ASR/DEF-damaged bent caps : shear tests and field implications.

DOT National Transportation Integrated Search

2009-08-01

Over the last decade, a number of reinforced concrete bent caps within Houston, Texas have exhibited premature concrete damage (cracking, spalling and a loss of material : strength) due to alkali-silica reaction (ASR) and/or delayed ettringite format...

Anchor Bolt Behavior in ASR/DEF-Damaged Drilled Shafts.

DOT National Transportation Integrated Search

2007-02-01

The primary objective of this research is to evaluate the effect of Alkali-Silica Reaction (ASR) and Delayed Ettringite Formation (DEF) on the structural performance of High Mast Illumination Pole (HMIP) foundations and if needed, to recommend a poss...

Structural assessment of "d" regions affected by premature concrete deterioration : technical report.

DOT National Transportation Integrated Search

2015-03-01

The current study is a continuation of the earlier study that investigated the effects of Alkali Silica Reaction (ASR) and Delayed : Ettringite Formation (DEF) induced deterioration on the D-Regions of structures. Of the four near full-scale C-Beam s...

Sulfate resistance of high calcium fly ash concrete

NASA Astrophysics Data System (ADS)

Dhole, Rajaram

-fly ash pastes confirmed that fly ash mortar or concrete mixes forming more monosulfate than ettringite before exposure to sulfates would offer poor sulfate resistance and vice versa. During quantitative Rietveld analysis carried out for determining ettringite, monosulfate and gypsum formed in the fly ash pastes, it was observed that fly ash mixtures showing more ettringite after exposures to sulfates, give poor sulfate resistance. A good relationship between the amounts of ettringite formed and expansions of mortar specimens in the ASTM C 1012 test was found.

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

Immobilization of MSWI fly ash through geopolymerization: effects of water-wash.

PubMed

Zheng, Lei; Wang, Chengwen; Wang, Wei; Shi, Yunchun; Gao, Xingbao

2011-02-01

The present research explored the role played by water-wash on geopolymerization for the immobilization and solidification of municipal solid waste incineration (MSWI) fly ash. The water-wash pretreatment substantially promoted the early strength of geopolymer and resulted in a higher ultimate strength compared to the counterpart without water-wash. XRD pattern of water-washed fly ash (WFA) revealed that NaCl and KCl were nearly eliminated in the WFA. Aside from geopolymer, ettringite (Ca(6)Al(2)(SO(4))(3)(OH)(12)·26H(2)O) was formed in MSWI fly ash-based geopolymer (Geo-FA). Meanwhile, calcium aluminate hydrate (Ca(2)Al(OH)(7)·3H(2)O), not ettringite, appeared in geopolymer that was synthesized with water-washed fly ash (Geo-WFA). Leached Geo-WFA (Geo-WFA-L) did not exhibit any signs of deterioration, while there was visual cracking on the surface of leached Geo-FA (Geo-FA-L). The crack may be caused by the migration of K(+), Na(+), and Cl(-) ions outside Geo-FA and the negative effect from crystallization of expansive compounds can not be excluded. Furthermore, transformation of calcium aluminate hydrate in Geo-WFA to ettringite in Geo-WFA-L allowed the reduction of the pore size of the specimen. IR spectrums suggested that Geo-WFA can supply more stable chemical encapsulation for heavy metals. Static monolithic leaching tests were conducted for geopolymers to estimate the immobilization efficiency. Heavy metal leaching was elucidated using the first-order reaction/diffusion model. Combined with the results from compressive strength and microstructure of samples, the effects of water-wash on immobilization were inferred in this study. Copyright © 2010 Elsevier Ltd. All rights reserved.

A thermodynamic and experimental study of the conditions of thaumasite formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schmidt, Thomas; Lothenbach, Barbara; Romer, Michael

2008-03-15

The formation of thaumasite was investigated with the progressive equilibrium approach (PEA). This approach experimentally simulates the conditions of various levels of sulfate addition in hardened cement pastes. The influence of limestone, time, C{sub 3}A content, temperature and leaching on thaumasite formation was investigated. The results show that thaumasite formation is favoured at lower temperatures (8 deg. C) independently of the type of cement clinker (high or low C{sub 3}A content) used. Thaumasite was found to form only in systems where limestone was present and where sufficient sulfate had been added. Thaumasite precipitated only in systems where the Al presentmore » has already been consumed to form ettringite and the molar SO{sub 3}/Al{sub 2}O{sub 3} ratio exceeded 3. In leached samples (reduction of portlandite and alkalis) slightly less thaumasite was formed whereas gypsum and ettringite are favoured under these conditions. The PEA, used to investigate the chemical aspects of sulfate attack was found to be a good tool for simulating external sulfate attack. Generally, thaumasite was detected were it was modelled to be stable in significant amounts. However, in this study equilibrium conditions were not reached after 9 months.« less

Portland cement hydration and early setting of cement stone intended for efficient paving materials

NASA Astrophysics Data System (ADS)

Grishina, A.

2017-10-01

Due to the growth of load on automotive roads, modern transportation engineering is in need of efficient paving materials. Runways and most advanced highways require Portland cement concretes. This makes important the studies directed to improvement of binders for such concretes. In the present work some peculiarities of the process of Portland cement hydration and early setting of cement stone with barium hydrosilicate sol were examined. It was found that the admixture of said sol leads to a shift in the induction period to later times without significant change in its duration. The admixture of a modifier with nanoscale barium hydrosilicates increases the degree of hydration of the cement clinker minerals and changes the phase composition of the hydration products; in particular, the content of portlandite and tricalcium silicate decreases, while the amount of ettringite increases. Changes in the hydration processes of Portland cement and early setting of cement stone that are caused by the nanoscale barium hydrosilicates, allow to forecast positive technological effects both at the stage of manufacturing and at the stage of operation. In particular, the formwork age can be reduced, turnover of molds can be increased, formation of secondary ettringite and corrosion of the first type can be eliminated.

Expansive Cements

DTIC Science & Technology

1970-10-01

plastic or semi- plastic concrete and place no stress on the restraint provided. If, on the other hand, the ettringite continues to form rapidly for too...yield, I and wp.ter-cement ratio. Such a change in cement content may cause a greater change in expansion caracteristics than the change in...the tendency toward plastic shrinkage is increased. During the w’nter znths most structural concrete installations hare had adequate heating and no

Influence of Titanium Dioxide Nanoparticles on the Sulfate Attack upon Ordinary Portland Cement and Slag-Blended Mortars

PubMed Central

Atta-ur-Rehman; Qudoos, Abdul; Kim, Hong Gi

2018-01-01

In this study, the effects of titanium dioxide (TiO2) nanoparticles on the sulfate attack resistance of ordinary Portland cement (OPC) and slag-blended mortars were investigated. OPC and slag-blended mortars (OPC:Slag = 50:50) were made with water to binder ratio of 0.4 and a binder to sand ratio of 1:3. TiO2 was added as an admixture as 0%, 3%, 6%, 9% and 12% of the binder weight. Mortar specimens were exposed to an accelerated sulfate attack environment. Expansion, changes in mass and surface microhardness were measured. Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), X-ray Diffraction (XRD), Thermogravimetry Analysis (TGA) and Differential Scanning Calorimetry (DSC) tests were conducted. The formation of ettringite and gypsum crystals after the sulfate attack were detected. Both these products had caused crystallization pressure in the microstructure of mortars and deteriorated the mortars. Our results show that the addition of nano-TiO2 accelerated expansion, variation in mass, loss of surface microhardness and widened cracks in OPC and slag-blended mortars. Nano-TiO2 containing slag-blended mortars were more resistant to sulfate attack than nano-TiO2 containing OPC mortars. Because nano-TiO2 reduced the size of coarse pores, so it increased crystallization pressure due to the formation of ettringite and gypsum thus led to more damage under sulfate attack. PMID:29495616

Reactive transport modelling of a high-pH infiltration test in concrete

NASA Astrophysics Data System (ADS)

Chaparro, M. Carme; Soler, Josep M.; Saaltink, Maarten W.; Mäder, Urs K.

2017-06-01

A laboratory-scale tracer test was carried out to characterize the transport properties of concrete from the Radioactive Waste Disposal Facility at El Cabril (Spain). A hyperalkaline solution (K-Ca-OH, pH = 13.2) was injected into a concrete sample under a high entry pressure in order to perform the experiment within a reasonable time span, obtaining a decrease of permeability by a factor of 1000. The concentrations of the tracers, major elements (Ca2+, SO4 2 - , K+ and Na+) and pH were measured at the outlet of the concrete sample. A reactive transport model was built based on a double porosity conceptual model, which considers diffusion between a mobile zone, where water can flow, and an immobile zone without any advective transport. The numerical model assumed that all reactions took place in the immobile zone. The cement paste consists of C-S-H gel, portlandite, ettringite, calcite and gypsum, together with residual alite and belite. Two different models were compared, one with portlandite in equilibrium (high initial surface area) and another one with portlandite reaction controlled by kinetics (low initial surface area). Overall the results show dissolution of alite, belite, gypsum, quartz, C-S-H gel and ettringite and precipitation of portlandite and calcite. Permeability could have decreased due to mineral precipitation.

Physio-chemical reactions in recycle aggregate concrete.

PubMed

Tam, Vivian W Y; Gao, X F; Tam, C M; Ng, K M

2009-04-30

Concrete waste constitutes the major proportion of construction waste at about 50% of the total waste generated. An effective way to reduce concrete waste is to reuse it as recycled aggregate (RA) for the production of recycled aggregate concrete (RAC). This paper studies the physio-chemical reactions of cement paste around aggregate for normal aggregate concrete (NAC) and RAC mixed with normal mixing approach (NMA) and two-stage mixing approach (TSMA) by differential scanning calorimetry (DSC) and scanning electron microscopy (SEM). Four kinds of physio-chemical reactions have been recorded from the concrete samples, including the dehydration of C(3)S(2)H(3), iron-substituted ettringite, dehydroxylation of CH and development of C(6)S(3)H at about 90 degrees C, 135 degrees C, 441 degrees C and 570 degrees C, respectively. From the DSC results, it is confirmed that the concrete samples with RA substitution have generated less amount of strength enhancement chemical products when compared to those without RA substitution. However, the results from the TSMA are found improving the RAC quality. The pre-mix procedure of the TSMA can effectively develop some strength enhancing chemical products including, C(3)S(2)H(3), ettringite, CH and C(6)S(3)H, which shows that RAC made from the TSMA can improve the hydration processes.

Identification of Candidate Zero Maintenance Paving Materials. Volume 1

DTIC Science & Technology

1977-05-01

an anhydrous calcium sulfoaluminate as a way to control ettringite-formarion reactions and patented it as an invention on 18 October 1961. Another... Sulfoaluminates of Calcium as Stable and Meta- stable Phases and Study of Portion of the Five-Component System CaO-SO 3 -Al0 3-Na20-H 2O at 25C. Ph. D...Berkeley, Jun 1972. 242. , "Effect of Lime on Hydration of Pastes Containing Gypsum and Calcium Aluminates or Calcium Sulfoaluminate ," Journal, American

Effect of blast furnace slag on self-healing of microcracks in cementitious materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Haoliang, E-mail: haoliang.huang@tudelft.nl; Ye, Guang; Magnel Laboratory for Concrete Research, Department of Structural Engineering, Ghent University

The physico-chemical process of self-healing in blast furnace slag cement paste was investigated in this paper. With a high slag content i.e., 66% in cement paste and saturated Ca(OH)₂ solution as activator, it was found that the reaction products formed in cracks are composed of C-S-H, ettringite, hydrogarnet and OH–hydrotalcite. The fraction of C-S-H in the reaction products is much larger than the other minerals. Large amount of ettringite formed in cracks indicates the leaching of SO₄⁻² ions from the bulk paste and consequently the recrystallization. Self-healing proceeds fast within 50 h and then slows down. According to thermodynamic modeling,more » when the newly formed reaction products are carbonated, the filling fraction of crack increases first and then decreases. Low soluble minerals such as silica gel, gibbsite and calcite are formed. Compared to Portland cement paste, the potential of self-healing in slag cement paste is higher when the percentage of slag is high. Highlights: • Self-healing reaction products in slag cement paste were characterized. • Self-healing reaction products formed in time were quantified with image analysis. • Self-healing in slag cement paste was simulated with a reactive transport model. • Effect of carbonation on self-healing was investigated by thermodynamic modeling. • Effect of slag on self-healing was discussed based on experiments and simulation.« less

In-situ early-age hydration study of sulfobelite cements by synchrotron powder diffraction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Álvarez-Pinazo, G.; Cuesta, A.; García-Maté, M.

Eco-friendly belite calcium sulfoaluminate (BCSA) cement hydration behavior is not yet well understood. Here, we report an in-situ synchrotron X-ray powder diffraction study for the first hours of hydration of BCSA cements. Rietveld quantitative phase analysis has been used to establish the degree of reaction (α). The hydration of a mixture of ye'elimite and gypsum revealed that ettringite formation (α ∼ 70% at 50 h) is limited by ye'elimite dissolution. Two laboratory-prepared BCSA cements were also studied: non-active-BCSA and active-BCSA cements, with β- and α′{sub H}-belite as main phases, respectively. Ye'elimite, in the non-active-BCSA system, dissolves at higher pace (αmore » ∼ 25% at 1 h) than in the active-BCSA one (α ∼ 10% at 1 h), with differences in the crystallization of ettringite (α ∼ 30% and α ∼ 5%, respectively). This behavior has strongly affected subsequent belite and ferrite reactivities, yielding stratlingite and other layered phases in non-active-BCSA. The dissolution and crystallization processes are reported and discussed in detail. -- Highlights: •Belite calcium sulfoaluminate cements early hydration mechanism has been determined. •Belite hydration strongly depends on availability of aluminum hydroxide. •Orthorhombic ye’elimite dissolved at a higher pace than cubic one. •Ye’elimite larger reaction degree yields stratlingite formation by belite reaction. •Rietveld method quantified gypsum, anhydrite and bassanite dissolution rates.« less

Use of hydraulic binders for reducing sulphate leaching: application to gypsiferous soil sampled in Ile-de-France region (France).

PubMed

Trincal, Vincent; Thiéry, Vincent; Mamindy-Pajany, Yannick; Hillier, Stephen

2018-06-01

Polluted soils are a serious environmental risk worldwide and consist of millions of tons of mineral waste to be treated. In order to ensure their sustainable management, various remediation options must be considered. Hydraulic binder treatment is one option that may allow a stabilisation of pollution and thus offer a valorisation as secondary raw materials rather than considering them as waste. In this study, we focused on sulphate-polluted soil and tested the effectiveness of several experimental hydraulic binders. The aim was to transform gypsum into ettringite, a much less soluble sulphate, and therefore to restrict the potential for sulphate pollutant release. The environmental assessment of five formulations using hydraulic binders was compared to the gypsiferous soil before treatment (contaminated in sulphate). The approach was to combine leaching tests with mineralogical quantifications using among others thermogravimetric and XRD methods. In the original soil and in the five formulations, leaching tests indicate sulphate release above environmental standards. However, hydraulic binders promote ettringite formation, as well as a gypsum content reduction as observed by SEM. The stabilisation of sulphates is, however, insufficient, probably as a result of the very high content of gypsum in the unusual soil used. The mineralogical reactions highlighted during the hydration of hydraulic binders are promising; they could pave the way for the development of new industrial mixtures that would have a positive environmental impact by allowing reuse of soils that would otherwise be classified as waste.

Composition, diagenetic transformation and alkalinity potential of oil shale ash sediments.

PubMed

Mõtlep, Riho; Sild, Terje; Puura, Erik; Kirsimäe, Kalle

2010-12-15

Oil shale is a primary fuel in the Estonian energy sector. After combustion 45-48% of the oil shale is left over as ash, producing about 5-7 Mt of ash, which is deposited on ash plateaus annually almost without any reuse. This study focuses on oil shale ash plateau sediment mineralogy, its hydration and diagenetic transformations, a study that has not been addressed. Oil shale ash wastes are considered as the biggest pollution sources in Estonia and thus determining the composition and properties of oil shale ash sediment are important to assess its environmental implications and also its possible reusability. A study of fresh ash and drillcore samples from ash plateau sediment was conducted by X-ray diffractometry and scanning electron microscopy. The oil shale is highly calcareous, and the ash that remains after combustion is derived from the decomposition of carbonate minerals. It is rich in lime and anhydrite that are unstable phases under hydrous conditions. These processes and the diagenetic alteration of other phases determine the composition of the plateau sediment. Dominant phases in the ash are hydration and associated transformation products: calcite, ettringite, portlandite and hydrocalumite. The prevailing mineral phases (portlandite, ettringite) cause highly alkaline leachates, pH 12-13. Neutralization of these leachates under natural conditions, by rainwater leaching/neutralization and slow transformation (e.g. carbonation) of the aforementioned unstable phases into more stable forms, takes, at best, hundreds or even hundreds of thousands of years. Copyright © 2010 Elsevier B.V. All rights reserved.

Evaluation of concrete structures affected by alkali-silica reaction and delayed ettringite formation - part 2.

DOT National Transportation Integrated Search

2012-12-01

This report details the results of a comprehensive research project aimed at evaluating the potential use of : non-destructive testing (NDT) to assess structures affected by ASR and/or DEF. This project was a : collaborative effort between the Univer...

Impact of natural and calcined starfish (Asterina pectinifera) on the stabilization of Pb, Zn and As in contaminated agricultural soil.

PubMed

Lim, Jung Eun; Sung, Jwa Kyung; Sarkar, Binoy; Wang, Hailong; Hashimoto, Yohey; Tsang, Daniel C W; Ok, Yong Sik

2017-04-01

Metal stabilization using soil amendments is an extensively applied, economically viable and environmentally friendly remediation technique. The stabilization of Pb, Zn and As in contaminated soils was evaluated using natural starfish (NSF) and calcined starfish (CSF) wastes at different application rates (0, 2.5, 5.0 and 10.0 wt%). An incubation study was conducted over 14 months, and the efficiency of stabilization for Pb, Zn and As in soil was evaluated by the toxicity characteristic leaching procedure (TCLP) test. The TCLP-extractable Pb was reduced by 76.3-100 and 91.2-100 % in soil treated with NSF and CSF, respectively. The TCLP-extractable Zn was also reduced by 89.8-100 and 93.2-100 % in soil treated with NSF and CSF, respectively. These reductions could be associated with the increased metal adsorption and the formation of insoluble metal precipitates due to increased soil pH following application of the amendments. However, the TCLP-extractable As was increased in the soil treated with NSF, possibly due to the competitive adsorption of phosphorous. In contrast, the TCLP-extractable As in the 10 % CSF treatment was not detectable because insoluble Ca-As compounds might be formed at high pH values. Thermodynamic modeling by visual MINTEQ predicted the formation of ettringite (Ca 6 Al 2 (SO 4 ) 3 (OH) 12 ·26H 2 O) and portlandite (Ca(OH) 2 ) in the 10 % CSF-treated soil, while SEM-EDS analysis confirmed the needle-like structure of ettringite in which Pb was incorporated and stabilized in the 10 % CSF treatment.

Réactivité du laitier de hauts fourneaux d'Annaba (Algérie) en substitution partielle du ciment

NASA Astrophysics Data System (ADS)

Behim, M.; Redjel, B.; Jauberthie, R.

2002-07-01

Iron industry provides blast-furnace slag production as waste. Blast-furnace slag are made of non ironic elements, flux and coke ash. These elements might have binding properties such as cement. Usually, only blastfurnace slag chemical composition is considered to evaluate its quality as a binder. Other properties such as crystal phases amount, grading, specific area or temperature are not considered Some studies have shown that binding properties exist when the blast-furnace slag is quenched and crushed in very fine grains, and that an increase of the temperature has a benefit aspect on the kinetic of the reaction. We have used X ray diffraction, SEM observations with micro analysis on different samples of blast-furnace slag that undergone different cure modes. At low temperature, only non complete crystal phases appear. At room temperature, calcium sulphate and hydrated aluminium sulphate (ettringite) exist such as for Portland cement while setting. Under a steam curing mode, there is very few lime in the blast-furnace slag because lime has reacted with silicate, therefore there is much more CSH in the binder. No ettringite can be detected, on the other hand, the steam curing mode produce formation of hydrated calcium aluminate. Les laitiers de haut fourneau sont des sous produit de l'élaboration de la fonte. lis sont formés de constituants non ferreux, des fondants et des cendres de coke. Leur composition chimique laisse présager des propriétés liantes comme celles que l'on obtient avec les ciments. Les qualités hydrauliques de ces matériaux sont actuellement estimées par des calculs basés sur leur composition chimique. Elles ne tiennent pas compte d'autres paramètres tels que le caractère vitreux ou cristallin, la granulométrie ou la surface spécifique, la température entre autres. Les propriétés liantes apparaissent lorsque le laitier est trempé et broyé très finement, la température augmentant la cinétique. Les produits formés analys

Characterization of basin concrete in support of structural integrity demonstration for extended storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Duncan, A.

Concrete core samples from C basin were characterized through material testing and analysis to verify the design inputs for structural analysis of the L Basin and to evaluate the type and extent of changes in the material condition of the concrete under extended service for fuel storage. To avoid the impact on operations, core samples were not collected from L area, but rather, several concrete core samples were taken from the C Basin prior to its closure. C basin was selected due to its similar environmental exposure and service history compared to L Basin. The microstructure and chemical composition ofmore » the concrete exposed to the water was profiled from the water surface into the wall to evaluate the impact and extent of exposure. No significant leaching of concrete components was observed. Ingress of carbonation or deleterious species was determined to be insignificant. No evidence of alkali-silica reactions (ASR) was observed. Ettringite was observed to form throughout the structure (in air voids or pores); however, the sulfur content was measured to be consistent with the initial concrete that was used to construct the facility. Similar ettringite trends were observed in the interior segments of the core samples. The compressive strength of the concrete at the mid-wall of the basin was measured, and similar microstructural analysis was conducted on these materials post compression testing. The microstructure was determined to be similar to near-surface segments of the core samples. The average strength was 4148 psi, which is well-above the design strength of 2500 psi. The analyses showed that phase alterations and minor cracking in a microstructure did not affect the design specification for the concrete.« less

Stabilization of chromium-bearing electroplating sludge with MSWI fly ash-based Friedel matrices.

PubMed

Qian, Guangren; Yang, Xiaoyan; Dong, Shixiang; Zhou, Jizhi; Sun, Ying; Xu, Yunfeng; Liu, Qiang

2009-06-15

This work investigated the feasibility and effectiveness of MSWI fly ash-based Friedel matrices on stabilizing/solidifying industrial chromium-bearing electroplating sludge using MSWI fly ash as the main raw material with a small addition of active aluminum. The compressive strength, leaching behavior and chemical speciation of heavy metals and hydration phases of matrices were characterized by TCLP, XRD, FTIR and other experimental methods. The results revealed that MSWI fly ash-based Friedel matrices could effectively stabilize chromium-bearing electroplating sludge, the formed ettringite and Friedel phases played a significant role in the fixation of heavy metals in electroplating sludge. The co-disposal of chromium-bearing electroplating sludge and MSWI fly ash-based Friedel matrices with a small addition of active aluminum is promising to be an effective way of stabilizing chromium-bearing electroplating sludge.

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

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

Hashemite, Ba(Cr,S)O4, a new mineral from Jordan.

USGS Publications Warehouse

Hauff, P.L.; Foord, E.E.; Rosenblum, S.

1983-01-01

Hashemite, Ba(Cr,S)O4, the isostructural chromate analogue of baryte, has been found in west-central Jordan. It is associated with chromian ettringite, apatite and calcite in a phosphatic carbonate rock analogous to the Hatrurim formation in Israel. The mineral is orthorhombic, Pnma, with a 9.112(2), b 5.541(1), c 7.343(1) A, Z = 4. Strongest XRD lines are 3.516(100), 3.171(80), 3.669(60), 2.175(60), 2.150(45) A. Hashemite occurs as small, euhedral, dark brown, commonly zoned crystals with an average D 4.59 g/cm3 and H. 31/2. It is biaxial positive; dark varieties have alpha 1.952(2), beta 1.960(2), gamma 1.977(2); light varieties have alpha 1.810(2), beta 1.813(2), gamma 1.824(2), 2Vgamma 35o-57o.-J.A.Z.

Porous media modeling and micro-structurally motivated material moduli determination via the micro-dilatation theory

NASA Astrophysics Data System (ADS)

Jeong, J.; Ramézani, H.; Sardini, P.; Kondo, D.; Ponson, L.; Siitari-Kauppi, M.

2015-07-01

In the present contribution, the porous material modeling and micro-structural material parameters determination are scrutinized via the micro-dilatation theory. The main goal is to take advantage of the micro-dilatation theory which belongs to the generalized continuum media. In the first stage, the thermodynamic laws are entirely revised to reach the energy balance relation using three variables, deformation, porosity change and its gradient underlying the porous media as described in the micro-dilatation theory or so-called void elasticity. Two experiments over cement mortar specimens are performed in order to highlight the material parameters related to the pore structure. The shrinkage due to CO2 carbonation, porosity and its gradient are calculated. The extracted values are verified via 14C-PMMA radiographic image method. The modeling of swelling phenomenon of Delayed Ettringite Formation (DEF) is studied later on. This issue is performed via the crystallization pressure application using the micro-dilatation theory.

Concrete alteration due to 55 years of exposure to river water: Chemical and mineralogical characterisation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rosenqvist, Martin; Bertron, Alexandra; Fridh, Katja

This article presents a study on concrete alteration mechanisms due to 55 years of exposure to river water. Many hydro power structures in cold regions suffer from concrete deterioration at the waterline. Progressive disintegration of the concrete surface leads to exposure of the coarse aggregate and eventually the reinforcing steel. Concrete cylinders drilled out at four vertically different locations on the upstream face of a concrete dam were analysed by electron microprobe analysis, X-ray diffraction, thermogravimetry and scanning electron microscopy. Long-term exposure to the river water, which is regarded as soft water, has led to chemical and mineralogical zonation ofmore » the cement paste. Up to five zones with different chemical and mineralogical composition, parallel to the upstream face, were observed in the outermost 8–9 mm of the concrete. Decalcification, precipitation of secondary ettringite and the formation of a magnesium-rich silica gel constitute the major changes that define the zones.« less

Surface treated polypropylene (PP) fibres for reinforced concrete

DOE Office of Scientific and Technical Information (OSTI.GOV)

López-Buendía, Angel M., E-mail: buendia@uv.es; Romero-Sánchez, María Dolores; Climent, Verónica

Surface treatments on a polypropylene (PP) fibre have contributed to the improvement of fibre/concrete adhesion in fibre-reinforced concrete. The treatments to the PP fibre were characterized by contact angle measurements, ATR-IR and XPS to analyse chemical alterations. The surface topography and fibre/concrete interaction were analysed by several microscopic techniques, namely optical petrographic, and scanning electron microscopy. Treatment modified the surface chemistry and topography of the fibre by introducing sodium moieties and created additional fibre surface roughness. Modifications in the fibre surface led to an increase in the adhesion properties between the treated fibres and concrete and an improvement in themore » mechanical properties of the fibre-reinforced concrete composite as compared to the concrete containing untreated PP fibres. Compatibility with the concrete and increased roughness and mineral surface was also improved by nucleated portlandite and ettringite mineral association anchored on the alkaline PP fibre surface, which is induced during treatment.« less

Calcium sulfoaluminate (Ye'elimite) hydration in the presence of gypsum, calcite, and vaterite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hargis, Craig W.; Telesca, Antonio; Monteiro, Paulo J.M., E-mail: monteiro@ce.berkeley.edu

Six calcium sulfoaluminate-based cementitious systems composed of calcium sulfoaluminate, calcite, vaterite, and gypsum were cured as pastes and mortars for 1, 7, 28 and 84 days. Pastes were analyzed with X-ray diffraction, thermogravimetric and differential thermal analyses. Mortars were tested for compressive strength, dimensional stability and setting time. Furthermore, pastes with a water/cementitious material mass ratio of 0.80 were tested for heat evolution during the first 48 h by means of isothermal conduction calorimetry. It has been found that: (1) both calcite and vaterite reacted with monosulfoaluminate to give monocarboaluminate and ettringite, with vaterite being more reactive; (2) gypsum loweredmore » the reactivity of both carbonates; (3) expansion was reduced by calcite and vaterite, irrespective of the presence of gypsum; and (4) both carbonates increased compressive strength in the absence of gypsum and decreased compressive strength less in the presence of gypsum, with vaterite's action more effective than that of calcite.« less

Advances in understanding hydration of Portland cement

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scrivener, Karen L., E-mail: Karen.scrivener@epfl.ch; Juilland, Patrick; Monteiro, Paulo J.M.

2015-12-15

Progress in understanding hydration is summarized. Evidence supports the geochemistry dissolution theory as an explanation for the induction period, in preference to the inhibiting layer theory. The growth of C–S–H is the principal factor controlling the main heat evolution peak. Electron microscopy indicates that C–S–H “needles” grow from the surface of grains. At the peak, the surface is covered, but deceleration cannot be attributed to diffusion control. The shoulder peak comes from renewed reaction of C{sub 3}A after depletion of sulfate in solution, but release of sulfate absorbed on C–S–H means that ettringite continues to form. After several days spacemore » becomes the major factor controlling hydration. The use of new analytical technique is improving our knowledge of the action of superplasticizers and leading to the design of molecules for different applications. Atomistic modeling is becoming a topic of increasing interest. Recent publications in this area are reviewed.« less

Chemical characteristics and leachability of organically contaminated heavy metal sludge solidified by silica fume and cement.

PubMed

Jun, K S; Hwang, B G; Shin, H S; Won, Y S

2001-01-01

This paper discusses the development of mixtures with silica fume as a stabilization/solidification agent and binder for industrial wastewater residue containing organic and heavy metal contaminants. The UCS (Unconfined Compressive Strength) gradually increased to 66.7% as the silica fume content increased to 15%. The leaching of TOC and chromium decreased as more OPC was substituted with silica fume. When the mix had 5% silica fume, it retained about 85% TOC, and chromium leached out 0.76 mg-Cr/g-Cr in acidic solution. Also, microstructural studies on the solidified wastes through the scanning electron microscopy/energy dispersive spectroscopy (SEM/EDS) and X-ray diffraction analysis showed that the silica fume caused an inhibition to the ettringite formation which did not contribute to setting, but coated the cement particles and retarded the setting reactions. The results indicated that the incorporation of silica fume into the cement matrix minimized the detrimental effects of organic materials on the cement hydration reaction and contaminant leachability.

Experimental study on microstructure characters of foamed lightweight soil

NASA Astrophysics Data System (ADS)

Qiu, Youqiang; Li, Yongliang; Li, Meixia; Liu, Yaofu; Zhang, Liujun

2018-01-01

In order to verify the microstructure of foamed lightweight soil and its characters of compressive strength, four foamed lightweight soil samples with different water-soild ratio were selected and the microstructure characters of these samples were scanned by electron microscope. At the same time, the characters of compressive strength of foamed lightweight soil were analyzed from the microstructure. The study results show that the water-soild ratio has a prominent effect on the microstructure and compressive strength of foamed lightweight soil, with the decrease of water-solid ratio, the amount and the perforation of pores would be reduced significantly, thus eventually forming a denser and fuller interior structure. Besides, the denser microstructure and solider pore-pore wall is benefit to greatly increase mechanical intensity of foamed lightweight soil. In addition, there are very few acicular ettringite crystals in the interior of foamed lightweight soil, its number is also reduced with the decrease in water-soild ratio.

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

Self-cementitious properties of fly ashes from CFBC boilers co-firing coal and high-sulphur petroleum coke

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sheng Guanghong; Li Qin; Zhai Jianping

2007-06-15

Self-cementitious properties of fly ash from circulating fluidized bed combustion boiler co-firing coal and high-sulphur petroleum coke (CPFA) were investigated. CPFA was self-cementitious which was affected by its fineness and chemical compositions, especially the contents of SO{sub 3} and free lime (f-CaO). Higher contents of SO{sub 3} and f-CaO were beneficial to self-cementitious strength; the self-cementitious strength increases with a decrease of its 45 {mu}m sieve residue. The expansive ratio of CPFA hardened paste was high because of generation of ettringite (AFt), which was influenced by its water to binder ratio (W/A), curing style and grinding of the ash. Themore » paste cured in water had the highest expansive ratio, and grinding of CPFA was beneficial to its volume stability. The hydration products of CPFA detected by X-ray diffraction (XRD) and scanning electron microscopy (SEM) were portlandite, gypsum, AFt and hydrated calcium silicate (C-S-H)« less

Hydration mechanisms of two polymorphs of synthetic ye'elimite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cuesta, A.; Álvarez-Pinazo, G.; Sanfélix, S.G.

2014-09-15

Ye'elimite is the main phase in calcium sulfoaluminate cements and also a key phase in sulfobelite cements. However, its hydration mechanism is not well understood. Here we reported new data on the hydration behavior of ye'elimite using synchrotron and laboratory powder diffraction coupled to the Rietveld methodology. Both internal and external standard methodologies have been used to determine the overall amorphous contents. We have addressed the standard variables: water-to-ye'elimite ratio and additional sulfate sources of different solubilities. Moreover, we report a deep study of the role of the polymorphism of pure ye'elimites. The hydration behavior of orthorhombic stoichiometric and pseudo-cubicmore » solid-solution ye'elimites is discussed. In the absence of additional sulfate sources, stoichiometric-ye'elimite reacts slower than solid-solution-ye'elimite, and AFm-type phases are the main hydrated crystalline phases, as expected. Moreover, solid-solution-ye'elimite produces higher amounts of ettringite than stoichiometric-ye'elimite. However, in the presence of additional sulfates, stoichiometric-ye'elimite reacts faster than solid-solution-ye'elimite.« less

Crystalline phases involved in the hydration of calcium silicate-based cements: Semi-quantitative Rietveld X-ray diffraction analysis.

PubMed

Grazziotin-Soares, Renata; Nekoofar, Mohammad H; Davies, Thomas; Hübler, Roberto; Meraji, Naghmeh; Dummer, Paul M H

2017-08-30

Chemical comparisons of powder and hydrated forms of calcium silicate cements (CSCs) and calculation of alterations in tricalcium silicate (Ca 3 SiO 5 ) calcium hydroxide (Ca(OH) 2 ) are essential for understanding their hydration processes. This study aimed to evaluate and compare these changes in ProRoot MTA, Biodentine and CEM cement. Powder and hydrated forms of tooth coloured ProRoot MTA, Biodentine and CEM cement were subjected to X-ray diffraction (XRD) analysis with Rietveld refinement to semi-quantitatively identify and quantify the main phases involved in their hydration process. Data were reported descriptively. Reduction in Ca 3 SiO 5 and formation of Ca(OH) 2 were seen after the hydration of ProRoot MTA and Biodentine; however, in the case of CEM cement, no reduction of Ca 3 SiO 5 and no formation of Ca(OH) 2 were detected. The highest percentages of amorphous phases were seen in Biodentine samples. Ettringite was detected in the hydrated forms of ProRoot MTA and CEM cement but not in Biodentine. © 2017 Australian Society of Endodontology Inc.

Modeling the long-term durability of concrete barriers in the context of low-activity waste storage

NASA Astrophysics Data System (ADS)

Protière, Y.; Samson, E.; Henocq, P.

2013-07-01

The paper investigates the long-term durability of concrete barriers in contact with a cementitious wasteform designed to immobilize low-activity nuclear waste. The high-pH pore solution of the wasteform contains high concentration level of sulfate, nitrate, nitrite and alkalis. The multilayer concrete/wasteform system was modeled using a multiionic reactive transport model accounting for coupling between species, dissolution/ precipitation reactions, and feedback effect. One of the primary objectives was to investigate the risk associated with the presence of sulfate in the wasteform on the durability of concrete. Simulation results showed that formation of expansive phases, such as gypsum and ettringite, into the concrete barrier was not extensive. Based on those results, it was not possible to conclude that concrete would be severely damaged, even after 5,000 years. Lab work was performed to provide data to validate the modeling results. Paste samples were immersed in sulfate contact solutions and analyzed to measure the impact of the aggressive environment on the material. The results obtained so far tend to confirm the numerical simulations.

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

Identification of concrete deteriorating minerals by polarizing and scanning electron microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gregerova, Miroslava, E-mail: mirka@sci.muni.cz; Vsiansky, Dalibor, E-mail: daliborv@centrum.cz

2009-07-15

The deterioration of concrete represents one of the most serious problems of civil engineering worldwide. Besides other processes, deterioration of concrete consists of sulfate attack and carbonation. Sulfate attack results in the formation of gypsum, ettringite and thaumasite in hardened concrete. Products of sulfate attack may cause a loss of material strength and a risk of collapse of the concrete constructions. The authors focused especially on the microscopical research of sulfate attack. Concrete samples were taken from the Charles Bridge in Prague, Czech Republic. A succession of degrading mineral formation was suggested. Microscope methods represent a new approach to solvingmore » the deterioration problems. They enable evaluation of the state of concrete constructions and in cooperation with hydro-geochemistry, mathematics and statistics permit prediction of the durability of a structure. Considering the number of concrete constructions and their age, research of concrete deterioration has an increasing importance. The results obtained can also be useful for future construction, because they identify the risk factors associated with formation of minerals known to degrade structures.« less

Aggregate-cement paste transition zone properties affecting the salt-frost damage of high-performance concretes

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.

Preparation and performance of arsenate (V) adsorbents derived from concrete wastes.

PubMed

Sasaki, Takeshi; Iizuka, Atsushi; Watanabe, Masayuki; Hongo, Teruhisa; Yamasaki, Akihiro

2014-10-01

Solid adsorbent materials, prepared from waste cement powder and concrete sludge were assessed for removal of arsenic in the form of arsenic (As(V)) from water. All the materials exhibited arsenic removal capacity when added to distilled water containing 10-700 mg/L arsenic. The arsenic removal isotherms were expressed by the Langmuir type equations, and the highest removal capacity was observed for the adsorbent prepared from concrete sludge with heat treatment at 105°C, the maximum removal capacity being 175 mg-As(V)/g. Based on changes in arsenic and calcium ion concentrations, and solution pH, the removal mechanism for arsenic was considered to involve the precipitation of calcium arsenate, Ca3(AsO4)2. The enhanced removal of arsenic for the adsorbent prepared from concrete sludge with heat treatment was thought to reflect ion exchange by ettringite. The prepared adsorbents, derived from waste cement and concrete using simple procedures, may offer a cost effective approach for arsenic removal and clean-up of contaminated waters, especially in developing countries. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effects of the restoration mortar on chalk stone buildings

NASA Astrophysics Data System (ADS)

Ion, R. M.; Teodorescu, S.; Ştirbescu, R. M.; Dulamă, I. D.; Şuică-Bunghez, I. R.; Bucurică, I. A.; Fierăscu, R. C.; Fierscu, I.; Ion, M. L.

2016-06-01

The monument buildings as components of cultural heritage are exposed to degradation of surfaces and chemical and mechanical degradation, often associated to soiling and irreversible deterioration of the building. In many conservative and restorative works, a cement-based mortar was used without knowing all the adverse effects of this material on the building. This paper deals with the study of the effects of natural cement used in restorative works in the particular case of the Basarabi-Murfatlar Churches Ensemble. Cement-based materials exposed to sulfate present in the chalk stone - gypsum (CaSO4.2H2O), can induce signs of deterioration, due to ettringite ([Ca3Al (OH)612H2O]2(SO4)32H2O) or thaumasite (Ca3[Si(OH)612H2O](CO3)SO4) formation. These phases contribute to strain within the material, inducing expansion, strength loss, spalling and severe degradation. Several combined techniques (XRD, EDXRF, ICP-AES, SEM, EDS, sulphates content, FT-IR and Raman analysis were carried out to put into evidence the effects of them on the building walls.

Resistance of class C fly ash belite cement to simulated sodium sulphate radioactive liquid waste attack.

PubMed

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.

Immobilization and Natural Attenuation of Arsenic in Surface and Subsurface Sediments

NASA Astrophysics Data System (ADS)

O'Day, P. A.; Illera, V.; Choi, S.; Vlassopoulos, D.

2008-12-01

Understanding of molecular-scale biogeochemical processes that control the mobilization and distribution of As and other oxyanions can be used to develop remediation strategies that take advantage of natural geochemical and hydrologic gradients. Arsenic and other toxic oxyanions can be mobilized at low bulk sediment concentrations (ppm range) and thus, treatment technologies are challenged by low contaminant concentrations, widespread sources, variable pH and Eh conditions, and inaccessibility of subsurface environments. In situ chemical amendments to soils and sediments can be used to decrease the mobility and bioaccessibility of As and oxyanions through sorption to, or precipitation with, stabilizing phases. At a site near San Francisco Bay (CA, USA), treatment of As-contaminated soils with sulfate-cement amendments has effectively immobilized As. Laboratory experiments with field soils and spectroscopic characterizations showed that in high pH cement-type treatments, As is precipitated in ettringite-type phases (Ca-Al sulfates), whereas in low pH ferrous sulfate treatments, As is associated with an iron-arsenate phase (angellelite). The presence of As-associated ettringite-type phases in field sediments amended more than a decade ago indicates long-term stability of these neophases, as long as environmental conditions are relatively constant. At sites of subsurface contamination, monitored natural attenuation (MNA) as a remediation approach for As is gaining interest and acceptance. Successful implementation of MNA requires a mechanistic understanding of As sequestration processes and of the subsurface conditions that may enhance or reduce long-term effectiveness. At a former military site (MA, USA), naturally occurring As was mobilized from sediments as a result of reducing conditions from addition of organic carbon as a biodegradation treatment of chlorinated solvents. Elevated As concentrations were not detected further than about 30 m downgradient of the

The Effects of Air-Cooled Blast Furnace Slag (ACBFS) Aggregate on the Chemistry of Pore Solution and the Interfacial Transition Zone

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

The hydrothermal decomposition of calcium monosulfoaluminate 14-hydrate to katoite hydrogarnet and β-anhydrite: An in-situ synchrotron X-ray diffraction study

NASA Astrophysics Data System (ADS)

Meller, Nicola; Kyritsis, Konstantinos; Hall, Christopher

2009-10-01

We apply in-situ synchrotron X-ray diffraction to study the transformation of calcium monosulfoaluminate 14-hydrate Ca 4Al 2O 6(SO 4)·14H 2O [monosulfate-14] to hydrogarnet Ca 3Al 2(OH) 12 on the saturated water vapor pressure curve up to 250 °C. We use an aqueous slurry of synthetic ettringite Ca 6Al 2(SO 4) 3(OH) 12·26H 2O as the starting material; on heating, this decomposes at about 115 °C to form monosulfate-14 and bassanite CaSO 4·0.5H 2O. Above 170 °C monosulfate-14 diffraction peaks slowly diminish in intensity, perhaps as a result of loss of crystallinity and the formation of an X-ray amorphous meta-monosulfate. Hydrogarnet nucleates only at temperatures above 210 °C. Bassanite transforms to β-anhydrite (insoluble anhydrite) at about 230 °C and this transformation is accompanied by a second burst of hydrogarnet growth. The transformation pathway is more complex than previously thought. The mapping of the transformation pathway shows the value of rapid in-situ time-resolved synchrotron diffraction.

Acid attack on hydrated cement — Effect of mineral acids on the degradation process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gutberlet, T.; Hilbig, H.; Beddoe, R.E., E-mail: robin.beddoe@tum.de

During acid attack on concrete structural components, a degraded layer develops whose properties as a protective barrier are decisive for durability. {sup 29}Si NMR spectroscopy and {sup 27}Al NMR spectroscopy were used with XRD to investigate the degraded layer on hardened cement paste exposed to HCl and H{sub 2}SO{sub 4}. The layer comprises an amorphous silica gel with framework silicates, geminate and single silanol groups in which Si is substituted by Al. Amorphous Al(OH){sub 3} and Fe(OH){sub 3} are present. The gel forms by polycondensation and cross-linking of C-A-S-H chains at AlO{sub 4} bridging tetrahedra. In the transition zone betweenmore » the degraded layer and the undamaged material, portlandite dissolves and Ca is removed from the C-A-S-H phases maintaining their polymer structure at first. With HCl, monosulphate in the transition zone is converted into Friedel's salt and ettringite. With H{sub 2}SO{sub 4}, gypsum precipitates near the degradation front reducing the thickness of the transition zone and the rate of degradation.« less

Decrease of non-point zinc runoff using porous concrete.

PubMed

Harada, Shigeki; Komuro, Yoshinori

2010-01-01

The use of porous concrete columns to decrease the amount of zinc in stormwater runoff is examined. The concentration of zinc in a simulated stormwater fluid (zinc acetate solution), fed through concrete columns (slashed circle10x10cm) decreased by 50-81%, suggesting physical adsorption of zinc by the porous concrete. We propose the use of porous concrete columns (slashed circle50x10cm) as the base of sewage traps. Longer-term, high-zinc concentration monitoring revealed that porous concrete blocks adsorb 38.6mgcm(-3) of zinc. A period of no significant zinc runoff (with an acceptable concentration of zinc in runoff of 0.03mgL(-1), a zinc concentration equal to the Japanese Environmental Standard) is estimated for 41years using a 1-ha catchment area with 20 porous concrete sewage traps. Scanning electron microscopy of the porous concrete used in this study indicates that the needle-like particles formed by hydration action significantly increase zinc adsorption. Evidence suggests that the hydrant is ettringite and has an important role in zinc adsorption, the resulting immobilization of zinc and the subsequent effects on groundwater quality. Copyright 2009 Elsevier Ltd. All rights reserved.

Phase Changes of Monosulfoaluminate in NaCl Aqueous Solution

DOE PAGES

Yoon, Seyoon; Ha, Juyoung; Chae, Sejung Rosie; ...

2016-05-21

Monosulfoaluminate (Ca 4Al 2(SO 4)(OH) 12∙6H 2O) plays an important role in anion binding in Portland cement by exchanging its original interlayer ions (SO 4 2- and OH -) with chloride ions. In this study, scanning transmission X-ray microscope (STXM), X-ray absorption near edge structure (XANES) spectroscopy, and X-ray diffraction (XRD) were used to investigate the phase change of monosulfoaluminate due to its interaction with chloride ions. Pure monosulfoaluminate was synthesized and its powder samples were suspended in 0, 0.1, 1, 3, and 5 M NaCl solutions for seven days. At low chloride concentrations, a partial dissolution of monosulfoaluminate formedmore » ettringite, while, with increasing chloride content, the dissolution process was suppressed. As the NaCl concentration increased, the dominant mechanism of the phase change became ion exchange, resulting in direct phase transformation from monosulfoaluminate to Kuzel’s salt or Friedel’s salt. The phase assemblages of the NaCl-reacted samples were explored using thermodynamic calculations and least-square linear combination (LC) fitting of measured XANES spectra. A comprehensive description of the phase change and its dominant mechanism are discussed.« less

A parallel reaction-transport model applied to cement hydration and microstructure development

NASA Astrophysics Data System (ADS)

Bullard, Jeffrey W.; Enjolras, Edith; George, William L.; Satterfield, Steven G.; Terrill, Judith E.

2010-03-01

A recently described stochastic reaction-transport model on three-dimensional lattices is parallelized and is used to simulate the time-dependent structural and chemical evolution in multicomponent reactive systems. The model, called HydratiCA, uses probabilistic rules to simulate the kinetics of diffusion, homogeneous reactions and heterogeneous phenomena such as solid nucleation, growth and dissolution in complex three-dimensional systems. The algorithms require information only from each lattice site and its immediate neighbors, and this localization enables the parallelized model to exhibit near-linear scaling up to several hundred processors. Although applicable to a wide range of material systems, including sedimentary rock beds, reacting colloids and biochemical systems, validation is performed here on two minerals that are commonly found in Portland cement paste, calcium hydroxide and ettringite, by comparing their simulated dissolution or precipitation rates far from equilibrium to standard rate equations, and also by comparing simulated equilibrium states to thermodynamic calculations, as a function of temperature and pH. Finally, we demonstrate how HydratiCA can be used to investigate microstructure characteristics, such as spatial correlations between different condensed phases, in more complex microstructures.

Mechanism and preparation of liquid alkali-free liquid setting accelerator for shotcrete

NASA Astrophysics Data System (ADS)

Qiu, Ying; Ding, Bei; Gan, Jiezhong; Guo, Zhaolai; Zheng, Chunyang; Jiang, Haidong

2017-03-01

A new alkali-free liquid accelerator for shotcrete was prepared through normal temperature drop process by using the nano activated alumina and the modified alcohol amine as the main raw materials. The effect of alkali-free liquid accelerator on the cement setting time and the mechanical properties of mortar, the effect of the penetration strength on the shotcrete rebound were investigated. And the accelerating mechanism of the as-prepared alkali-free liquid accelerator was also analyzed via XRD and SEM characterization methods. The experimental results indicated that the hydration of C3A was accelerated by the polyamine complexation of accelerator, resulting in forming a large number of acicular ettringite and reducing the amount of Ca(OH)2 crystal, which would not affect the later hydration of cement. When the content of alkali-free liquid accelerator was 6%, the initial setting time and final setting time were less than 3min and 8min respectively, and 1d and 28d compressive strength ratios reached 207.6% and 114.2% respectively; beside that, the shotcrete rebound was very low because of the high penetration strength within 30min.

Stabilization of Pb²⁺ and Cu²⁺ contaminated firing range soil using calcined oyster shells and waste cow bones.

PubMed

Moon, Deok Hyun; Cheong, Kyung Hoon; Khim, Jeehyeong; Wazne, Mahmoud; Hyun, Seunghun; Park, Jeong-Hun; Chang, Yoon-Young; Ok, Yong Sik

2013-05-01

Pb(2+) and Cu(2+) contamination at army firing ranges poses serious environmental and health risks to nearby communities necessitating an immediate and prompt remedial action. In this study, a novel mixture of calcined oyster shells (COSs) and waste cow bones (WCBs) was utilized to immobilize Pb(2+) and Cu(2+) in army firing range soils. The effectiveness of the treatment was evaluated based on the Korean Standard leaching test. The treatment results showed that Pb(2+) and Cu(2+) immobilization in the army firing range soil was effective in significantly reducing Pb(2+) and Cu(2+) leachability upon the combined treatment with COS and WCB. A drastic reduction in Pb(2+) (99%) and Cu(2+) leachability (95%) was obtained as compared to the control sample, upon treatment with 5 wt.% COS and 5 wt.% WCB. The combination treatment of COS and WCB was more effective for Pb immobilization, than the treatment with COS or WCB alone. The 5 wt.% COS alone treatment resulted in 95% reduction in Cu(2+) leachability. The SEM-EDX results suggested that Pb(2+) and Cu(2+) immobilization was most probably associated with the formation of ettringite, pozzolanic reaction products and pyromorphite-like phases at the same time. Copyright © 2013 Elsevier Ltd. All rights reserved.

Production of Synthetic Phosphoanhydrite and Its Use as a Binder in Self-Leveling Underlayments (SLU).

PubMed

Schaefer, Cecília Ogliari; Cheriaf, Malik; Rocha, Janaíde Cavalcante

2017-08-17

An experimental study was conducted to investigate the potential use of phosphogypsum (PG) to produce self-leveling underlayments. The study was designed in two stages. Initially a phosphoanhydrite (PA) was produced by heating phosphogypsum at temperatures of 350 °C, 450 °C, 550 °C, and 650 °C. Two periods of heating were applied (2 and 4 h). The formation of anhydrite was determined by thermogravimetric analysis (DTA-TG) and confirmed by X-ray diffraction (XRD). The results show that anhydrite II was obtained at temperatures above 450 °C, and at higher calcination temperatures the PA solubility was lower. In the second stage of this research, the PA was used in self-leveling underlayments as the main binder in the ternary system comprised of calcium sulfate, calcium aluminate cement, and Portland cement. Self-leveling mortar screeds produced using PA (550 °C/4 h) and PA (650 °C/4 h) showed the best performance in terms of mechanical strength and no degradation was observed after immersion and immersion-drying tests. The formation of ettringite, identified by scanning electron microscopy (SEM), may have contributed to these results. Morphological changes were studied using the scanning electron microscopy (SEM) technique.

Production of Synthetic Phosphoanhydrite and Its Use as a Binder in Self-Leveling Underlayments (SLU)

PubMed Central

Schaefer, Cecília Ogliari; Cheriaf, Malik

2017-01-01

An experimental study was conducted to investigate the potential use of phosphogypsum (PG) to produce self-leveling underlayments. The study was designed in two stages. Initially a phosphoanhydrite (PA) was produced by heating phosphogypsum at temperatures of 350 °C, 450 °C, 550 °C, and 650 °C. Two periods of heating were applied (2 and 4 h). The formation of anhydrite was determined by thermogravimetric analysis (DTA-TG) and confirmed by X-ray diffraction (XRD). The results show that anhydrite II was obtained at temperatures above 450 °C, and at higher calcination temperatures the PA solubility was lower. In the second stage of this research, the PA was used in self-leveling underlayments as the main binder in the ternary system comprised of calcium sulfate, calcium aluminate cement, and Portland cement. Self-leveling mortar screeds produced using PA (550 °C/4 h) and PA (650 °C/4 h) showed the best performance in terms of mechanical strength and no degradation was observed after immersion and immersion-drying tests. The formation of ettringite, identified by scanning electron microscopy (SEM), may have contributed to these results. Morphological changes were studied using the scanning electron microscopy (SEM) technique. PMID:28817091

Alkali-activated complex binders from class C fly ash and Ca-containing admixtures.

PubMed

Guo, Xiaolu; Shi, Huisheng; Chen, Liming; Dick, Warren A

2010-01-15

Processes that maximize utilization of industrial solid wastes are greatly needed. Sodium hydroxide and sodium silicate solution were used to create alkali-activated complex binders (AACBs) from class C fly ash (CFA) and other Ca-containing admixtures including Portland cement (PC), flue gas desulfurization gypsum (FGDG), and water treatment residual (WTR). Specimens made only from CFA (CFA100), or the same fly ash mixed with 40 wt% PC (CFA60-PC40), with 10 wt% FGDG (CFA90-FGDG10), or with 10 wt% WTR (CFA90-WTR10) had better mechanical performance compared to binders using other mix ratios. The maximum compressive strength of specimens reached 80.0 MPa. Geopolymeric gel, sodium polysilicate zeolite, and hydrated products coexist when AACB reactions occur. Ca from CFA, PC, and WTR precipitated as Ca(OH)(2), bonded in geopolymers to obtain charge balance, or reacted with dissolved silicate and aluminate species to form calcium silicate hydrate (C-S-H) gel. However, Ca from FGDG probably reacted with dissolved silicate and aluminate species to form ettringite. Utilization of CFA and Ca-containing admixtures in AACB is feasible. These binders may be widely utilized in various applications such as in building materials and for solidification/stabilization of other wastes, thus making the wastes more environmentally benign.

Influences of specific ions in groundwater on concrete degradation in subsurface engineered barrier system.

PubMed

Lin, Wen-Sheng; Liu, Chen-Wuing; Li, Ming-Hsu

2016-01-01

Many disposal concepts currently show that concrete is an effective confinement material used in engineered barrier systems (EBS) at a number of low-level radioactive waste (LLW) disposal sites. Cement-based materials have properties for the encapsulation, isolation, or retardation of a variety of hazardous contaminants. The reactive chemical transport model of HYDROGEOCHEM 5.0 was applied to simulate the effect of hydrogeochemical processes on concrete barrier degradation in an EBS which has been proposed to use in the LLW disposal site in Taiwan. The simulated results indicated that the main processes that are responsible for concrete degradation are the species induced from hydrogen ion, sulfate, and chloride. The EBS with the side ditch drainage system effectively discharges the infiltrated water and lowers the solute concentrations that may induce concrete degradation. The redox processes markedly influence the formations of the degradation materials. The reductive environment in the EBS reduces the formation of ettringite in concrete degradation processes. Moreover, the chemical conditions in the concrete barriers maintain an alkaline condition after 300 years in the proposed LLW repository. This study provides a detailed picture of the long-term evolution of the hydrogeochemical environment in the proposed LLW disposal site in Taiwan.

Leaching mechanisms of constituents from fly ash under the influence of humic acid.

PubMed

Zhao, Shengxin; Chen, Zhonglin; Shen, Jimin; Kang, Jing; Zhang, Jin; Shen, Yanqing

2017-01-05

As a low-cost material for adsorption, FA is one of the most efficient adsorbents of HA. However, the leaching of elements from FA is problematic during utilization in water treatment. In this investigation, the potential leaching behaviors of Calcium, Arsenic, Born, Chromium, and other elements from FA in HA solution were studied via batch test. The data show that HA had an effect on the leaching of each element of FA, depending on the pH, the initial concentration of HA and the addition of calcium oxide (CaO). The Langmuir isotherm could better fit the equilibrium data in different initial concentrations of HA from 10 to 100mg/L. Because of the interaction between HA and the FA leaching elements, multi-layer adsorption occurred when the initial concentration of HA was more than 100mg/L. The pH and free CaO content played major roles in HA adsorption and FA leaching. Using SEM and XRD to characterize the solid of FA being mixed with CaO treated in solution, the results demonstrated that the reaction between FA and CaO could generate crystal minerals, such as portlandite, gismondine, ettringite (AFt) and calcite, which effectively restrained the leaching of elements, reduced secondary pollution. Copyright © 2016 Elsevier B.V. All rights reserved.

Formulation of portland composite cement using waste glass as a supplementary cementitious material

NASA Astrophysics Data System (ADS)

Manullang, Ria Julyana; Samadhi, Tjokorde Walmiki; Purbasari, Aprilina

2017-09-01

Utilization of waste glass in cement is an attractive options because of its pozzolanic behaviour and the market of glass-composite cement is potentially available. The objective of this research is to evaluate the formulation of waste glass as supplementary cementitious material (SCM) by an extreme vertices mixture experiment, in which clinker, waste glass and gypsum proportions are chosen as experimental variables. The composite cements were synthesized by mixing all of powder materials in jar mill. The compressive strength of the composite cement mortars after being cured for 28 days ranges between 229 to 268 kg/cm2. Composite cement mortars exhibit lower compressive strength than ordinary Portland cement (OPC) mortars but is still capable of meeting the SNI 15-7064-2004 standards. The highest compressive strength is obtained by shifting the cement blend composition to the direction of increasing clinker and gypsum proportions as well as reducing glass proportion. The lower compressive strength of composite cement is caused by expansion due to ettringite and ASR gel. Based on the experimental result, the composite cement containing 80% clinker, 15% glass and 5% gypsum has the highest compressive strength. As such, the preliminary technical feasibility of reuse of waste glass as SCM has been confirmed.

Mineralogical and chemical assessment of concrete damaged by the oxidation of sulfide-bearing aggregates: Importance of thaumasite formation on reaction mechanisms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rodrigues, A.; Duchesne, J., E-mail: josee.duchesne@ggl.ulaval.ca; Fournier, B.

Damages in concrete containing sulfide-bearing aggregates were recently observed in the Trois-Rivieres area (Quebec, Canada), characterized by rapid deterioration within 3 to 5 years after construction. A petrographic examination of concrete core samples was carried out using a combination of tools including: stereomicroscopic evaluation, polarized light microscopy, scanning electron microscopy, X-ray diffraction and electron microprobe analysis. The aggregate used to produce concrete was an intrusive igneous rock with different metamorphism degrees and various proportions of sulfide minerals. In the rock, sulfide minerals were often surrounded by a thin layer of carbonate minerals (siderite). Secondary reaction products observed in the damagedmore » concrete include 'rust' mineral forms (e.g. ferric oxyhydroxides such as goethite, limonite (FeO (OH) nH{sub 2}O) and ferrihydrite), gypsum, ettringite and thaumasite. In the presence of water and oxygen, pyrrhotite oxidizes to form iron oxyhydroxides and sulphuric acid. The acid then reacts with the phases of the cement paste/aggregate and provokes the formation of sulfate minerals. Understanding both mechanisms, oxidation and internal sulfate attack, is important to be able to duplicate the damaging reaction in laboratory conditions, thus allowing the development of a performance test for evaluating the potential for deleterious expansion in concrete associated with sulfide-bearing aggregates.« less

Thermomagnetic Analyses to Test Concrete Stability

NASA Astrophysics Data System (ADS)

Geiss, C. E.; Gourley, J. R.

2017-12-01

Over the past decades pyrrhotite-containing aggregate has been used in concrete to build basements and foundations in central Connecticut. The sulphur in the pyrrhotite reacts to several secondary minerals, and associated changes in volume lead to a loss of structural integrity. As a result hundreds of homes have been rendered worthless as remediation costs often exceed the value of the homes and the value of many other homes constructed during the same time period is in question as concrete provenance and potential future structural issues are unknown. While minor abundances of pyrrhotite are difficult to detect or quantify by traditional means, the mineral is easily identified through its magnetic properties. All concrete samples from affected homes show a clear increase in magnetic susceptibility above 220°C due to the γ - transition of Fe9S10 [1] and a clearly defined Curie-temperature near 320°C for Fe7S8. X-ray analyses confirm the presence of pyrrhotite and ettringite in these samples. Synthetic mixtures of commercially available concrete and pyrrhotite show that the method is semiquantitative but needs to be calibrated for specific pyrrhotite mineralogies. 1. Schwarz, E.J., Magnetic properties of pyrrhotite and their use in applied geology and geophysics. 1975, Geological Survey of Canada : Ottawa, ON, Canada: Canada.

Quantification of synthesized hydration products using synchrotron microtomography and spectral analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deboodt, Tyler; Ideker, Jason H.; Isgor, O. Burkan

2017-12-01

The use of x-ray computed tomography (CT) as a standalone method has primarily been used to characterize pore structure, cracking and mechanical damage in cementitious systems due to low contrast in the hydrated phases. These limitations have resulted in the inability to extract quantifiable information on such phases. The goal of this research was to address the limitations caused by low contrast and improving the ability to distinguish the four primary hydrated phases in portland cement; C-S-H, calcium hydroxide, monosulfate, and ettringite. X-ray CT on individual layers, binary mixtures of phases, and quaternary mixtures of phases to represent a hydratedmore » portland cement paste were imaged with synchrotron radiation. Known masses of each phase were converted to a volume and compared to the segmented image volumes. It was observed that adequate contrast in binary mixing of phases allowed for segmentation, and subsequent image analysis indicated quantifiable volumes could be extracted from the tomographic volume. However, low contrast was observed when C-S-H and monosulfate were paired together leading to difficulties segmenting in an unbiased manner. Quantification of phases in quaternary mixtures included larger errors than binary mixes due to histogram overlaps of monosulfate, C-S-H, and calcium hydroxide.« less

Phase formation and chemical phase equilibria in aqueous-based systems pertinent to waste-management: calcium oxide-alluminum oxide-borate-water, calcium oxide-lead oxide-phosphate-water and calcium oxide-arsenate-water

NASA Astrophysics Data System (ADS)

Bothe, James Vincent, Jr.

This thesis explores three aqueous-based systems that have importance in the area of waste-management: (1) CaO-Alsb2Osb3-Bsb2Osb3-Hsb2O, (2) CaO-PbO-Psb2Osb5-Hsb2O and (3) CaO-Assb2Osb5-Hsb2O. More specifically, the objective of this research is to identify various precipitated compounds that can effectively immobilize certain elements that either directly or indirectly have an adverse effect on the environment. In the first quaternary system, CaO-Alsb2Osb3-Bsb2Osb3-Hsb2O, boron is the element desired to be ``fixed'' because ``free'' boron is the cause of delayed hardening in cement paste intended for the encapsulation of nuclear waste. Soluble boron also causes the cement paste to prematurely set, a phenomenon called ``flash-set.'' Isothermal calorimetry was used to track the progress of tricalcium aluminate hydration in the presence of boric acid and Ca(OH)sb2 and revealed the presence of a pronounced induction period, the length of which varied with both temperature and boric acid concentration. It was determined that a diffusion barrier, most likely an amorphous calcium borate, deposited onto the active anhydrous tricalcium aluminate grains inhibiting further hydration. Also, under certain conditions, the precipitation of crystalline 4CaO{*}Alsb2Osb3{*}1/2Bsb2Osb3{*}12Hsb2O may be responsible for the observed flash-set due to its flat, plate-like morphology. Another quaternary hydrate, 6CaO{*}Alsb2Osb3{*}2Bsb2Osb3{*}39Hsb2O (boro-ettringite) was also synthesized during this research and crystallized as hexagonal prisms. In contrast to the fast crystallization of 4CaO{*}Alsb2Osb3{*}1/2Bsb2Osb3{*}12Hsb2O, boro-ettringite was observed to form slowly and in stages with the precipitation of the transient phase CaO-Bsb2Osb3{*}6Hsb2O preceding it. Further investigation of these two hydrates lead to the construction of a quaternary phase diagram and to the determination of their solubility products (pKsp = -logKsp), which were determined to be 44.23 for boro-ettringite

Evaluation of blends bauxite-calcination-method red mud with other industrial wastes as a cementitious material: properties and hydration characteristics.

PubMed

Zhang, Na; Liu, Xiaoming; Sun, Henghu; Li, Longtu

2011-01-15

Red mud is generated from alumina production, and its disposal is currently a worldwide problem. In China, large quantities of red mud derived from bauxite calcination method are being discharged annually, and its utilization has been an urgent topic. This experimental research was to evaluate the feasibility of blends red mud derived from bauxite calcination method with other industrial wastes for use as a cementitious material. The developed cementitious material containing 30% of the bauxite-calcination-method red mud possessed compressive strength properties at a level similar to normal Portland cement, in the range of 45.3-49.5 MPa. Best compressive strength values were demonstrated by the specimen RSFC2 containing 30% bauxite-calcination-method red mud, 21% blast-furnace slag, 10% fly ash, 30% clinker, 8% gypsum and 1% compound agent. The mechanical and physical properties confirm the usefulness of RSFC2. The hydration characteristics of RSFC2 were characterized by XRD, FTIR, (27)Al MAS-NMR and SEM. As predominant hydration products, ettringite and amorphous C-S-H gel are principally responsible for the strength development of RSFC2. Comparing with the traditional production for ordinary Portland cement, this green technology is easier to be implemented and energy saving. This paper provides a key solution to effectively utilize bauxite-calcination-method red mud. Copyright © 2010 Elsevier B.V. All rights reserved.

Investigation on the potential of waste cooking oil as a grinding aid in Portland cement.

PubMed

Li, Haoxin; Zhao, Jianfeng; Huang, Yuyan; Jiang, Zhengwu; Yang, Xiaojie; Yang, Zhenghong; Chen, Qing

2016-12-15

Although there are several methods for managing waste cooking oil (WCO), a significant result has not been achieved in China. A new method is required for safe WCO management that minimizes the environmental threat. In this context, this work was developed in which cement clinker and gypsum were interground with various WCOs, and their properties, such as grindability, water-cement ratio required to achieve a normal consistency, setting times, compressive strength, contents of calcium hydroxide and ettringite in the hardened paste, microstructure and economic and environmental considerations, were addressed in detail. The results show that, overall, WCO favorably improves cement grinding. WCO prolonged the cement setting times and resulted in longer setting times. Additionally, more remarkable effects were found in cements in which WCO contained more unsaturated fatty acid. WCOs increased the cement strength. However, this enhancement was rated with respect to the WCO contents and components. WCOs decreased the CH and AFt contents in the cement hardened paste. Even the AFt content at later ages was reduced when WCO was used. WCO also densify microstructure of the hardened cement paste. It is economically and environmentally feasible to use WCOs as grinding aids in the cement grinding process. These results contribute to the application of WCOs as grinding aids and to the safe management of WCO. Copyright © 2016 Elsevier Ltd. All rights reserved.

Geochemically structural characteristics of municipal solid waste incineration fly ash particles and mineralogical surface conversions by chelate treatment.

PubMed

Kitamura, Hiroki; Sawada, Takaya; Shimaoka, Takayuki; Takahashi, Fumitake

2016-01-01

Leaching behaviors of heavy metals contained in municipal solid waste incineration (MSWI) fly ash have been studied well. However, micro-characteristics of MSWI fly ash particles are still uncertain and might be non-negligible to describe their leaching behaviors. Therefore, this study investigated micro-characteristics of MSWI fly ash particles, especially their structural properties and impacts of chelate treatment on surface characteristics. According to SEM observations, raw fly ash particles could be categorized into four types based on their shapes. Because chelate treatment changed the surface of fly ash particles dramatically owing to secondary mineral formations like ettringite, two more types could be categorized for chelate-treated fly ash particles. Acid extraction experiments suggest that fly ash particles, tested in this study, consist of Si-base insoluble core structure, Al/Ca/Si-base semi-soluble matrices inside the body, and KCl/NaCl-base soluble aggregates on the surface. Scanning electron microscope (SEM) observations of the same fly ash particles during twice moistening treatments showed that KCl/NaCl moved under wet condition and concentrated at different places on the particle surface. However, element mobility depended on secondary mineral formations. When insoluble mineral like gypsum was generated and covered the particle surface, it inhibited element transfer under wet condition. Surface characteristics including secondary mineral formation of MSWI fly ash particles are likely non-negligible to describe trace element leaching behaviors.

Reductive solidification/stabilization of chromate in municipal solid waste incineration fly ash by ascorbic acid and blast furnace slag.

PubMed

Zhou, Xian; Zhou, Min; Wu, Xian; Han, Yi; Geng, Junjun; Wang, Teng; Wan, Sha; Hou, Haobo

2017-09-01

Fly ash is a hazardous byproduct of municipal solid waste incineration (MSWI). Cementitious material that is based on ground-granulated blast furnace slag (GGBFS) has been tested and proposed as a binder to stabilize Pb, Cd, and Zn in MSWI fly ash (FA). Cr, however, still easily leaches from MSWI FA. Different reagents, such as ascorbic acid (VC), NaAlO 2 , and trisodium salt nonahydrate, were investigated as potential Cr stabilizers. The results of the toxicity characteristic leaching procedure (TCLP) showed that VC significantly improved the stabilization of Cr via the reduction of Cr(VI) to Cr(III). VC, however, could interfere with the hydration process. Most available Cr was transformed into stable Cr forms at the optimum VC content of 2 wt%. Cr leaching was strongly pH dependent and could be represented by a quintic polynomial model. The results of X-ray diffraction and scanning electron microscopy-energy dispersive analysis revealed that hollow spheres in raw FA were partially filled with hydration products, resulting in the dense and homogeneous microstructure of the solidified samples. The crystal structures of C-S-H and ettringite retained Zn and Cr ions. In summary, GGBFS-based cementitious material with the low addition of 2 wt% VC effectively immobilizes Cr-bearing MSWI FA. Copyright © 2017. Published by Elsevier Ltd.

Assessment of Pb-slag, MSWI bottom ash and boiler and fly ash for using as a fine aggregate in cement mortar.

PubMed

Saikia, Nabajyoti; Cornelis, Geert; Mertens, Gilles; Elsen, Jan; Van Balen, Koenraad; Van Gerven, Tom; Vandecasteele, Carlo

2008-06-15

Three types of wastes, metallurgical slag from Pb production (SLG), the sand-sized (0.1-2 mm) fraction of MSWI bottom ash from a grate furnace (SF), and boiler and fly ash from a fluidised bed incinerator (BFA), were characterized and used to replace the fine aggregate during preparation of cement mortar. The chemical and mineralogical behaviour of these wastes along with the reactivities of the wastes with lime and the hydration behaviour of ordinary Portland cement paste with and without these wastes added were evaluated by various chemical and instrumental techniques. The compressive strengths of the cement mortars containing waste as a partial substitution of fine aggregates were also assessed. Finally, leaching studies of the wastes and waste containing cement mortars were conducted. SLG addition does not show any adverse affect during the hydration of cement, or on the compressive strengths behaviours of mortars. Formation of expansive products like ettringite, aluminium hydroxide and H2 gas due to the reaction of some constituents of BFA and SF with alkali creates some cracks in the paste as well as in the cement mortars, which lower the compressive strength of the cement mortars. However, utilization of all materials in cement-based application significantly improves the leaching behaviour of the majority of the toxic elements compared to the waste as such.

Self-healing of drying shrinkage cracks in cement-based materials incorporating reactive MgO

NASA Astrophysics Data System (ADS)

Qureshi, T. S.; Al-Tabbaa, A.

2016-08-01

Excessive drying shrinkage is one of the major issues of concern for longevity and reduced strength performance of concrete structures. It can cause the formation of cracks in the concrete. This research aims to improve the autogenous self-healing capacity of traditional Portland cement (PC) systems, adding expansive minerals such as reactive magnesium oxide (MgO) in terms of drying shrinkage crack healing. Two different reactive grades (high ‘N50’and moderately high ‘92-200’) of MgO were added with PC. Cracks were induced in the samples with restraining end prisms through natural drying shrinkage over 28 days after casting. Samples were then cured under water for 28 and 56 days, and self-healing capacity was investigated in terms of mechanical strength recovery, crack sealing efficiency and improvement in durability. Finally, microstructures of the healing materials were investigated using FT-IR, XRD, and SEM-EDX. Overall N50 mixes show higher expansion and drying shrinkage compared to 92-200 mixes. Autogenous self-healing performance of the MgO containing samples were much higher compared to control (only PC) mixes. Cracks up to 500 μm were sealed in most MgO containing samples after 28 days. In the microstructural investigations, highly expansive Mg-rich hydro-carbonate bridges were found along with traditional calcium-based, self-healing compounds (calcite, portlandite, calcium silicate hydrates and ettringite).

Effect of temperature on the durability of class C fly ash belite cement in simulated radioactive liquid waste: synergy of chloride and sulphate ions.

PubMed

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.

Importance of microscopy in durability studies of solidified and stabilized contaminated soils

USGS Publications Warehouse

Klich, I.; Wilding, L.P.; Drees, L.R.; Landa, E.R.

1999-01-01

Solidification/stabilization (S/S) is recognized by the U.S. EPA as a best demonstrated available technology for the containment of contaminated soils and other hazardous wastes that cannot be destroyed by chemical, thermal, or biological means. Despite the increased use of S/S technologies, little research has been conducted on the weathering and degradation of solidified and stabilized wastes once the treated materials have been buried. Published data to verify the performance and durability of landfilled treated wastes over time are rare. In this preliminary study, optical and electron microscopy (scanning electron microscopy [SEM], transmission electron microscopy [TEM] and electron probe microanalyses [EPMA]) were used to evaluate weathering features associated with metal-bearing contaminated soil that had been solidified and stabilized with Portland cement and subsequently buried on site, stored outdoors aboveground, or achieved in a laboratory warehouse for up to 6 yr. Physical and chemical alteration processes identified include: freeze-thaw cracking, cracking caused by the formation of expansive minerals such as ettringite, carbonation, and the movement of metals from waste aggregates into the cement micromass. Although the extent of degradation after 6 yr is considered slight to moderate, results of this study show that the same environmental concerns that affect the durability of concrete must be considered when evaluating the durability and permanence of the solidification and stabilization of contaminated soils with cement. In addition, such evaluations cannot be based on leaching and chemical analyses alone. The use of all levels of microscopic analyses must be incorporated into studies of the long-term performance of S/S technologies.Solidification/stabilization (S/S) is recognized by the U.S. EPA as a best demonstrated available technology for the containment of contaminated soils and other hazardous wastes that cannot be destroyed by chemical

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

Treatment of air pollution control residues with iron rich waste sulfuric acid: does it work for antimony (Sb)?

PubMed

Okkenhaug, Gudny; Breedveld, Gijs D; Kirkeng, Terje; Lægreid, Marit; Mæhlum, Trond; Mulder, Jan

2013-03-15

Antimony (Sb) in air pollution control (APC) residues from municipal solid waste incineration has gained increased focus due to strict Sb leaching limits set by the EU landfill directive. Here we study the chemical speciation and solubility of Sb at the APC treatment facility NOAH Langøya (Norway), where iron (Fe)-rich sulfuric acid (∼3.6M, 2.3% Fe(II)), a waste product from the industrial extraction of ilmenite, is used for neutralization. Antimony in water extracts of untreated APC residues occurred exclusively as pentavalent antimonate, even at low pH and Eh values. The Sb solubility increased substantially at pH<10, possibly due to the dissolution of ettringite (at alkaline pH) or calcium (Ca)-antimonate. Treated APC residues, stored anoxically in the laboratory, simulating the conditions at the NOAH Langøya landfill, gave rise to decreasing concentrations of Sb in porewater, occurring exclusively as Sb(V). Concentrations of Sb decreased from 87-918μgL(-1) (day 3) to 18-69μgL(-1) (day 600). We hypothesize that an initial sorption of Sb to Fe(II)-Fe(III) hydroxides (green rust) and eventually precipitation of Ca- and Fe-antimonates (tripuhyite; FeSbO4) occurred. We conclude that Fe-rich, sulfuric acid waste is efficient to immobilize Sb in APC residues from waste incineration. Copyright © 2013 Elsevier B.V. All rights reserved.

Biodeterioration of the Cement Composites

NASA Astrophysics Data System (ADS)

Luptáková, Alena; Eštoková, Adriana; Mačingová, Eva; Kovalčíková, Martina; Jenčárová, Jana

2016-10-01

The destruction of natural and synthetic materials is the spontaneous and irreversible process of the elements cycling in nature. It can by accelerated or decelerated by physical, chemical and biological influences. Biological influences are represented by the influence of the vegetation and microorganisms (MO). The destruction of cement composites by different MO through the diverse mechanisms is entitled as the concrete biodeterioration. Several sulphur compounds and species of MO are involved in this complex process. Heterotrophic and chemolithotrophic bacteria together with fungi have all been found in samples of corroding cement composites. The MO involved in the process metabolise the presented sulphur compounds (hydrogen sulphide, elemental sulphur etc.) to sulphuric acid reacting with concrete. When sulphuric acid reacts with a concrete matrix, the first step involves a reaction between the acid and the calcium hydroxide forming calcium sulphate. This is subsequently hydrated to form gypsum, the appearance of which on the surface of concrete pipes takes the form of a white, mushy substance which has no cohesive properties. In the continuing attack, the gypsum would react with the calcium aluminate hydrate to form ettringite, an expansive product. The use supplementary cementing composite materials have been reported to improve the resistance of concrete to biodeterioration. The aim of this work was the study of the cement composites biodeterioration by the bacteria Acidithiobacillus thiooxidans. Experimental works were focused on the comparison of special cement composites and its resistance affected by the activities of used sulphur-oxidising

Calcium sulfoaluminate cement blended with OPC: A potential binder to encapsulate low-level radioactive slurries of complex chemistry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cau Dit Coumes, Celine; Courtois, Simone; Peysson, Sandrine

Investigations were carried out in order to solidify in cement a low-level radioactive waste of complex chemistry obtained by mixing two process streams, a slurry produced by ultra-filtration and an evaporator concentrate with a salinity of 600 gxL{sup -1}. Direct cementation with Portland cement (OPC) was not possible due to a very long setting time of cement resulting from borates and phosphates contained in the waste. According to a classical approach, this difficulty could be solved by pre-treating the waste to reduce adverse cement-waste interactions. A two-stage process was defined, including precipitation of phosphates and sulfates at 60 deg. Cmore » by adding calcium and barium hydroxide to the waste stream, and encapsulation with a blend of OPC and calcium aluminate cement (CAC) to convert borates into calcium quadriboroaluminate. The material obtained with a 30% waste loading complied with specifications. However, the pre-treatment step made the process complex and costly. A new alternative was then developed: the direct encapsulation of the waste with a blend of OPC and calcium sulfoaluminate cement (CSA) at room temperature. Setting inhibition was suppressed, which probably resulted from the fact that, when hydrating, CSA cement formed significant amounts of ettringite and calcium monosulfoaluminate hydrate which incorporated borates into their structure. As a consequence, the waste loading could be increased to 56% while keeping acceptable properties at the laboratory scale.« less

Utilization of air pollution control residues for the stabilization/solidification of trace element contaminated soil.

PubMed

Travar, I; Kihl, A; Kumpiene, J

2015-12-01

The aim of this study was to evaluate the stabilization/solidification (S/S) of trace element-contaminated soil using air pollution control residues (APCRs) prior to disposal in landfill sites. Two soil samples (with low and moderate concentrations of organic matter) were stabilized using three APCRs that originated from the incineration of municipal solid waste, bio-fuels and a mixture of coal and crushed olive kernels. Two APCR/soil mixtures were tested: 30% APCR/70% soil and 50% APCR/50% soil. A batch leaching test was used to study immobilization of As and co-occurring metals Cr, Cu, Pb and Zn. Solidification was evaluated by measuring the unconfined compression strength (UCS). Leaching of As was reduced by 39-93% in APCR/soil mixtures and decreased with increased amounts of added APCR. Immobilization of As positively correlated with the amount of Ca in the APCR and negatively with the amount of soil organic matter. According to geochemical modelling, the precipitation of calcium arsenate (Ca3(AsO4)2/4H2O) and incorporation of As in ettringite (Ca6Al2(SO4)3(OH)12 · 26H2O) in soil/APCR mixtures might explain the reduced leaching of As. A negative effect of the treatment was an increased leaching of Cu, Cr and dissolved organic carbon. Solidification of APCR/soil was considerably weakened by soil organic matter.

Combining Mineral Identification Techniques to Help Homeowners of Northeastern Connecticut Diagnose Pyrrhotite Laced Concrete Foundations

NASA Astrophysics Data System (ADS)

Gourley, J. R.; Geiss, C. E.

2017-12-01

Crumbling concrete linked to the mineral pyrrhotite is an emerging home owner crisis in northeastern Connecticut as new home foundations are failing within only several years. Potentially thousands of homes that have been built between the mid 1980's and 2016 are affected. Homes have been rendered worthless as basement concrete is crumbling and the cost of repair often exceeds the value of the home. In all of the failing concrete cases the presence of pyrrhotite from a local quarry is the common denominator. Testing for pyrrhotite, until now, has been costly and often invasive, with large core samples required. In working with a local advocacy group, The Connecticut Coalition Against Crumbling Basements (CCACB), we have developed a rapid analysis method that uses a combination of magnetic susceptibility and high resolution X-ray diffraction to identify both the mineral pyrrhotite and/or its expansive product mineral, ettringite. The goal of this method to give homeowners a reliable diagnosis that could help in mitigation decisions and/or the determination of the resale value of their homes. The partnership of Trinity College's Environmental Science Program with the CCACB has built a rewarding bridge between education and the community. Faculty, students and local advocates are collaborating to solve a problem that will help homeowners diagnose a potentially devastating non-natural "geo" hazard that can adversely affect home values where concrete is of an unknown provenance.

Interaction processes at the concrete-bentonite interface after 13 years of FEBEX-Plug operation. Part II: Bentonite contact

NASA Astrophysics Data System (ADS)

Fernández, Raúl; Torres, Elena; Ruiz, Ana I.; Cuevas, Jaime; Alonso, María Cruz; García Calvo, José Luis; Rodríguez, Enrique; Turrero, María Jesús

2017-06-01

The in situ FEBEX experiment performed at the URL in Grimsel (Swizerland) was dismantled after 18 years of operation. Interface samples between bentonite and a shotcreted concrete plug that was constructed in a second operational phase have been studied after 13 years of interaction. Mineralogical and geochemical characterization of samples have been performed by XRD, SEM-EDX, TG and FTIR techniques in addition to determinations of major ions by chemical analysis of aqueous extracts, δ18O and δ13C stable isotopes both in concrete paste and bentonite, and exchangeable cations in bentonite. Low mineralogical alteration impact was observed in bentonite that is only affected by a few millimeters. A large accumulation of Mg was observed at the bentonite side of the interface precipitating as silicates in various forms. In addition, heterogeneous carbonation was observed at the interface, but mostly affecting the concrete side. Migration of aqueous species occurred, being the most relevant the diffusion of chloride and sulfate from bentonite to concrete, in agreement with Part I of this study. Chloride advanced more into the concrete, while sulfates reacted to form ettringite, which has an evident alteration impact at the very interface (<0.5 mm rim) within the concrete. The ionic mobility has also redistributed the exchangeable cations in bentonite, increasing the content in Ca2+ and Na+, compensated by a decrease in Mg2+. The results presented in this paper complement those presented in Part I, focusing on the alteration of concrete by the bentonite and the granite groundwater.

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

The leaching behavior of cement stabilized air pollution control residues: a comparison of field and laboratory investigations.

PubMed

Baur, I; Ludwig, C; Johnson, C A

2001-07-01

The factors controlling leachate composition of cement stabilized air pollution control (APC) residues (41% APC residues, 22% cement, 3% Na2CO3, and 32% water, w/w) have been investigated both in the laboratory and in a pilot landfill. Batch leaching and tank leaching tests were carried out in the laboratory in order to determine solubility controlling phases and diffusion controlled species. The major species Ca, SO4, Al, and Si could be partially modeled by assuming calcium silicate hydrate (C-S-H), portlandite, and ettringite to be the solubility controlling phases both in field and laboratory. There were obviously additional minerals that could not be taken into account in calculations because of the lack of data. The determined effective diffusion coefficients (De) for Na and K (2.18e-12 and 5.43e-12 m2s-1) were used to model field concentrations. Agreement with field data was good. Heavy metal concentrations were in the range of 10(-8) mol dm-1 (Cd, Co, Cu, Mn, Ni) to 10(-6) mol dm-1 (Mo, Pb, W, Zn) in all experiments and often lower in the field leachate than expected from batch experiments. In laboratory experiments, the solubility of Mo and W was most probably controlled by their calcium metalates, Cu by CuO, Ni by Ni(OH)2, and Zn probably by a Zn containing C-S-H phase. In the field, diffusion seems to control Mo and W leachability, with calculated De values of 3.49e-14 and 1.35e-15 m2s-1.

Real-time high-resolution X-ray imaging and nuclear magnetic resonance study of the hydration of pure and Na-doped C3A in the presence of sulfates

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

Improvement of Early Strength of Cement Mortar Containing Granulated Blast Furnace Slag Using Industrial Byproducts.

PubMed

Kim, Jin-Hyoung; Lee, Han-Seung

2017-09-07

In the field of construction, securing the early strength of concrete (on the first and third days of aging) has been an important problem in deciding the mold release time (i.e., shortening the construction time period). Therefore, the problem of reduced compressive strength in the early aging stage caused by mixing granulated blast furnace slag (GBFS) with concrete must certainly be resolved. In this study, we conduct experiments to explore methods for generating a concrete that develops an early strength equivalent to that of 100% OPC. The objective of this study is the development of an early-strength accelerator (ESA) made from an industrial by-product, for a GBFS-mixed cement mortar. This study also analyzes the mechanism of the early-strength generation in the concrete to evaluate the influence of the burning temperature of ESA on the optimal compressive strength of the concrete. According to the results of the experiment, GBFS, whose ESA is burnt at 800 °C, shows an activation factor of 102.6-104.7% in comparison with 100% OPC on the first and third days during early aging, thereby meeting the target compressive strength. The results of the micro-analytic experiment are as follows: ESA showed a pH of strongly alkaline. In addition, it was found that the content of SO₃ was high in the chemical components, thus activating the hydration reaction of GBFS in the early age. This initial hydration reaction was thought to be due to the increase in the filling effect of the hydrate and the generation of C-S-H of the early age by the mass production of Ettringite.

Improvement of Early Strength of Cement Mortar Containing Granulated Blast Furnace Slag Using Industrial Byproducts

PubMed Central

Kim, Jin-Hyoung; Lee, Han-Seung

2017-01-01

In the field of construction, securing the early strength of concrete (on the first and third days of aging) has been an important problem in deciding the mold release time (i.e., shortening the construction time period). Therefore, the problem of reduced compressive strength in the early aging stage caused by mixing granulated blast furnace slag (GBFS) with concrete must certainly be resolved. In this study, we conduct experiments to explore methods for generating a concrete that develops an early strength equivalent to that of 100% OPC. The objective of this study is the development of an early-strength accelerator (ESA) made from an industrial by-product, for a GBFS-mixed cement mortar. This study also analyzes the mechanism of the early-strength generation in the concrete to evaluate the influence of the burning temperature of ESA on the optimal compressive strength of the concrete. According to the results of the experiment, GBFS, whose ESA is burnt at 800 °C, shows an activation factor of 102.6–104.7% in comparison with 100% OPC on the first and third days during early aging, thereby meeting the target compressive strength. The results of the micro-analytic experiment are as follows: ESA showed a pH of strongly alkaline. In addition, it was found that the content of SO3 was high in the chemical components, thus activating the hydration reaction of GBFS in the early age. This initial hydration reaction was thought to be due to the increase in the filling effect of the hydrate and the generation of C-S-H of the early age by the mass production of Ettringite. PMID:28880256

Tatarinovite Ca3Al(SO4)[B(OH)4](OH)6 · 12H2O, a new ettringite-group mineral from the Bazhenovskoe deposit, Middle Urals, Russia, and its crystal structure

NASA Astrophysics Data System (ADS)

Chukanov, N. V.; Kasatkin, A. V.; Zubkova, N. V.; Britvin, S. N.; Pautov, L. A.; Pekov, I. V.; Varlamov, D. A.; Bychkova, Ya. V.; Loskutov, A. B.; Novgorodova, E. A.

2016-12-01

A new mineral, tatarinovite, ideally Ca3Al(SO4)[B(OH)4](OH)6 · 12H2O, has been found in cavities of rhodingites at the Bazhenovskoe chrysotile asbestos deposit, Middle Urals, Russia. It occurs (1) colorless, with vitreous luster, bipyramidal crystals up to 1 mm across in cavities within massive diopside, in association with xonotlite, clinochlore, pectolite and calcite, and (2) as white granular aggregates up to 5 mm in size on grossular with pectolite, diopside, calcite, and xonotlite. The Mohs hardness is 3; perfect cleavage on (100) is observed. D meas = 1.79(1), D calc = 1.777 g/cm3. Tatarinovite is optically uniaxial (+), ω = 1.475(2), ɛ = 1.496(2). The IR spectrum contains characteristic bands of SO4 2-, CO3 2-, B(OH)4 -, B(OH)3, Al(OH)6 3-, Si(OH)6 2-, OH-, and H2O. The chemical composition of tatarinovite (wt %; ICP-AES; H2O was determined by the Alimarin method; CO2 was determined by selective sorption on askarite) is as follows: 27.40 CaO, 4.06 B2O3, 6.34 A12O3, 0.03 Fe2O3, 2.43 SiO2, 8.48 SO3, 4.2 CO2, 46.1 H2O, total is 99.04. The empirical formula (calculated on the basis of 3Ca apfu) is H31.41Ca3.00(Al0.76Si0.25)Σ1.01 · (B0.72S0.65C0.59)Σ1.96O24.55. Tatarinovite is hexagonal, space gr. P63, a = 11.1110(4) Å, c = 10.6294(6) Å, V = 1136.44(9) A3, Z = 2. Its crystal chemical formula is Ca3(Al0.70Si0.30) · {[SO4]0.34[B(OH)4]0.33[CO3]0.24}{[SO4]0.30[B(OH)4]0.34[CO3]0.30[B(OH)3]0.06}(OH5·73O0.27) · 12H2O. The strongest reflections of the powder X-ray diffraction pattern [ d, Å ( I, %) ( hkl)] are 9.63 (100) (100), 5.556 (30) (110), 4.654 (14) (102), 3.841 (21) (112), 3.441 (12) (211), 2.746 (10) (302), 2.538 (12) (213). Tatarinovite was named in memory of the Russian geologist and petrologist Pavel Mikhailovich Tatarinov (1895-1976), a well-known specialist in chrysotile asbestos deposits. Type specimens have been deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow.

Solid state NMR and LVSEM studies on the hardening of latex modified tile mortar systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rottstegge, J.; Arnold, M.; Herschke, L.

Construction mortars contain a broad variety of both inorganic and organic additives beside the cement powder. Here we present a study of tile mortar systems based on portland cement, quartz, methyl cellulose and different latex additives. As known, the methyl cellulose stabilizes the freshly prepared cement paste, the latex additive enhances final hydrophobicity, flexibility and adhesion. Measurements were performed by solid state nuclear magnetic resonance (NMR) and low voltage scanning electron microscopy (LVSEM) to probe the influence of the latex additives on the hydration, hardening and the final tile mortar properties. While solid state NMR enables monitoring of the bulkmore » composition, scanning electron microscopy affords visualization of particles and textures with respect to their shape and the distribution of the different phases. Within the alkaline cement paste, the poly(vinyl acetate) (VAc)-based latex dispersions stabilized by poly(vinyl alcohol) (PVA) were found to be relatively stable against hydrolysis. The influence of the combined organic additives methyl cellulose, poly(vinyl alcohol) and latexes stabilized by poly(vinyl alcohol) on the final silicate structure of the cement hydration products is small. But even small amounts of additives result in an increased ratio of ettringite to monosulfate within the final hydrated tile mortar as monitored by {sup 27}Al NMR. The latex was found to be adsorbed to the inorganic surfaces, acting as glue to the inorganic components. For similar latex water interfaces built up by poly(vinyl alcohol), a variation in the latex polymer composition results in modified organic textures. In addition to the networks of the inorganic cement and of the latex, there is a weak network build up by thin polymer fibers, most probably originating from poly(vinyl alcohol). Besides the weak network, polymer fibers form well-ordered textures covering inorganic crystals such as portlandite.« less

Mechanism of Hg(II) Immobilization in Sediments by Sulfate-Cement Amendment.

PubMed

Serrano, Susana; Vlassopoulos, Dimitri; O'Day, Peggy A

2016-04-01

Reactive amendments such as Portland and super-sulfate cements offer a promising technology for immobilizing metalloid contaminants such as mercury (Hg) in soils and sediments through sequestration in less bioavailable solid forms. Tidal marsh sediments were reacted with dissolved Hg(II) in synthetic seawater and fresh water solutions, treated with Portland cement and FeSO 4 amendment, and aged for up to 90 days. Reacted solids were analyzed with bulk sequential extraction methods and characterized by powder X-ray diffraction (XRD), electron microscopy, and synchrotron X-ray absorption spectroscopy at the Hg L III - and S K-edge. In amended sediments, XRD, SEM and sulfur K-edge XANES indicated formation of gypsum in seawater experiments or ettringite-type (Ca 6 Al 2 (SO 4 ) 3 (OH) 12 . 26H 2 O) phases in fresh water experiments, depending on the final solution pH (seawater ∼8.5; freshwater ∼10.5). Analysis of Hg EXAFS spectra showed Cl and Hg ligands in the first- and second-coordination shells at distances characteristic of a polynuclear chloromercury(II) salt, perhaps as a nanoparticulate phase, in both seawater and fresh water experiments. In addition to the chloromercury species, a smaller fraction (∼20-25%) of Hg was bonded to O atoms in fresh water sample spectra, suggesting the presence of a minor sorbed Hg fraction. In the absence of amendment treatment, Hg sorption and resistance to extraction can be accounted for by relatively strong binding by reduced S species present in the marsh sediment detected by S XANES. Thermodynamic calculations predict stable aqueous Hg-Cl species at seawater final pH, but higher final pH in fresh water favors aqueous Hg-hydroxide species. The difference in Hg coordination between aqueous and solid phases suggests that the initial Hg-Cl coordination was stabilized in the cement hydration products and did not re-equilibrate with the bulk solution with aging. Collectively, results suggest physical encapsulation of Hg as a

Crystal structures of Boro-AFm and sBoro-AFt phases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Champenois, Jean-Baptiste; Mesbah, Adel; Clermont Universite, ENSCCF, Institut de Chimie de Clermont-Ferrand, BP 10448, F-63000 Clermont-Ferrand

2012-10-15

Crystal structures of boron-containing AFm (B-AFm) and AFt (B-AFt) phases have been solved ab-initio and refined from X-ray powder diffraction. {sup 11}B NMR and Raman spectroscopies confirm the boron local environment in both compounds: three-fold coordinated in B-AFm corresponding to HBO{sub 3}{sup 2-} species, and four-fold coordinated in B-AFt corresponding to B (OH){sub 4}{sup -} species. B-AFm crystallizes in the rhombohedral R3{sup Macron }c space group and has the 3CaO{center_dot}Al{sub 2}O{sub 3}{center_dot}CaHBO{sub 3}{center_dot}12H{sub 2}O (4CaO{center_dot}Al{sub 2}O{sub 3}{center_dot}1/2B{sub 2}O{sub 3}{center_dot}12.5H{sub 2}O, C{sub 4}AB{sub 1/2}H{sub 12.5}) general formulae with planar trigonal HBO{sub 3}{sup 2-} anions weakly bonded at the centre of themore » interlayer region. One HBO{sub 3}{sup 2-} anion is statistically distributed with two weakly bonded water molecules on the same crystallographic site. B-AFt crystallizes in the trigonal P3cl space group and has the 3CaO{center_dot}Al{sub 2}O{sub 3}{center_dot}Ca(OH){sub 2}{center_dot}2Ca(B (OH){sub 4}){sub 2}{center_dot}24H{sub 2}O (6CaO{center_dot}Al{sub 2}O{sub 3}{center_dot}2B{sub 2}O{sub 3}{center_dot}33H{sub 2}O, C{sub 6}AB{sub 2}H{sub 33}) general formulae with tetrahedral B (OH){sub 4}{sup -} anions located in the channel region of the structure. All tetrahedral anions are oriented in a unique direction, leading to a hexagonal c lattice parameter about half that of ettringite.« less

Hydrological and geochemical factors affecting leachate composition in municipal solid waste incinerator bottom ash. Part II. The geochemistry of leachate from Landfill Lostorf, Switzerland

NASA Astrophysics Data System (ADS)

Johnson, C. Annette; Kaeppeli, Michael; Brandenberger, Sandro; Ulrich, Andrea; Baumann, Werner

1999-12-01

The leachate composition of the Landfill Lostorf, Buchs, Switzerland has been examined as a function rain events and dry periods between November 1994 and November 1996. Discharge and electrical conductivity of the central drainage discharge were monitored continuously, whilst samples for chemical analysis were taken at discrete intervals. The average total concentrations of Na, Cl, K, Mg, Ca and SO 4 are 44.5, 47.1, 11.8, 0.63, 8.2 and 12.4 mM, respectively. During rain events, the leachate is diluted by the preferential flow of rainwater into the drainage discharge. Drainage discharge pH values range between 8.68 and 11.28, the latter under dry conditions. Thermodynamic calculations indicate that CaSO 4, ettringite (3CaOAl 2O 3CaSO 4·32H 2O) and Al(OH) 3 may control the concentrations of the components Ca, SO 4 and Al. Dissolved Si may be in thermodynamic equilibrium with either Ca silicate hydrate or imogolite. Cadmium, Mo, V, Mn and Zn are also diluted during rain events and concentration changes agree with those of conductivity (representing the major constituents). Average concentrations are 0.012, 5.4, 2.3, 0.085, and 0.087 μM, respectively. Components such as Al, Cu, Sb and Cr increase in concentration with increased discharge. Average concentrations are 1.6, 0.27 and 0.21 μM, respectively. For Cu, the explanation lies in its affinity for total organic carbon (TOC). Thermodynamic calculations indicate that whilst dissolution/precipitation reactions with metal hydroxides and carbonates can explain the observed concentrations of Cd, sorption and complexation reactions probably influence the concentrations of Cu, Pb (average measurable concentration 0.013 μM), Zn and Mn. For the oxyanion species such as MoO 4 and WO 4 (average concentration 0.61 μM), it is probable that Ca metallate formation plays a dominant role in determining concentration ranges. Geochemical processes appear to determine concentration ranges and the hydrological factors, the

Modeling the Hydrogeochemical Transport of Radionuclides through Engineered Barriers System in the Proposed LLW Disposal Site of Taiwan - 12082

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Wen-Sheng; Liu, Chen-Wuing; Tsao, Jui-Hsuan

2012-07-01

A proposed site for final disposal of low-level radioactive waste located in Daren Township of Taitung County along the southeastern coast has been on the selected list in Taiwan. The geology of the Daren site consists of argillite and meta-sedimentary rocks. A mined cavern design with a tunnel system of 500 m below the surface is proposed. Concrete is used as the main confinement material for the engineered barrier. To investigate the hydrogeochemical transport of radionuclides through engineered barriers system, HYDROGEOCHEM5.0 model was applied to simulate the complex chemical interactions among radionuclides, the cement minerals of the concrete, groundwater flow,more » and transport in the proposed site. The simulation results showed that the engineered barriers system with the side ditch efficiently drained the ground water and lowered the concentration of the concrete degradation induced species (e.g., hydrogen ion, sulfate, and chloride). The velocity of groundwater observed at side ditch gradually decreased with time due to the fouling of pore space by the mineral formation of ettringite and thaumasite. The short half-life of Co-60, Sr-90 and Cs-137 significantly reduced the concentrations, whereas the long half-life of I-129(1.57x10{sup 7} years) and Am-241(432 years) remain stable concentrations at the interface of waste canister and concrete barrier after 300 years. The mineral saturation index (SI) was much less than zero due to the low aqueous concentration of radionuclide, so that the precipitation formation of Co-60, Sr-90, I-129, Cs-137 and Am-241 related minerals were not found. The effect of adsorption/desorption (i.e., surface complexation model) could be a crucial geochemical mechanism for the modeling of liquid-solid phase behavior of radionuclide in geochemically dynamic environments. Moreover, the development of advanced numerical models that are coupled with hydrogeochemical transport and dose assessment of radionuclide is required in the

Deciphering mineralogical changes and carbonation development during hydration and ageing of a consolidated ternary blended cement paste

PubMed Central

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

Steam Cured Self-Consolidating Concrete and the Effects of Limestone Filler

NASA Astrophysics Data System (ADS)

Aqel, Mohammad A.

The purpose of this thesis is to determine the effect and the mechanisms associated with replacing 15% of the cement by limestone filler on the mechanical properties and durability performance of self-consolidating concrete designed and cured for precast/prestressed applications. This study investigates the role of limestone filler on the hydration kinetics, mechanical properties (12 hours to 300 days), microstructural and durability performance (rapid chloride permeability, linear shrinkage, sulfate resistance, freeze-thaw resistance and salt scaling resistance) of various self-consolidating concrete mix designs containing 5% silica fume and steam cured at a maximum holding temperature of 55°C. This research also examines the resistance to delayed ettringite formation when the concrete is steam cured at 70°C and 82°C and its secondary consequences on the freeze-thaw resistance. The effect of several experimental variables related to the concrete mix design and also the curing conditions are examined, namely: limestone filler fineness, limestone filler content, cement type, steam curing duration and steam curing temperature. In general, the results reveal that self-consolidating concrete containing 15% limestone filler, steam cured at 55°C, 70°C and 82°C, exhibited similar or superior mechanical and transport properties as well as long term durability performance compared to similar concrete without limestone filler. When the concrete is steam cured at 55°C, the chemical reactivity of limestone filler has an important role in enhancing the mechanical properties at 16 hours (compared to the concrete without limestone filler) and compensating for the dilution effect at 28 days. Although, at 300 days, the expansion of all concrete mixes are below 0.05%, the corresponding freeze-thaw durability factors vary widely and are controlled by the steam curing temperature and the chemical composition of the cement. Overall, the material properties indicate that the use

Calcinaksite, KNaCa(Si4O10) H2O, a new mineral from the Eifel volcanic area, Germany

NASA Astrophysics Data System (ADS)

Chukanov, Nikita V.; Aksenov, Sergey M.; Rastsvetaeva, Ramiza K.; Blass, Günter; Varlamov, Dmitry A.; Pekov, Igor V.; Belakovskiy, Dmitry I.; Gurzhiy, Vladislav V.

2015-08-01

The new mineral calcinaksite, ideally KNaCa(Si4O10) · H2O, the first hydrous and Ca-dominant member of the litidionite group, is found in a xenolith of metamorphosed carbonate-rich rock from the southern lava flow of the Bellerberg volcano, Eastern Eifel region, Rheinland-Pfalz, Germany. It is associated with wollastonite, gehlenite, brownmillerite, Ca2SiO4 (larnite or calcio-olivine), quartz, aragonite, calcite, jennite, tobermorite and ettringite. Calcinaksite occurs as clusters of colourless to light-grey subhedral prismatic crystals. The mineral is brittle, with Mohs' hardness of 5; Dmeas is 2.62(2) g/cm3 and Dcalc is 2.623 g/cm3. The IR spectrum shows the presence of H2O molecules forming three different H-bonds. Calcinaksite is optically biaxial (+), α = 1.542(2), β = 1.550(2), γ = 1.565(3), 2 V meas = 75(10). The chemical composition (electron-microprobe data, H2O determined by the Alimarin method, wt%) is: Na2O 6.69, K2O 12.01, CaO 15.04, FeO 0.59, SiO2 61.46, H2O 4.9, total 100.69. The empirical formula is H2.11 K0.99Na0.84Ca1.04Fe0.03Si3.98O11. The crystal structure was solved and refined to R 1 = 0.053, wR 2 = 0.075 based upon 3057 reflections having I > 3σ( I). Calcinaksite is triclinic, space group P , a = 7.021(2), b = 8.250(3), c = 10.145(2) Å. α = 102.23(2)°, β = 100.34(2)°, γ = 115.09(3)°, V = 495.4(3) Å3, Z = 2. The strongest reflections of the X-ray powder pattern [ d, Å ( I,%) ( hkl)] are: 3.431 (70) (-121, -211, -210, 012, 0-22), 3.300 (67) (-031), 3.173 (95) (-103, -201, -220, 003, 111), 3.060 (100) (-212, 2-11, -221, 200, -1-13, 021, -202), 2.851 (83) (0-23, -122, 1-13, 1-31), 2.664 (62) (1-23, -222, 201).

Abiotic hydrogen production in fresh and altered MSWI-residues: texture and microstructure investigation.

PubMed

Heuss-Assbichler, S; Magel, G; Fehr, K T

2010-10-01

Long-term hydrogen generation was observed in a Bavarian mono-landfill for municipal solid waste incineration (MSWI) residues. Hydration reactions of non-noble metals, especially aluminum, predominantly produce hydrogen at alkaline reaction conditions. Microscopic investigations show that aluminum metal may occur in different forms: as larger single grains, as small particles embedded in a vitrified matrix or less frequently in blowholes together with metallic silica. Four types of corrosion texture were observed, indicating different reaction mechanisms: aluminum hydroxide rims caused by hydration reactions at alkaline reaction conditions (reaction type 1) and multiphase rims with ettringite and hydrocalumite due to the reaction of aluminum hydroxide with sulfate and chloride ions which are solved in the pore water (reaction type 2). Galvanic corrosion textures due to the electric potential difference between aluminum and embedded intermetallic Fe- or Cu-rich exsolution phases lead to two further corrosion textures: Strong hydration effects of aluminum except a border of aluminum remnant directly beside the Fe- or Cu-rich segregations were only observed in fresh samples (reaction type 3). The reaction type 4 shows a network of Al-hydroxide veins occurring along the embedded intermetallic Fe- or Cu-rich exsolution segregation pattern within the metallic aluminum grain. Metal particles enclosed in vitrified particles offers the potential for future corrosion processes. The occurrence of corrosion types 1, 2 and 3 in fresh bottom ashes indicates that these reaction mechanisms predominate during the first reaction period in the presence of chlorine in an alkaline solution. Corrosion type 4, however, was additionally observed in aged samples. Here aluminum acts as sacrificed anode implying electrochemical reaction due to electrolytic pore water. Chloride in the system keeps the reaction alive as Al-hydroxide is solved which normally builds a protection shield around

Incorporation of gypsum waste in ceramic block production: Proposal for a minimal battery of tests to evaluate technical and environmental viability of this recycling process.

PubMed

Godinho-Castro, Alcione P; Testolin, Renan C; Janke, Leandro; Corrêa, Albertina X R; Radetski, Claudemir M

2012-01-01

Civil engineering-related construction and demolition debris is an important source of waste disposed of in municipal solid waste landfills. After clay materials, gypsum waste is the second largest contributor to the residential construction waste stream. As demand for sustainable building practices grows, interest in recovering gypsum waste from construction and demolition debris is increasing, but there is a lack of standardized tests to evaluate the technical and environmental viability of this solid waste recycling process. By recycling gypsum waste, natural deposits of gypsum might be conserved and high amounts of the waste by-product could be reused in the civil construction industry. In this context, this paper investigates a physical property (i.e., resistance to axial compression), the chemical composition and the ecotoxicological potential of ceramic blocks constructed with different proportions of clay, cement and gypsum waste, and assesses the feasibility of using a minimal battery of tests to evaluate the viability of this recycling process. Consideration of the results for the resistance to axial compression tests together with production costs revealed that the best formulation was 35% of plastic clay, 35% of non-plastic clay, 10% of Portland cement and 20% of gypsum waste, which showed a mean resistance of 4.64MPa. Energy dispersive X-ray spectrometry showed calcium and sulfur to be the main elements, while quartz, gypsum, ettringite and nacrite were the main crystalline compounds found in this formulation. Ecotoxicity tests showed that leachate from this formulation is weakly toxic toward daphnids and bacteria (EC(20%)=69.0 and 75.0, respectively), while for algae and fish the leachate samples were not toxic at the EC(50%) level. Overall, these results show that the addition of 20% of gypsum waste to the ceramic blocks could provide a viable substitute for clay in the ceramics industry and the tests applied in this study proved to be a useful tool

Properties of mortars made by uncalcined FGD gypsum-fly ash-ground granulated blast furnace slag composite binder

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhong Shiyun, E-mail: tjzhongshiyun@163.com; Ni Kun; Li Jinmei

2012-07-15

Highlights: Black-Right-Pointing-Pointer The mortar with uncalcined FGD gypsum has suitable workability. Black-Right-Pointing-Pointer The strength of mortar with uncalcined FGD gypsum is higher than that of mortar without uncalcined FGD gypsum. Black-Right-Pointing-Pointer The dry shrinkage of mortar with uncalcined FGD gypsum is lower than that of mortar without uncalcined FGD gypsum. Black-Right-Pointing-Pointer The leaching of sulfate ion of mortar is studied. - Abstract: A series of novel mortars were developed from composite binder of uncalcined FGD gypsum, fly ash (FA) and ground granulated blast furnace slag (GGBFS) for the good utilization of flue gas desulphurization (FGD) gypsum. At a fixed ratiomore » (20%) of GGBFS to the composite binder, keeping consistency of the mortar between 9.5 and 10.0 cm, the properties of the composite mortar were studied. The results show that higher water/binder (W/B) is required to keep the consistency when increasing the percentage of FGD gypsum. No obvious influences of the W/B and content of FGD gypsum on the bleeding of paste were observed which keeps lower than 2% under all experimental conditions tried. The highest compressive and flexural strengths (ratio is 20% FGD gypsum, 20% GGBFS and 60% FA) are 22.6 and 4.3 MPa at 28 days, respectively. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) results indicate that massive ettringite crystals and C-S-H gels exist in the hydration products. At 90 days the mortars with FGD gypsum is dramatically smaller drying shrinkage (563-938 micro strain) than that without FGD gypsum (about 2250 micro strain). The release of the SO{sub 4}{sup 2-} from the mortar was analyzed, indicating that the dissolution of sulfate increases with FGD gypsum. The concentration of SO{sub 4}{sup 2-} releasing from the mortar with 10% FGD gypsum is almost equal to that obtained from the mortar without FGD gypsum. The release of SO{sub 4}{sup 2-} from the mortar with 20% FGD gypsum is

In-Situ Production of Calcium Carbonate Nanoparticles in Fresh Concrete Using Pre-carbonation Method

NASA Astrophysics Data System (ADS)

Qian, Xin

To reduce the carbon footprint of ordinary Portland cement (OPC)-based concrete, a novel technique, pre-carbonation process, has been developed to produce CaCO3 nanoparticles in fresh concrete. In this technique, gaseous CO2 is first absorbed into a slurry of calcium-rich minerals which is then blended with other ingredients to produce mortar/concrete. The objective of this work is to obtain an in-depth understanding of the underlying scientific mechanisms associated with the enhancement of strength and durability of the concrete induced by the new method. A comprehensive research plan has been carried out to study the carbonated slaked lime slurry and the effect of carbonated slaked lime slurry on the performance of OPC-based concrete, and to evaluate the potentials of the pre-carbonation method. Experimental studies show that carbonating the calcium-rich mineral slurry with CO2 can produce CaCO3 nanoparticles and Ca(HCO 3)2 in the slurry, and these carbonation products were dictated by four parameters of the pre-carbonation method: the duration and temperature of the carbonation, the concentration of the calcium source slurry, and the stirring method of the calcium source slurry during the carbonation. The mechanical properties and durability of the mortar/concrete made with the carbonated slurry were significantly improved, which can be attributed to major mechanisms induced by the pre-carbonation method: promoted hydration of the cement and denser microstructure of the mortar/concrete. Calorimetry testing showed that the hydration of OPC was greatly improved by the pre-carbonation because of the extra heterogenous nucleation sites provided by the CaCO3 nanoparticles. XRD and TGA results revealed that more ettringite was produced in the mortar/concrete with pre-carbonated slaked lime slurry. The overall volume of the hydration products of the cement was increased by the pre-carbonation, leading to denser microstructure of the mortar/concrete. It has been found

Apatite formation on bioactive calcium-silicate cements for dentistry affects surface topography and human marrow stromal cells proliferation.

PubMed

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

MTA and F-doped MTA cements used as sealers with warm gutta-percha. Long-term study of sealing ability.

PubMed

Gandolfi, M G; Prati, C

2010-10-01

-like ettringite crystals and round formations of calcium silicate hydrate gel. Fluoride-doped MTA demonstrated stable sealing during a period of up to 6 months and significantly better than conventional calcium silicate MTA cements and comparable to AH Plus. The study supports the suitability of calcium silicate MTA cements as sealers in association with warm gutta-percha for root filling. © 2010 International Endodontic Journal.

Hydration characteristics of zirconium oxide replaced Portland cement for use as a root-end filling material.

PubMed

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

DEMONSTRATION OF LEACHXS/ORCHESTRA CAPABILITIES BY SIMULATING CONSTITUENT RELEASE FROM A CEMENTITIOUS WASTE FORM IN A REINFORCED CONCRETE VAULT

DOE Office of Scientific and Technical Information (OSTI.GOV)

Langton, C.; Meeussen, J.; Sloot, H.

2010-03-31

The objective of the work described in this report is to demonstrate the capabilities of the current version of LeachXS{trademark}/ORCHESTRA for simulating chemical behavior and constituent release processes in a range of applications that are relevant to the CBP. This report illustrates the use of LeachXS{trademark}/ORCHESTRA for the following applications: (1) Comparing model and experimental results for leaching tests for a range of cementitious materials including cement mortars, grout, stabilized waste, and concrete. The leaching test data includes liquid-solid partitioning as a function of pH and release rates based on laboratory column, monolith, and field testing. (2) Modeling chemical speciationmore » of constituents in cementitious materials, including liquid-solid partitioning and release rates. (3) Evaluating uncertainty in model predictions based on uncertainty in underlying composition, thermodynamic, and transport characteristics. (4) Generating predominance diagrams to evaluate predicted chemical changes as a result of material aging using the example of exposure to atmospheric conditions. (5) Modeling coupled geochemical speciation and diffusion in a three layer system consisting of a layer of Saltstone, a concrete barrier, and a layer of soil in contact with air. The simulations show developing concentration fronts over a time period of 1000 years. (6) Modeling sulfate attack and cracking due to ettringite formation. A detailed example for this case is provided in a separate article by the authors (Sarkar et al. 2010). Finally, based on the computed results, the sensitive input parameters for this type of modeling are identified and discussed. The chemical speciation behavior of substances is calculated for a batch system and also in combination with transport and within a three layer system. This includes release from a barrier to the surrounding soil as a function of time. As input for the simulations, the physical and chemical properties of

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

Fiber-Reinforced Rocks Akin to Roman Concrete Help Explain Ground Deformation at Campi Flegrei Caldera

NASA Astrophysics Data System (ADS)

Vanorio, Tiziana; Kanitpanyacharoen, Waruntorn

2016-04-01

The caldera of Campi Flegrei is one of the active hydrothermal systems of the Mediterranean region experiencing notable unrest episodes in a densely populated area. During the last crisis of 1982-1984, nearly 40,000 people were evacuated for almost two years from the main town of Pozzuoli, the Roman Puteoli, due to the large uplifts (~2 m over two years) and the persistent seismic activity. The evacuation severely hampered the economy and the social make-up of the community, which included the relocation of schools and commercial shops as well as the harbor being rendered useless for docking. Despite the large uplifts, the release of strain appears delayed. Seismicity begins and reaches a magnitude of 4.0 only upon relatively large uplifts (~ 70-80 cm) contrary to what is generally observed for calderas exhibiting much lower deformation levels. Over and above the specific mechanism causing the unrest and the lack of identification of a shallow magmatic reservoir (< 4 km) by seismic data, there is a core question of how the subsurface rocks of Campi Flegrei withstand a large strain and have high strength. We performed a series of direct measurements on deep well cores by combining high-resolution microstructural and mineralogical analyses with the elastic and mechanical properties of well cores from the deep wells drilled in the area right before the unrest of 1982-1984 - San Vito (SV1 and SV2) and Mofete (MF1, MF2, MF5). The rock physics analysis of the well cores provides evidence for the existence of two horizons, above and below the seismogenic area, underlying a natural, coupled process. The basement is a calc-silicate rock housing hydrothermal decarbonation reactions, which provide lime-rich fluids. The caprock above the seismogenic area has a pozzolanic composition and a fibril-rich matrix made of intertwining filaments of ettringite and tobemorite, resulting from lime-pozzolanic reactions. These findings provide evidence for a natural process reflecting that

Raman spectroscopy for characterizing and determining the pozzolanic reactivity of fly ashes

NASA Astrophysics Data System (ADS)

Garg, Nishant

The efficacy and potential of Raman spectroscopy in characterization of a commercial Ordinary Portland Cement (OPC) and three fly ashes (FA's), and their evolving hydration products were studied in this Master's thesis work. While there have been several studies focusing on the application of Raman spectroscopy to synthetic, pure samples, work on commercial cementitious systems is scarce. This work covers this gap by evaluating mixtures containing cements and fly ashes. The study first involved determination followed by establishment of instrumental configuration and testing parameters optimum for studying cementitious materials both in the dry and wet form. It was found that by tweaking several parameters, collection methodologies and analysis techniques, improved, representative and reproducible data could be obtained. Mapping a representative area to determine the spatial distribution and concentration of sulfates and hydroxides on sample surfaces was found to be the most effective way to study these complex and heterogeneous systems. The Raman dry analysis of OPC and three different FA's of varying calcium contents and reactivity was able to identify the major mineralogical phases in these binders and the results were in correlation with the X-ray diffraction data. The observed calcium and sulfate phases and their relative concentration also agreed well with the supplementary compositional data obtained from X-ray fluorescence and Atomic absorption spectrometry. The wet analysis of pastes prepared with 100% OPC and 50%OPC+50%FA(1,2,3) followed the hydration process of the systems for 56 days (0, 0.2, 2, 4, 8, 12, 16, 20, 24, 48, 72 hours, 7, 14, 21, 28, and 56 days). Consistency of trends in the hydration mechanism of such pastes was only obtained when studies were focused on narrow wavenumber ranges: 950--1050 cm-1 for evolution of sulfates and 3600--3700cm-1 for evolution of hydroxides. Gradual disappearance of Gypsum with a parallel formation of Ettringite

Characterization of cementitiously stabilized subgrades for mechanistic-empirical pavement design

NASA Astrophysics Data System (ADS)

Solanki, Pranshoo

ettringite, responsible for sulfate-induced heaving, is also discussed. For Level 2 design of pavements, a total of four stress-based statistical models and two feed-forward-type artificial neural network (ANN) models, are evaluated for predicting resilient modulus of 28-day cured stabilized specimens. Specifically, one semi-log stress-based, three log-log stress-based, one Multi-Layer Perceptrons Network (MLPN), and one Radial Basis Function Network (RBFN) are developed. Overall, semi-log stress-based and MLPN neural network are found to show best acceptable performance for the present evaluation and validation datasets. Further, correlations are presented for stress-based models to correlate Mr with compacted specimen characteristics and soil/additive properties. Additionally, the effect of type of additive on indirect tensile and fatigue characteristics of selected stabilized P- and V-soil is evaluated. This study is based on the fact that stabilized layer is subjected to tensile stresses under wheel loading. Thus, the resilient modulus in tension (M rt), fatigue life and strength in tension (sigmat) or flexure (represented by modulus of rupture, MOR) becomes another important design parameter within the mechanistic framework. Cylindrical specimens are prepared, cured for 28 days and subjected to different stress sequences in indirect tension to study the Mrt. On the other hand, stabilized beam specimens are compacted using a Linear Kneading Compactor and subjected to repeated cycles of reloading-unloading after 28 days of curing in a four-point beam fatigue apparatus for evaluating fatigue life and flexural stiffness. It is found that all three additives improved the Mrt, sigmat and MOR values; however, degree of improvement varied with the type of additive and soil. This study encompasses the differences in the design of semi-rigid pavements developed using AASHTO 1993 and AASHTO 2002 MEPDG methodologies. Further, the design curves for fatigue performance prediction of

Spectroscopic characterisation of biological vaterite: relations to synthetic and geological vaterites

NASA Astrophysics Data System (ADS)

Jacob, D. E.; Wehrmeister, U.; Soldati, A. L.; Hofmeister, W.

2009-04-01

vaterite. Additionally, the influence of magnesium on the widths of the Raman bands (FWHM = full width at half maximum) is studied in order to detect a potential correlation between the magnesium content and the FWHMs in analogy to similar studies on aragonite and calcite. The results imply that, although a hexagonal symmetry and the space group P63/mmc are commonly used in the literature, it is equally possible that there are at least three structurally non-equivalent carbonate groups in the vaterite structure. It could be speculated that the (CO3) layers are generally similar, whereas the stacking sequence of these layers may lead to a lower symmetry. Non-beaded freshwater cultured pearls from China and Japan, grown in mussels of the genus Hyriopsis were studied for their different CaCO3- polymorphs and chemical composition. Vaterite was identified by Micro-Raman spectroscopy in polished cross-sections. Vaterite forms relatively small areas (1-1.5 mm diameter) which are spherical to irregular and always in close proximity to the centre of the pearl. Trace elements in different CaCO3 polymorphs were measured using LA-ICP-MS (New Wave Research 213 nm Laser/Agilent 7500ce quadrupole ICP-MS). Geological samples come from the Bellerberg (Eifel Mountains, Germany). The rocks contain a mixture of minerals (e.g. ettringite, calcite, aragonite and tobermorite) including white to dark yellow microcrystalline mineral aggregates of vaterite. Synthetic vaterite samples were produced in collaboration with the Department of Inorganic and Analytical Chemistry at the University of Mainz by precipitation from a solution of CaCl2 and poly(aspartic acid), in the presence of (NH4)2CO3 (Loges et al., 2006). The Raman band position and FWHM of all samples are in relative good agreement, independent of their origin. The characteristic features of the Raman spectrum of vaterite are: at least eight relative broad bands in the region of the external lattice modes, splitting of the most intense