently, the particles accumulate near the pore entrance, rapidly approaching the packing limit. These colloidal dynamics have important implications for the clogging of a porous medium, where particles that are orders of magnitude smaller than the pore width can accumulate and block the pores within a short period of time. As a result, we also show that this effect can be exploited as a useful tool for preconcentrating biomolecules for rapid bioassays.« less
NASA Astrophysics Data System (ADS)
Zentmyer, R. A.; Pufahl, P. K.; James, N. P.; Hiatt, E. E.
2011-06-01
The Denault Formation (2.1-1.9 Ga) crops out in the Labrador Trough, northeastern Québec and western Labrador. Rocks surrounding the town of Schefferville, Quebec contain textural characteristics consistent with deposition on the middle and outer portions of a storm-influenced shallow ramp. Mid-ramp facies consist of intraclastic grainstones with hummocky cross-stratification (HCS), swaley cross-stratification (SCS), current ripples, and graded event beds. Further outboard, grainstones grade into deeper-water laminites that are composed of even, mm-scale couplets of flat-lying organic and dolomudstone laminae. Scours within the laminites suggest periodic storm activity. Laminites gradually grade into outer ramp deep-water shales. An isolated eastern stromatolitic buildup is separated from these ramp facies by 50 km (present day). This succession can be interpreted as the remnant of a near-continuous margin or may simply represent an isolated accumulation that developed on a pre-existing topographic high. The presence of gypsum pseudomorphs in all lithofacies indicates that the Denault margin was restricted and evaporitic. Four paragenetic stages are recognized in the diagenetic evolution of the Denault Formation: (1) carbonate deposition, contemporaneous marine cementation, authigenic gypsum growth, and precipitation of authigenic chert; (2) synsedimentary mimetic dolomite precipitation; (3) pore-rimming and pore-occluding shallow burial dolomite cement; and (4) fabric destructive, sutured, anhedral burial dolomite. Gypsum crystals occur in all lithofacies, form the nuclei of interstitial dolomite rhombs, average 10 μm in length, and often display swallowtail twinning. Paleoproterozoic ocean water had very low concentrations of dissolved sulfate and evaporation in restricted settings would have been required to form gypsum. Formation of microcrystalline gypsum across this restricted ramp facilitated dolomite precipitation by increasing pore water Mg/Ca ratios and lowering its dissolved sulfate concentrations. Such an interpretation may explain why there is an abundance of synsedimentary dolostone in the Precambrian and the relative paucity of Phanerozoic analogs.
Environmental controls for the precipitation of different fibrous calcite cement fabrics
NASA Astrophysics Data System (ADS)
Ritter, Ann-Christine; Wiethoff, Felix; Neuser, Rolf D.; Richter, Detlev K.; Immenhauser, Adrian
2016-04-01
Abiogenic calcite cements are widely used as climate archives. They can yield information on environmental change and climate dynamics at the time when the sediment was lithified in a (marine) diagenetic environment. Radiaxial-fibrous (RFC) and fascicular-optic fibrous (FOFC) calcite cements are two very common and similar pore-filling cement fabrics in Palaeozoic and Mesozoic carbonate rocks (Richter et al., 2011) and in Holocene Mg-calcitic speleothems (Richter et al., 2015). Both fabrics are characterised by distinct crystallographic properties. Current research has shown that these fabrics are often underexplored and that a careful combination of conservative and innovative proxies allows for a better applicability of these carbonate archives to paleoenvironmental reconstructions (Ritter et al., 2015). A main uncertainty in this context is that it is still poorly understood which parameters lead to the formation of either RFC or FOFC and if differential crystallographic parameters affect proxy data from these fabrics. This study aims at a better understanding of the environmental factors that may control either RFC or FOFC precipitation. Therefore, suitable samples (a stalagmite and a Triassic marine cement succession), each with clearly differentiable layers of RFC and FOFC, were identified and analysed in high detail using a multi-proxy approach. Detailed thin section and cathodoluminescence analysis of the samples allowed for a precise identification of layers consisting solely of either RFC or FOFC. Isotopic (δ13C, δ18O) as well as trace elemental compositions have been determined and the comparison of data obtained from these different carbonate archives sheds light on changes in environmental parameters during RFC or FOFC precipitation. References: Richter, D.K., et al., 2011. Radiaxial-fibrous calcites: A new look at an old problem. Sedimentary Geology, 239, 26-36 Richter, D.K., et al., 2015. Radiaxial-fibrous and fascicular-optic Mg-calcitic cave cements: a characterization usig electron backscattered diffraction (EBSD). International Journal of Speleology, 44, 91-98 Ritter, A.-C., et al., 2015. Application of redox sensitive proxies and carbonate clumped isotopes to Mesozoic and Palaeozoic radiaxial fibrous calcite cements. Chemical Geology, 417, 306-321
Consolidation of archaeological gypsum plaster by bacterial biomineralization of calcium carbonate.
Jroundi, Fadwa; Gonzalez-Muñoz, Maria Teresa; Garcia-Bueno, Ana; Rodriguez-Navarro, Carlos
2014-09-01
Gypsum plasterworks and decorative surfaces are easily degraded, especially when exposed to humidity, and thus they require protection and/or consolidation. However, the conservation of historical gypsum-based structural and decorative materials by conventional organic and inorganic consolidants shows limited efficacy. Here, a new method based on the bioconsolidation capacity of carbonatogenic bacteria inhabiting the material was assayed on historical gypsum plasters and compared with conventional consolidation treatments (ethyl silicate; methylacrylate-ethylmethacrylate copolymer and polyvinyl butyral). Conventional products do not reach in-depth consolidation, typically forming a thin impervious surface layer which blocks pores. In contrast, the bacterial treatment produces vaterite (CaCO3) biocement, which does not block pores and produces a good level of consolidation, both at the surface and in-depth, as shown by drilling resistance measurement system analyses. Transmission electron microscopy analyses show that bacterial vaterite cement formed via oriented aggregation of CaCO3 nanoparticles (∼20nm in size), resulting in mesocrystals which incorporate bacterial biopolymers. Such a biocomposite has superior mechanical properties, thus explaining the fact that drilling resistance of bioconsolidated gypsum plasters is within the range of inorganic calcite materials of equivalent porosity, despite the fact that the bacterial vaterite cement accounts for only a 0.02 solid volume fraction. Bacterial bioconsolidation is proposed for the effective consolidation of this type of material. The potential applications of bacterial calcium carbonate consolidation of gypsum biomaterials used as bone graft substitutes are discussed. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Qiao, Peng-yan; Li, Fang-fang; Dong, Li-min; Xu, Tao; Xie, Qiu-fei
2014-01-01
Objective: To deliver cells deep into injectable calcium phosphate cement (CPC) through alginate-chitosan (AC) microcapsules and investigate the biological behavior of the cells released from microcapsules into the CPC. Methods: Mouse osteoblastic MC3T3-E1 cells were embedded in alginate and AC microcapsules using an electrostatic droplet generator. The two types of cell-encapsulating microcapsules were then mixed with a CPC paste. MC3T3-E1 cell viability was investigated using a Wst-8 kit, and osteogenic differentiation was demonstrated by an alkaline phosphatase (ALP) activity assay. Cell attachment in CPC was observed by an environment scanning electron microscopy. Results: Both alginate and AC microcapsules were able to release the encapsulated MC3T3-E1 cells when mixed with CPC paste. The released cells attached to the setting CPC scaffolds, survived, differentiated, and formed mineralized nodules. Cells grew in the pores concomitantly created by the AC microcapsules in situ within the CPC. At Day 21, cellular ALP activity in the AC group was approximately four times that at Day 7 and exceeded that of the alginate microcapsule group (P<0.05). Pores formed by the AC microcapsules had a diameter of several hundred microns and were spherical compared with those formed by alginate microcapsules. Conclusions: AC microcapsule is a promising carrier to release seeding cells deep into an injectable CPC scaffold for bone engineering. PMID:24711359
Quantifying moisture transport in cementitious materials using neutron radiography
NASA Astrophysics Data System (ADS)
Lucero, Catherine L.
A portion of the concrete pavements in the US have recently been observed to have premature joint deterioration. This damage is caused in part by the ingress of fluids, like water, salt water, or deicing salts. The ingress of these fluids can damage concrete when they freeze and expand or can react with the cementitious matrix causing damage. To determine the quality of concrete for assessing potential service life it is often necessary to measure the rate of fluid ingress, or sorptivity. Neutron imaging is a powerful method for quantifying fluid penetration since it can describe where water has penetrated, how quickly it has penetrated and the volume of water in the concrete or mortar. Neutrons are sensitive to light atoms such as hydrogen and thus clearly detect water at high spatial and temporal resolution. It can be used to detect small changes in moisture content and is ideal for monitoring wetting and drying in mortar exposed to various fluids. This study aimed at developing a method to accurately estimate moisture content in mortar. The common practice is to image the material dry as a reference before exposing to fluid and normalizing subsequent images to the reference. The volume of water can then be computed using the Beer-Lambert law. This method can be limiting because it requires exact image alignment between the reference image and all subsequent images. A model of neutron attenuation in a multi-phase cementitious composite was developed to be used in cases where a reference image is not available. The attenuation coefficients for water, un-hydrated cement, and sand were directly calculated from the neutron images. The attenuation coefficient for the hydration products was then back-calculated. The model can estimate the degree of saturation in a mortar with known mixture proportions without using a reference image for calculation. Absorption in mortars exposed to various fluids (i.e., deionized water and calcium chloride solutions) were investigated. It has been found through this study that small pores, namely voids created by chemical shrinkage, gel pores, and capillary pores, ranging from 0.5 nm to 50 microm, fill quickly through capillary action. However, large entrapped and entrained air voids ranging from 0.05 to 1.25 mm remain empty during the initial filling process. In mortar exposed to calcium chloride solution, a decrease in sorptivity was observed due to an increase in viscosity and surface tension of the solution as proposed by Spragg et al 2011. This work however also noted a decrease in the rate of absorption due to a reaction between the salt and matrix which results in the filling of the pores in the concrete. The results from neutron imaging can help in the interpretation of standard absorption tests. ASTM C1585 test results can be further analyzed in several ways that could give an accurate indication of the durability of the concrete. Results can be reported in depth of penetration versus the square root of time rather than mm3 of fluid per mm2 of exposed surface area. Since a known fraction of pores are initially filling before reaching the edge of the sample, the actual depth of penetration can be calculated. This work is compared with an 'intrinsic sorptivity' that can be used to interpret mass measurements. Furthermore, the influence of shrinkage reducing admixtures (SRAs) on drying was studied. Neutron radiographs showed that systems saturated in water remain "wetter" than systems saturated in 5% SRA solution. The SRA in the system reduces the moisture diffusion coefficient due an increase in viscosity and decrease in surface tension. Neutron radiography provided spatial information of the drying front that cannot be achieved using other methods.
A multi-scale network method for two-phase flow in porous media
DOE Office of Scientific and Technical Information (OSTI.GOV)
Khayrat, Karim, E-mail: khayratk@ifd.mavt.ethz.ch; Jenny, Patrick
Pore-network models of porous media are useful in the study of pore-scale flow in porous media. In order to extract macroscopic properties from flow simulations in pore-networks, it is crucial the networks are large enough to be considered representative elementary volumes. However, existing two-phase network flow solvers are limited to relatively small domains. For this purpose, a multi-scale pore-network (MSPN) method, which takes into account flow-rate effects and can simulate larger domains compared to existing methods, was developed. In our solution algorithm, a large pore network is partitioned into several smaller sub-networks. The algorithm to advance the fluid interfaces withinmore » each subnetwork consists of three steps. First, a global pressure problem on the network is solved approximately using the multiscale finite volume (MSFV) method. Next, the fluxes across the subnetworks are computed. Lastly, using fluxes as boundary conditions, a dynamic two-phase flow solver is used to advance the solution in time. Simulation results of drainage scenarios at different capillary numbers and unfavourable viscosity ratios are presented and used to validate the MSPN method against solutions obtained by an existing dynamic network flow solver.« less
Pore fluid pressure and the seismic cycle
NASA Astrophysics Data System (ADS)
French, M. E.; Zhu, W.; Hirth, G.; Belzer, B.
2017-12-01
In the brittle crust, the critical shear stress required for fault slip decreases with increasing pore fluid pressures according to the effective stress criterion. As a result, higher pore fluid pressures are thought to promote fault slip and seismogenesis, consistent with observations that increasing fluid pressure as a result of wastewater injection is correlated with increased seismicity. On the other hand, elevated pore fluid pressure is also proposed to promote slow stable failure rather than seismicity along some fault zones, including during slow slip in subduction zones. Here we review recent experimental evidence for the roles that pore fluid pressure and the effective stress play in controlling fault slip behavior. Using two sets of experiments on serpentine fault gouge, we show that increasing fluid pressure does decrease the shear stress for reactivation under brittle conditions. However, under semi-brittle conditions as expected near the base of the seismogenic zone, high pore fluid pressures are much less effective at reducing the shear stress of reactivation even though deformation is localized and frictional. We use an additional study on serpentinite to show that cohesive fault rocks, potentially the product of healing and cementation, experience an increase in fracture energy during faulting as fluid pressures approach lithostatic, which can lead to more stable failure. Structural observations show that the increased fracture energy is associated with a greater intensity of transgranular fracturing and delocalization of deformation. Experiments on several lithologies indicate that the stabilizing effect of fluid pressure occurs independent of rock composition and hydraulic properties. Thus, high pore fluid pressures have the potential to either enhance seismicity or promote stable faulting depending on pressure, temperature, and fluid pressure conditions. Together, the results of these studies indicate that pore fluid pressure promotes seismogenesis in the brittle shallow crust where fluid pressures are elevated but sub-lithostatic and promote slow, stable failure near seismic to aseismic transitions and under near-lithostatic fluid pressures.
NASA Astrophysics Data System (ADS)
Leitner, Daniel; Bodner, Gernot; Raoof, Amir
2013-04-01
Understanding root-soil interactions is of high importance for environmental and agricultural management. Root uptake is an essential component in water and solute transport modeling. The amount of groundwater recharge and solute leaching significantly depends on the demand based plant extraction via its root system. Plant uptake however not only responds to the potential demand, but in most situations is limited by supply form the soil. The ability of the plant to access water and solutes in the soil is governed mainly by root distribution. Particularly under conditions of heterogeneous distribution of water and solutes in the soil, it is essential to capture the interaction between soil and roots. Root architecture models allow studying plant uptake from soil by describing growth and branching of root axes in the soil. Currently root architecture models are able to respond dynamically to water and nutrient distribution in the soil by directed growth (tropism), modified branching and enhanced exudation. The porous soil medium as rooting environment in these models is generally described by classical macroscopic water retention and sorption models, average over the pore scale. In our opinion this simplified description of the root growth medium implies several shortcomings for better understanding root-soil interactions: (i) It is well known that roots grow preferentially in preexisting pores, particularly in more rigid/dry soil. Thus the pore network contributes to the architectural form of the root system; (ii) roots themselves can influence the pore network by creating preferential flow paths (biopores) which are an essential element of structural porosity with strong impact on transport processes; (iii) plant uptake depend on both the spatial location of water/solutes in the pore network as well as the spatial distribution of roots. We therefore consider that for advancing our understanding in root-soil interactions, we need not only to extend our root models, but also improve the description of the rooting environment. Until now there have been no attempts to couple root architecture and pore network models. In our work we present a first attempt to join both types of models using the root architecture model of Leitner et al., (2010) and a pore network model presented by Raoof et al. (2010). The two main objectives of coupling both models are: (i) Representing the effect of root induced biopores on flow and transport processes: For this purpose a fixed root architecture created by the root model is superimposed as a secondary root induced pore network to the primary soil network, thus influencing the final pore topology in the network generation. (ii) Representing the influence of pre-existing pores on root branching: Using a given network of (rigid) pores, the root architecture model allocates its root axes into these preexisting pores as preferential growth paths with thereby shape the final root architecture. The main objective of our study is to reveal the potential of using a pore scale description of the plant growth medium for an improved representation of interaction processes at the interface of root and soil. References Raoof, A., Hassanizadeh, S.M. 2010. A New Method for Generating Pore-Network Models. Transp. Porous Med. 81, 391-407. Leitner, D, Klepsch, S., Bodner, G., Schnepf, S. 2010. A dynamic root system growth model based on L-Systems. Tropisms and coupling to nutrient uptake from soil. Plant Soil 332, 177-192.
Polymer nanocomposites for sealing microannulus cracks in wellbores cement-steel interface
NASA Astrophysics Data System (ADS)
Genedy, M.; Fernandez, S. G.; Stormont, J.; Matteo, E. N.; Dewers, T. A.; Reda Taha, M.
2017-12-01
Seal integrity of production and storage wellbores has become a critical challenge with the increasing oil and gas leakage incidents. The general consensus is that one of the potential leakage pathways is micro-annuli at the cement-steel interface. In this paper, we examine the efficiency of proposed polymer nanocomposite to seal microannulus cracks at the cement-steel interface. The repair material efficiency is defined as the ability of the repair material to reduce or eliminate the gas permeability of the cement-steel interface. The flow rate of an inert gas (Nitrogen) at the cement-steel interface was investigated for three cases: 1) repaired test samples with traditional repair material (microfine cement), 2) polymer nanocomposites, and 3) unrepaired test samples. Flow rates were measured and compared for all three cases. The experimental results show up to 99.5% seal efficiency achieved by using polymer nanocomposites compared to 20% efficiency achieved in the case of microfine cement. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA-0003525. SAND2017-8094 A.
Photoactive glazed polymer-cement composite
NASA Astrophysics Data System (ADS)
Baltes, Liana; Patachia, Silvia; Tierean, Mircea; Ekincioglu, Ozgur; Ozkul, Hulusi M.
2018-04-01
Macro defect free cements (MDF), a kind of polymer-cement composites, are characterized by remarkably high mechanical properties. Their flexural strengths are 20-30 times higher than those of conventional cement pastes, nearly equal to that of an ordinary steel. The main drawback of MDF cements is their sensitivity to water. This paper presents a method to both diminish the negative impact of water on MDF cements mechanical properties and to enlarge their application by conferring photoactivity. These tasks were solved by glazing MDF cement with an ecological glaze containing nano-particles of TiO2. Efficiency of photocatalytic activity of this material was tested against methylene blue aqueous solution (4.4 mg/L). Influence of the photocatalyst concentration in the glaze paste and of the contact time on the photocatalysis process (efficiency and kinetic) was studied. The best obtained photocatalysis yield was of 97.35%, after 8 h of exposure to 254 nm UV radiation when used an MDF glazed with 10% TiO2 in the enamel paste. Surface of glazed material was characterized by optic microscopy, scratch test, SEM, XRD, and EDS. All these properties were correlated with the aesthetic aspect of the glazed surface aiming to propose using of this material for sustainable construction development.
Sener, Isil; Turker, Begum; Valandro, Luiz Felipe; Ozcan, Mutlu
2014-01-01
This in vitro study evaluated the marginal gap, cement thickness, and microleakage of glass-ionomer cement (GIC) and phosphate monomer-containing resin cement (MDP-RC) under 2 zirconia crown systems (Cercon and DC-Zirkon). Forty human premolars were prepared for all-ceramic zirconia crowns with a 1 mm circumferential finish line and a 1.5 mm occlusal reduction. The crowns (n = 10 per group) from each zirconia system were randomly divided into 2 groups and cemented either with GIC (Vivaglass CEM) or MDP-RC (Panavia F 2.0) cement. The cemented crowns were thermocycled 5000 times (5°-55°C). The crowns were immersed in 0.5% basic fuchsine dye solution for 24 hours and sectioned buccolingually and mesiodistally. Specimens were examined under optical microscope (100X). Data were analyzed using Student t-test and chi-square tests (α = 0.05). Mean marginal gap values for Cercon (85 ± 11.4 μm) were significantly higher than for DC-Zircon (75.3 ± 13.2 μm) (P = 0.018). The mean cement thickness values of GIC (81.7 ± 13.9 μm) and MDP-RC (78.5 ± 12.5 μm) were not significantly different (P = 0.447). Microleakage scores did not demonstrate significant difference between GIC (P = 0.385) and MDP-RC (P = 0.631) under Cercon or DC-Zircon. Considering the cement thickness values and microleakage scores obtained, both zirconia crown systems could be cemented in combination with either GIC or MDP-RC.
NASA Astrophysics Data System (ADS)
Tittarelli, Francesca; Giosuè, Chiara; Mobili, Alessandra
2017-08-01
The use of stainless or galvanized steel reinforcements, a hydrophobic admixture or a flexible polymer-cement coating were compared as methods to improve the corrosion resistance of sound or cracked reinforced concrete specimens exposed to chloride rich solutions. The results show that in full immersion condition, negligible corrosion rates were detected in all cracked specimens, except those treated with the flexible polymer-cement mortar as preventive method against corrosion and the hydrophobic concrete specimens. High corrosion rates were measured in all cracked specimens exposed to wet-dry cycles, except for those reinforced with stainless steel, those treated with the flexible polymer-cement coating as restorative method against reinforcement corrosion and for hydrophobic concrete specimens reinforced with galvanized steel reinforcements.
NASA Astrophysics Data System (ADS)
Zhang, Chuan; Luo, Wenjun; Wen, Xin; Guan, Zhongjie; Zou, Zhigang
2017-11-01
P-type Cu(In,Ga)S2 semiconductors are promising candidates to be used as photocathodes for solar water splitting. Porous structures have been widely used to improve the performances of photoelectrodes due to good minority carrier transport. However, a porous photoelectrode has longer transport distance of majority carriers, which limits its performance. Controlling pore volume of a photoelectrode can balance minority and majority carrier transport and improve the performance. Here, a porous Cu(In,Ga)S2 film is prepared by facile spin-coating method. The pore volume of Cu(In,Ga)S2 film is controlled by adjusting relative humidity (RH) of air during spin-coating process. Further studies suggest that polyvinyl acetate (PVAc) in precursor solution is a humidity sensitive polymer and plays a key role to form different pore volume. The 40% RH sample has the best performance due to its optimum pore volume. After further coated with CdS surface passivation layer and Pt electrocatalyst on the surface, a 40% RH Cu(In,Ga)S2 photocathode indicates a photocurrent density of 8.6 mA cm-2 at 0 V RHE, which is one of the highest photocurrents of Cu(In,Ga)S2 photocathodes. This new strategy for adjusting pore volume is also suitable to prepare other solution-processed inorganic materials.
Gandolfi, Maria Giovanna; Ciapetti, Gabriela; Taddei, Paola; Perut, Francesca; Tinti, Anna; Cardoso, Marcio Vivan; Van Meerbeek, Bart; Prati, Carlo
2010-10-01
The effect of ageing in phosphate-containing solution of bioactive calcium-silicate cements on the chemistry, morphology and topography of the surface, as well as on in vitro human marrow stromal cells viability and proliferation was investigated. A calcium-silicate cement (wTC) mainly based on dicalcium-silicate and tricalcium-silicate was prepared. Alpha-TCP was added to wTC to obtain wTC-TCP. Bismuth oxide was inserted in wTC to prepare a radiopaque cement (wTC-Bi). A commercial calcium-silicate cement (ProRoot MTA) was tested as control. Cement disks were aged in DPBS for 5 h ('fresh samples'), 14 and 28 days, and analyzed by ESEM/EDX, SEM/EDX, ATR-FTIR, micro-Raman techniques and scanning white-light interferometry. Proliferation, LDH release, ALP activity and collagen production of human marrow stromal cells (MSC) seeded for 1-28 days on the cements were evaluated. Fresh samples exposed a surface mainly composed of calcium-silicate hydrates CSH (from the hydration of belite and alite), calcium hydroxide, calcium carbonate, and ettringite. Apatite nano-spherulites rapidly precipitated on cement surfaces within 5 h. On wTC-TCP the Ca-P deposits appeared thicker than on the other cements. Aged cements showed an irregular porous calcium-phosphate (Ca-P) coating, formed by aggregated apatite spherulites with interspersed calcite crystals. All the experimental cements exerted no acute toxicity in the cell assay system and allowed cell growth. Using biochemical results, the scores were: fresh cements>aged cements for cell proliferation and ALP activity (except for wTC-Bi), whereas fresh cements
Scaling and saturation laws for the expansion of concrete exposed to sulfate attack.
Monteiro, Paulo J M
2006-08-01
Reinforced concrete structures exposed to aggressive environments often require repair or retrofit even though they were designed to last >50 years. This statement is especially true for structures subjected to sulfate attack. It is critical that fundamental models of life prediction be developed for durability of concrete. Based on experimental results obtained over a 40-year period, scaling and saturation laws were formulated for concrete exposed to sulfate solution. These features have not been considered in current models used to predict life cycle of concrete exposed to aggressive environment. The mathematical analysis shows that porous concrete made with high and moderate water-to-cement ratios develops a definite scaling law after an initiation time. The scaling coefficient depends on the cement composition but does not depend on the original water-to-cement ratio. Dense concrete made with low water-to-cement ratios develops a cyclic saturation curve. An index for "potential of damage" is created to allow engineers to design concrete structures with better precision and cement chemists to develop portland cements with optimized composition.
2013-08-01
there are some data alluding to their ability to be used in implantable bone cement placed into wounds.27,28 In this study, we have shown that...2012;46:369 372. 27. Grimsrud C, Raven R, Fothergill AW, et al. The in vitro elution charac- teristics of antifungal-loaded PMMA bone cement and calcium
Arora, Sheen Juneja; Arora, Aman; Upadhyaya, Viram; Jain, Shilpi
2016-01-01
As, the longevity of provisional restorations is related to, a perfect adaptation and a strong, long-term union between restoration and teeth structures, therefore, evaluation of marginal leakage of provisional restorative materials luted with cements using the standardized procedures is essential. To compare the marginal leakage of the provisional crowns fabricated from Autopolymerizing acrylic resin crowns and bisphenol A-glycidyl dimethacrylate (BIS-GMA) resin crowns. To compare the marginal leakage of the provisional crowns fabricated from autopolymerizing acrylic resin crowns and BIS-GMA resin crowns cemented with different temporary luting cements. To compare the marginal leakage of the provisional crowns fabricated from autopolymerizing acrylic resin (SC-10) crowns cemented with different temporary luting cements. To compare the marginal leakage of the provisional crowns fabricated from BIS-GMA resin crowns (Protemp 4) cemented with different temporary luting cements. Freshly extracted 60 maxillary premolars of approximately similar dimensions were mounted in dental plaster. Tooth reduction with shoulder margin was planned to use a customized handpiece-holding jig. Provisional crowns were prepared using the wax pattern fabricated from computer aided designing/computer aided manufacturing milling machine following the tooth preparation. Sixty provisional crowns were made, thirty each of SC-10 and Protemp 4 and were then cemented with three different luting cements. Specimens were thermocycled, submerged in a 2% methylene blue solution, then sectioned and observed under a stereomicroscope for the evaluation of marginal microleakage. A five-level scale was used to score dye penetration in the tooth/cement interface and the results of this study was analyzed using the Chi-square test, Mann-Whitney U-test, Kruskal-Wallis H-test and the results were statistically significant P < 0.05 the power of study - 80%. Marginal leakage was significant in both provisional crowns cemented with three different luting cements along the axial walls of teeth (P < 0.05) confidence interval - 95%. The temporary cements with eugenol showed more microleakage than those without eugenol. SC-10 crowns showed more microleakage compared to Protemp 4 crowns. SC-10 crowns cemented with Kalzinol showed maximum microleakage and Protemp 4 crowns cemented with HY bond showed least microleakage.
NASA Astrophysics Data System (ADS)
Bijeljic, B.
2008-05-01
This talk will describe and highlight the advantages offered by a methodology that unifies pore network modeling, CTRW theory and experiment in description of solute dispersion in porous media. Solute transport in a porous medium is characterized by the interplay of advection and diffusion (described by Peclet number, Pe) that cause spreading of solute particles. This spreading is traditionally described by dispersion coefficients, D, defined by σ 2 = 2Dt, where σ 2 is the variance of the solute position and t is the time. Using a pore-scale network model based on particle tracking, the rich Peclet- number dependence of dispersion coefficient is predicted from first principles and is shown to compare well with experimental data for restricted diffusion, transition, power-law and mechanical dispersion regimes in the asymptotic limit. In the asymptotic limit D is constant and can be used in an averaged advection-dispersion equation. However, it is highly important to recognize that, until the velocity field is fully sampled, the particle transport is non-Gaussian and D possesses temporal or spatial variation. Furthermore, temporal probability density functions (PDF) of tracer particles are studied in pore networks and an excellent agreement for the spectrum of transition times for particles from pore to pore is obtained between network model results and CTRW theory. Based on the truncated power-law interpretation of PDF-s, the physical origin of the power-law scaling of dispersion coefficient vs. Peclet number has been explained for unconsolidated porous media, sands and a number of sandstones, arriving at the same conclusion from numerical network modelling, analytic CTRW theory and experiment. Future directions for further applications of the methodology presented are discussed in relation to the scale- dependent solute dispersion and reactive transport. Significance of pre-asymptotic dispersion in porous media is addressed from pore-scale upwards and the impact of heterogeneity is discussed. The length traveled by solute plumes before Gaussian behaviour is reached increases with an increase in heterogeneity and/or Pe. This opens up the question on the nature of dispersion in natural systems where the heterogeneities at the larger scales will profoundly increase the range of velocities in the aquifer, thus considerably delaying the asymptotic approach to Gaussian behaviour. As a consequence, the asymptotic behaviour might not be reached at the field scale.
Anisotropy of permeability of reservoir rocks over Miaoli area, NW Taiwan.
NASA Astrophysics Data System (ADS)
Bo-Siang, Xiong; Loung-Yie, Tsai
2013-04-01
The amount of the CO2 has risen since the Industrial Evolution. In order to reduce the amount of CO2 in atmosphere, CO2 sequestration is considered to be the most effective way. In recent years, research about subsurface storage of CO2 into geological formations has increased rapidly. Assessment of storage capability is needed before selecting a site for sequestration. Porosity and permeability are important assessment factors for CO2 sequestration in reservoir rocks. In order to improve the assessment, reservoir rock properties are important and need to be evaluated in advance. Porosity of sandstone is controlled by texture and degree of cementation, whereas permeability is controlled by pore-throat size, pore types and connectivity of pore throat. Sandstones of Miocene to Pleistocene in Miaoli area, NW Taiwan, were collected in this study. YOKO2 porosity/permeability detector is used to measure their permeability perpendicular and parallel to bedding planes under 3 to 60MPa confining pressure with Helium as media. Optical microscope and scanning electron microscope (SEM) were then used to observe the mineral composition, lithology, texture and pore type of sandstones, so as to explore the influence of rock properties on porosity and anisotropy of permeability, as well as the storage potential for CO2 sequestration in the future. The experimental results show that most of the horizontal permeability exceeds the vertical permeability and the anisotropy increases with increasing confining pressure. Mineral composition of sandstones studied were mainly quartz and lithic with little feldspar content. The pore types were mainly primary pores and micropores in this study. The correlation between quantity of macropores and permeability were higher than total porosity and permeability, mainly due to total porosity contains micropores which contribute little to permeability.
Li, Yin; Fu, Jie; Deng, Shuguang; Lu, Xiuyang
2014-06-15
Sixteen mesoporous carbon adsorbents were synthesized by varying the ratio of soft to hard templates in order to optimize the pore textural properties of these adsorbents. The mesoporous carbon adsorbents have a high BET specific surface area (1590.3-2193.5 m(2)/g), large pore volume (1.72-2.56 cm(3)/g), and uniform pore size distribution with a median pore diameter ranging from 3.51 nm to 4.52 nm. It was observed that pore textural properties of the carbon adsorbents critically depend on the molar ratio of carbon sources to templates, and the hard template plays a more important role than the soft template in manipulating the pore textures. Adsorption isotherms of berberine hydrochloride at 303 K were measured to evaluate the adsorption efficacy of these adsorbents. The adsorption of berberine hydrochloride from aqueous solutions on the sixteen mesoporous carbon adsorbents synthesized in this work is very efficient, and the adsorption equilibrium capacities on all samples are more than double the adsorption capacities of berberine hydrochloride of the benchmark adsorbents (polymer resins and spherical activated carbons) at similar conditions. It was observed from the adsorption experiments that the equilibrium adsorption amounts of berberine hydrochloride are strongly correlated with the BET specific surface area and pore volume of the adsorbents. The adsorbent with the highest BET of 2193.5 m(2)/g displayed the largest adsorption capacity of 574 mg/g at an equilibrium concentration of 0.10mg/mL of berberine hydrochloride in an aqueous solution. Copyright © 2014 Elsevier Inc. All rights reserved.
Pore-water chemistry explains zinc phytotoxicity in soil.
Kader, Mohammed; Lamb, Dane T; Correll, Ray; Megharaj, Mallavarapu; Naidu, Ravi
2015-12-01
Zinc (Zn) is a widespread soil contaminant arising from a numerous anthropogenic sources. However, adequately predicting toxicity of Zn to ecological receptors remains difficult due to the complexity of soil characteristics. In this study, we examined solid-solution partitioning using pore-water data and toxicity of Zn to cucumber (Cucumis sativus L.) in spiked soils. Pore-water effective concentration (ECx, x=10%, 20% and 50% reduction) values were negatively related to pH, indicating lower Zn pore water concentration were needed to cause phytotoxicity at high pH soils. Total dissolved zinc (Znpw) and free zinc (Zn(2+)) in soil-pore water successfully described 78% and 80.3% of the variation in relative growth (%) in the full dataset. When the complete data set was used (10 soils), the estimated EC50pw was 450 and 79.2 µM for Znpw and Zn(2+), respectively. Total added Zn, soil pore water pH (pHpw) and dissolve organic carbon (DOC) were the best predictors of Znpw and Zn(2+) in pore-water. The EC10 (total loading) values ranged from 179 to 5214 mg/kg, depending on soil type. Only pH measurements in soil were related to ECx total Zn data. The strongest relationship to ECx overall was pHca, although pHw and pHpw were in general related to Zn ECx. Similarly, when a solution-only model was used to predict Zn in shoot, DOC was negatively related to Zn in shoot, indicating a reduction in uptake/ translocation of Zn from solution with increasing DOC. Copyright © 2015 Elsevier Inc. All rights reserved.
Rajasekharan, Sivaprakash; Vercruysse, Chris; Martens, Luc; Verbeeck, Ronald
2018-01-13
Tricalcium silicate cements (TSC) are used in dental traumatology and endodontics for their bioactivity which is mostly attributed to formation of calcium hydroxide during TSC hydration and its subsequent release of calcium and hydroxide ions. The aim of this study was to determine the effect of volume (Vol), exposed surface area (ESA) and pH of surrounding medium on calcium ion release. Three commercially available hydraulic alkaline dental cements were mixed and condensed into cylindrical tubes of varying length and diameter ( n = 6/group). For the effect of ESA and Vol, tubes were immersed in 10 mL of deionized water. To analyze the effect of environmental pH, the tubes were randomly immersed in 10 mL of buffer solutions with varying pH (10.4, 7.4 or 4.4). The solutions were collected and renewed at various time intervals. pH and/or calcium ion release was measured using a pH glass electrode and atomic absorption spectrophotometer respectively. The change of pH, short-term calcium ion release and rate at which calcium ion release reaches maximum were dependent on ESA ( p < 0.05) while maximum calcium ion release was dependent on Vol of TSC ( p < 0.05). Maximum calcium ion release was significantly higher in acidic solution followed by neutral and alkaline solution ( p < 0.05).
Rajasekharan, Sivaprakash; Vercruysse, Chris; Martens, Luc; Verbeeck, Ronald
2018-01-01
Tricalcium silicate cements (TSC) are used in dental traumatology and endodontics for their bioactivity which is mostly attributed to formation of calcium hydroxide during TSC hydration and its subsequent release of calcium and hydroxide ions. The aim of this study was to determine the effect of volume (Vol), exposed surface area (ESA) and pH of surrounding medium on calcium ion release. Three commercially available hydraulic alkaline dental cements were mixed and condensed into cylindrical tubes of varying length and diameter (n = 6/group). For the effect of ESA and Vol, tubes were immersed in 10 mL of deionized water. To analyze the effect of environmental pH, the tubes were randomly immersed in 10 mL of buffer solutions with varying pH (10.4, 7.4 or 4.4). The solutions were collected and renewed at various time intervals. pH and/or calcium ion release was measured using a pH glass electrode and atomic absorption spectrophotometer respectively. The change of pH, short-term calcium ion release and rate at which calcium ion release reaches maximum were dependent on ESA (p < 0.05) while maximum calcium ion release was dependent on Vol of TSC (p < 0.05). Maximum calcium ion release was significantly higher in acidic solution followed by neutral and alkaline solution (p < 0.05). PMID:29342837
Dessì, M; Alvarez-Perez, M A; De Santis, R; Ginebra, M P; Planell, J A; Ambrosio, L
2014-02-01
An alternative approach to bone repair for less invasive surgical techniques, involves the development of biomaterials directly injectable into the injury sites and able to replicate a spatially organized platform with features of bone tissue. Here, the preparation and characterization of an innovative injectable bone analogue made of calcium deficient hydroxyapatite and foamed gelatin is presented. The biopolymer features and the cement self-setting reaction were investigated by rheological analysis. The porous architecture, the evolution of surface morphology and the grains dimension were analyzed with electron microscopy (SEM/ESEM/TEM). The physico-chemical properties were characterized by X-ray diffraction and FTIR analysis. Moreover, an injection test was carried out to prove the positive effect of gelatin on the flow ensuing that cement is fully injectable. The cement mechanical properties are adequate to function as temporary substrate for bone tissue regeneration. Furthermore, MG63 cells and bone marrow-derived human mesenchymal stem cells (hMSCs) were able to migrate and proliferate inside the pores, and hMSCs differentiated to the osteoblastic phenotype. The results are paving the way for an injectable bone substitute with properties that mimic natural bone tissue allowing the successful use as bone filler for craniofacial and orthopedic reconstructions in regenerative medicine.
Hydration Characteristics of Low-Heat Cement Substituted by Fly Ash and Limestone Powder.
Kim, Si-Jun; Yang, Keun-Hyeok; Moon, Gyu-Don
2015-09-01
This study proposed a new binder as an alternative to conventional cement to reduce the heat of hydration in mass concrete elements. As a main cementitious material, low-heat cement (LHC) was considered, and then fly ash (FA), modified FA (MFA) by vibrator mill, and limestone powder (LP) were used as a partial replacement of LHC. The addition of FA delayed the induction period at the hydration heat curve and the maximum heat flow value ( q max ) increased compared with the LHC based binder. As the proportion and fineness of the FA increased, the induction period of the hydration heat curve was extended, and the q max increased. The hydration production of Ca(OH)₂ was independent of the addition of FA or MFA up to an age of 7 days, beyond which the amount of Ca(OH)₂ gradually decreased owing to their pozzolanic reaction. In the case of LP being used as a supplementary cementitious material, the induction period of the hydration heat curve was reduced by comparison with the case of LHC based binder, and monocarboaluminate was observed as a hydration product. The average pore size measured at an age of 28 days was smaller for LHC with FA or MFA than for 100% LHC.