Accurate Characterization of the Pore Volume in Microporous Crystalline Materials
2017-01-01
Pore volume is one of the main properties for the characterization of microporous crystals. It is experimentally measurable, and it can also be obtained from the refined unit cell by a number of computational techniques. In this work, we assess the accuracy and the discrepancies between the different computational methods which are commonly used for this purpose, i.e, geometric, helium, and probe center pore volumes, by studying a database of more than 5000 frameworks. We developed a new technique to fully characterize the internal void of a microporous material and to compute the probe-accessible and -occupiable pore volume. We show that, unlike the other definitions of pore volume, the occupiable pore volume can be directly related to the experimentally measured pore volumes from nitrogen isotherms. PMID:28636815
Accurate Characterization of the Pore Volume in Microporous Crystalline Materials
Ongari, Daniele; Boyd, Peter G.; Barthel, Senja; ...
2017-06-21
Pore volume is one of the main properties for the characterization of microporous crystals. It is experimentally measurable, and it can also be obtained from the refined unit cell by a number of computational techniques. In this work, we assess the accuracy and the discrepancies between the different computational methods which are commonly used for this purpose, i.e, geometric, helium, and probe center pore volumes, by studying a database of more than 5000 frameworks. We developed a new technique to fully characterize the internal void of a microporous material and to compute the probe-accessible and -occupiable pore volume. Lasty, wemore » show that, unlike the other definitions of pore volume, the occupiable pore volume can be directly related to the experimentally measured pore volumes from nitrogen isotherms.« less
Violi, Ianina L; Perez, M Dolores; Fuertes, M Cecilia; Soler-Illia, Galo J A A
2012-08-01
Highly porous (V(mesopore) = 25-50%) and ordered mesoporous titania thin films (MTTF) were prepared on ITO (indium tin oxide)-covered glass by a fast two-step method. The effects of substrate surface modification and thermal treatment on pore order, accessibility and crystallinity of the MTTF were systematically studied for MTTF deposited onto bare and titania-modified ITO. MTTF exposed briefly to 550 °C resulted in highly ordered films with grid-like structures, enlarged pore size, and increased accessible pore volume when prepared onto the modified ITO substrate. Mesostructure collapse and no significant change in pore volume were observed for MTTF deposited on bare ITO substrates. Highly crystalline anatase was obtained for MTTF prepared on the modified-ITO treated at high temperatures, establishing the relationship between grid-like structures and titania crystallization. Photocatalytic activity was maximized for samples with increased crystallization and high accessible pore volume. In this manner, a simple way of designing materials with optimized characteristics for optoelectronic applications was achieved through the modification of the ITO surface and a controlled thermal treatment.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ongari, Daniele; Boyd, Peter G.; Barthel, Senja
Pore volume is one of the main properties for the characterization of microporous crystals. It is experimentally measurable, and it can also be obtained from the refined unit cell by a number of computational techniques. In this work, we assess the accuracy and the discrepancies between the different computational methods which are commonly used for this purpose, i.e, geometric, helium, and probe center pore volumes, by studying a database of more than 5000 frameworks. We developed a new technique to fully characterize the internal void of a microporous material and to compute the probe-accessible and -occupiable pore volume. Lasty, wemore » show that, unlike the other definitions of pore volume, the occupiable pore volume can be directly related to the experimentally measured pore volumes from nitrogen isotherms.« less
NASA Astrophysics Data System (ADS)
Akbari, A.; Ghoshal, S.
2016-12-01
We define a new parameter, "bioaccessible porosity", the fraction of aggregate volume accessible to soil bacteria, towards a priori assessment of hydrocarbon bioremediation end points. Microbial uptake of poorly soluble hydrocarbons occurs through direct uptake or micellar solubilzation/emulsification associated with biosurfactant production, and requires close proximity of bacteria and hydrocarbon phase. In subsurface microporous environments, bioremediation rates are attenuated when residual hydrophobic contamination is entrapped in sterically restrictive environments which is not accessible to soil bacteria. This study presents new approaches for characterization of the microstructure of porous media and as well, the ability of indigenous hydrocarbon degraders to access to a range of pore sizes. Bacterial access to poorly soluble hydrocarbons in soil micro pores were simulated with bioreactors with membranes with different pore sizes containing the hydrocarbon degrading bacteria, Dietzia maris. D. maris is Gram-positive, and nonmotile that we isolated as the major hydrocarbon degrader from a fine-grained, weathered, hydrocarbon-contaminated site soil. Under nutritional stress, planktonic D. maris cells were aggregated and accessed 5 µm but not 3 µm and smaller pores. However, when hexadecane was available at the pore mouth, D. maris colonized the pore mouth, and accessed pores as small as 0.4 µm. This suggests bacterial accessibility to different pore sizes is regulated by nutritional conditions. A combination of X-ray micro-CT scanning, gas adsorption and mercury intrusion porosimetry was used to characterize the range of pore sizes of soil aggregates. In case of the studied contaminated soil, the bioaccessible porosity were determined as 25% , 27% and 29% (assuming 4, 1, 0.4 µm respectively as accessibility criteria), and about 2.7% of aggregate volume was attributed to 0.006-0.4 µm pores. The 2% aggregate volume at an assumed saturation of 10% could accommodate 1000 mg/ kg soil of oil. The remediation endpoint after extended biotreatment was at similar order of magnitude of 600 mg/kg. The approach introduced here could be used for qualitative assessment of attainable bioremediation endpoint in soils with different microstructure and hydrocarbon degrading bacterial community.
Ion beam promoted lithium absorption in glassy polymeric carbon
NASA Astrophysics Data System (ADS)
Ila, D.; Zimmerman, R. L.; Jenkins, G. M.; Maleki, H.; Poker, D. B.
1995-12-01
Glassy Polymeric Carbon (GPC) samples prepared from a precursor possess accessible pore volume that depends on the heat treatment temperature. We have shown that lithium percolates without diffusion into the accessible pores of GPC samples immersed in a molten lithium salt bath at 700°C. Ion bombardment with 10 MeV Au atoms increases the total pore volume available for lithium occupation even for samples normally impermeable to lithium. The lithium concentration depth profile is measured using Li7(p,2α) nuclear reaction analysis. We will report on lithium percolation into GPC prepared at temperatures between 500°C and 1000°C and activated by a 10 MeV gold ion bombardment.
Changes in pore structure of coal caused by coal-to-gas bioconversion
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhang, Rui; Liu, Shimin; Bahadur, Jitendra
Microbial enhanced coalbed methane (ME-CBM) recovery is critically examined as a viable technology for natural gas recovery from coalbed methane (CBM) reservoirs. Since the majority of gas-in-place (GIP) is stored as an adsorbed phase in fine pores of coal matrix, the nano-pore structure directly influences gas storage and transport properties. Only limited studies have quantified the alteration of the nano-pore structure due to ME-CBM treatment. This study examines the evolution of the pore structure using a combination of small angle X-ray scattering (SAXS), low-pressure N 2 and CO 2 adsorption (LPGA) and high-pressure methane adsorption methods. The results show thatmore » the surface fractal dimension decreases for the two bioconverted coals compared to the untreated coal. After bio-treatment, the mesopore surface area and pore volume decrease with the average pore diameter increases, while the micropore surface area increases with pore volume decreases. Both inaccessible meso-/micropore size distributions decrease after bioconversion, while the accessible micropore size distribution increases, making a portion of closed micropore network accessible. In addition, the methane adsorption capacities increase after bio-treatment, which is confirmed by the increase of micropore surface area. A conceptual physical model of methanogenesis is proposed based on the evolution of the pore structure.« less
Changes in pore structure of coal caused by coal-to-gas bioconversion
Zhang, Rui; Liu, Shimin; Bahadur, Jitendra; ...
2017-06-19
Microbial enhanced coalbed methane (ME-CBM) recovery is critically examined as a viable technology for natural gas recovery from coalbed methane (CBM) reservoirs. Since the majority of gas-in-place (GIP) is stored as an adsorbed phase in fine pores of coal matrix, the nano-pore structure directly influences gas storage and transport properties. Only limited studies have quantified the alteration of the nano-pore structure due to ME-CBM treatment. This study examines the evolution of the pore structure using a combination of small angle X-ray scattering (SAXS), low-pressure N 2 and CO 2 adsorption (LPGA) and high-pressure methane adsorption methods. The results show thatmore » the surface fractal dimension decreases for the two bioconverted coals compared to the untreated coal. After bio-treatment, the mesopore surface area and pore volume decrease with the average pore diameter increases, while the micropore surface area increases with pore volume decreases. Both inaccessible meso-/micropore size distributions decrease after bioconversion, while the accessible micropore size distribution increases, making a portion of closed micropore network accessible. In addition, the methane adsorption capacities increase after bio-treatment, which is confirmed by the increase of micropore surface area. A conceptual physical model of methanogenesis is proposed based on the evolution of the pore structure.« less
Ion beam promoted lithium absorption in glassy polymeric carbon
NASA Astrophysics Data System (ADS)
Zimmerman, R. L.; Ila, D.; Jenkins, G. M.; Maleki, H.; Poker, D. B.
1995-12-01
Glassy Polymeric Carbon (GPC) samples prepared from a precursor possess accessible pore volume that depends on the heat treatment temperature [G.M. Jenkins and K. Kawamura, Polymeric Carbons - Carbon Fiber, Glass and Char (Cambridge University Press, Cambridge, 1976) p. 140]. We have shown that lithium percolates without diffusion into the accessible pores of GPC samples immersed in a molten lithium salt bath at 700°C [D. Ila, G.M. Jenkins, L.R. Holland, A.L. Evelyn and H. Jena, Vacuum 45 (1994) 451]. Ion bombardment with 10 MeV Au atoms increases the total pore volume available for lithium occupation even for samples normally impermeable to lithium. The lithium concentration depth profile is measured using Li 7(p,2α) nuclear reaction analysis. We will report on lithium percolation into GPC prepared at temperatures between 500°C and 1000°C and activated by a 10 MeV gold ion bombardment.
Effects of exchanged cation on the microporosity of montmorillonite
Rutherford, David W.; Chiou, Cary T.; Eberl, Dennis D.
1997-01-01
The micropore volumes of 2 montmorillonites (SAz-1 and SWy-1), each exchanged with Ca, Na, K, Cs and tetramethylammonium (TMA) ions, were calculated from the measured vapor adsorption data of N2 and neo-hexane by use of t- and αs-plots. The corresponding surface areas of the exchanged clays were determined from Brunauer-Emmett-Teller (BET) plots of N2 adsorption data. Micropore volumes and surface areas of the samples increased with the size of exchanged cation: TMA > Cs > K > Ca > Na. The SAz-1 exchanged clays showed generally greater micropore volumes and surface areas than the corresponding SWy-1 clays. The vapor adsorption data and d(001) measurements for dry clay samples were used together to evaluate the likely locations and accessibility of clay micropores, especially the relative accessibility of their interlayer spacing. For both source clays exchanged with Na, Ca and K ions, the interlayer spacing appeared to be too small to admit nonpolar gases and the accessible micropores appeared to have dimensions greater than 5.0 Å, the limiting molecular dimension of neo-hexane. In these systems, there was a good consistency of micropore volumes detected by N2 and neo-hexane. When the clays were intercalated with relatively large cations (TMA and possibly Cs), the large layer expansion created additional microporosity, which was more readily accessible to small N2 than to relatively large neo-hexane. Hence, the micropore volume as detected by N2 was greater than that detected by neo-hexane. The micropore volumes with pore dimensions greater than 5 Å determined for clays exchanged with Na, Ca and K likely resulted from the pores on particle edges and void created by overlap regions of layers. The increase in micropore volumes with pore dimensions less than 5 Å determined for clays exchanged with TMA and possibly Cs could be caused by opening of the interlayer region by the intercalation of these large cations.
Gu, Xin; Mildner, David F. R.; Cole, David R.; ...
2016-04-28
Pores within organic matter (OM) are a significant contributor to the total pore system in gas shales. These pores contribute most of the storage capacity in gas shales. Here we present a novel approach to characterize the OM pore structure (including the porosity, specific surface area, pore size distribution, and water accessibility) in Marcellus shale. By using ultrasmall and small-angle neutron scattering, and by exploiting the contrast matching of the shale matrix with suitable mixtures of deuterated and protonated water, both total and water-accessible porosity were measured on centimeter-sized samples from two boreholes from the nanometer to micrometer scale withmore » good statistical coverage. Samples were also measured after combustion at 450 °C. Analysis of scattering data from these procedures allowed quantification of OM porosity and water accessibility. OM hosts 24–47% of the total porosity for both organic-rich and -poor samples. This porosity occupies as much as 29% of the OM volume. In contrast to the current paradigm in the literature that OM porosity is organophilic and therefore not likely to contain water, our results demonstrate that OM pores with widths >20 nm exhibit the characteristics of water accessibility. In conclusion, our approach reveals the complex structure and wetting behavior of the OM porosity at scales that are hard to interrogate using other techniques.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Gu, Xin; Mildner, David F. R.; Cole, David R.
Pores within organic matter (OM) are a significant contributor to the total pore system in gas shales. These pores contribute most of the storage capacity in gas shales. Here we present a novel approach to characterize the OM pore structure (including the porosity, specific surface area, pore size distribution, and water accessibility) in Marcellus shale. By using ultrasmall and small-angle neutron scattering, and by exploiting the contrast matching of the shale matrix with suitable mixtures of deuterated and protonated water, both total and water-accessible porosity were measured on centimeter-sized samples from two boreholes from the nanometer to micrometer scale withmore » good statistical coverage. Samples were also measured after combustion at 450 °C. Analysis of scattering data from these procedures allowed quantification of OM porosity and water accessibility. OM hosts 24–47% of the total porosity for both organic-rich and -poor samples. This porosity occupies as much as 29% of the OM volume. In contrast to the current paradigm in the literature that OM porosity is organophilic and therefore not likely to contain water, our results demonstrate that OM pores with widths >20 nm exhibit the characteristics of water accessibility. In conclusion, our approach reveals the complex structure and wetting behavior of the OM porosity at scales that are hard to interrogate using other techniques.« less
NASA Astrophysics Data System (ADS)
Seredych, Mykola; Koscinski, Mikolaj; Sliwinska-Bartkowiak, Malgorzata; Bandosz, Teresa J.
2012-12-01
Composites of commercial graphene and nanoporous sodium-salt-polymer-derived carbons were prepared with 5 or 20 weight% graphene. The materials were characterized using the adsorption of nitrogen, SEM/EDX, thermal analysis, Raman spectroscopy and potentiometric titration. The samples' conductivity was also measured. The performance of the carbon composites in energy storage was linked to their porosity and electronic conductivity. The small pores (<0.7) were found as very active for double layer capacitance. It was demonstrated that when double layer capacitance is a predominant mechanism of charge storage, the degree of the pore space utilization for that storage can be increased by increasing the conductivity of the carbons. That active pore space utilization is defined as gravimetric capacitance per unit pore volume in pores smaller than 0.7 nm. Its magnitude is affected by conductivity of the carbon materials. The functional groups, besides pseudocapacitive contribution, increased the wettability and thus the degree of the pore space utilization. Graphene phase, owing to its conductivity, also took part in an insitu increase of the small pore accessibility and thus the capacitance of the composites via enhancing an electron transfer to small pores and thus imposing the reduction of groups blocking the pores for electrolyte ions.
Partitioning of habitable pore space in earthworm burrows.
Gorres, Josef H; Amador, Jose A
2010-03-01
Earthworms affect macro-pore structure of soils. However, some studies suggest that earthworm burrow walls and casts themselves differ greatly in structure from surrounding soils, potentially creating habitat for microbivorours nematodes which accelerate the decomposition and C and N mineralization. In this study aggregates were sampled from the burrow walls of the anecic earthworm Lumbricus terrestris and bulk soil (not altered by earthworms) from mesocosm incubated in the lab for 0, 1, 3, 5 and 16 weeks. Pore volumes and pore sizes were measured in triplicate with Mercury Intrusion Porosimetry (MIP). This method is well suited to establish pore size structure in the context of habitat, because it measures the stepwise intrusion of mercury from the outside of the aggregate into ever smaller pores. The progress of mercury into the aggregate interior thus resembles potential paths of a nematode into accessible habitable pore spaces residing in an aggregate. Total specific pore volume, V(s), varied between 0.13 and 0.18 mL/g and increased from 3 to 16 weeks in both burrow and bulk soil. Differences between total V(s) of bulk and burrow samples were not significant on any sampling date. However, differences were significant for pore size fractions at the scale of nematode body diameter.
Partitioning of habitable pore space in earthworm burrows
Amador, Jose A.
2010-01-01
Earthworms affect macro-pore structure of soils. However, some studies suggest that earthworm burrow walls and casts themselves differ greatly in structure from surrounding soils, potentially creating habitat for microbivorours nematodes which accelerate the decomposition and C and N mineralization. In this study aggregates were sampled from the burrow walls of the anecic earthworm Lumbricus terrestris and bulk soil (not altered by earthworms) from mesocosm incubated in the lab for 0, 1, 3, 5 and 16 weeks. Pore volumes and pore sizes were measured in triplicate with Mercury Intrusion Porosimetry (MIP). This method is well suited to establish pore size structure in the context of habitat, because it measures the stepwise intrusion of mercury from the outside of the aggregate into ever smaller pores. The progress of mercury into the aggregate interior thus resembles potential paths of a nematode into accessible habitable pore spaces residing in an aggregate. Total specific pore volume, Vs, varied between 0.13 and 0.18 mL/g and increased from 3 to 16 weeks in both burrow and bulk soil. Differences between total Vs of bulk and burrow samples were not significant on any sampling date. However, differences were significant for pore size fractions at the scale of nematode body diameter. PMID:22736839
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hong, Seok -Min; Jang, Eunji; Dysart, Arthur D.
Here, microporous carbon compartments (MCCs) were developed via controlled carbonization of wheat flour producing large cavities that allow CO 2 gas molecules to access micropores and adsorb effectively. KOH activation of MCCs was conducted at 700 °C with varying mass ratios of KOH/C ranging from 1 to 5, and the effects of activation conditions on the prepared carbon materials in terms of the characteristics and behavior of CO 2 adsorption were investigated. Textural properties, such as specific surface area and total pore volume, linearly increased with the KOH/C ratio, attributed to the development of pores and enlargement of pores withinmore » carbon. The highest CO 2 adsorption capacities of 5.70 mol kg -1 at 0 °C and 3.48 mol kg -1 at 25 °C were obtained for MCC activated with a KOH/C ratio of 3 (MCC-K3). In addition, CO 2 adsorption uptake was significantly dependent on the volume of narrow micropores with a pore size of less than 0.8 nm rather than the volume of larger pores or surface area. MCC-K3 also exhibited excellent cyclic stability, facile regeneration, and rapid adsorption kinetics. As compared to the pseudofirst-order model, the pseudo-second-order kinetic model described the experimental adsorption data methodically.« less
CO 2 capture in the sustainable wheat-derived activated microporous carbon compartments
Hong, Seok -Min; Jang, Eunji; Dysart, Arthur D.; ...
2016-10-04
Here, microporous carbon compartments (MCCs) were developed via controlled carbonization of wheat flour producing large cavities that allow CO 2 gas molecules to access micropores and adsorb effectively. KOH activation of MCCs was conducted at 700 °C with varying mass ratios of KOH/C ranging from 1 to 5, and the effects of activation conditions on the prepared carbon materials in terms of the characteristics and behavior of CO 2 adsorption were investigated. Textural properties, such as specific surface area and total pore volume, linearly increased with the KOH/C ratio, attributed to the development of pores and enlargement of pores withinmore » carbon. The highest CO 2 adsorption capacities of 5.70 mol kg -1 at 0 °C and 3.48 mol kg -1 at 25 °C were obtained for MCC activated with a KOH/C ratio of 3 (MCC-K3). In addition, CO 2 adsorption uptake was significantly dependent on the volume of narrow micropores with a pore size of less than 0.8 nm rather than the volume of larger pores or surface area. MCC-K3 also exhibited excellent cyclic stability, facile regeneration, and rapid adsorption kinetics. As compared to the pseudofirst-order model, the pseudo-second-order kinetic model described the experimental adsorption data methodically.« less
CO2 Capture in the Sustainable Wheat-Derived Activated Microporous Carbon Compartments
NASA Astrophysics Data System (ADS)
Hong, Seok-Min; Jang, Eunji; Dysart, Arthur D.; Pol, Vilas G.; Lee, Ki Bong
2016-10-01
Microporous carbon compartments (MCCs) were developed via controlled carbonization of wheat flour producing large cavities that allow CO2 gas molecules to access micropores and adsorb effectively. KOH activation of MCCs was conducted at 700 °C with varying mass ratios of KOH/C ranging from 1 to 5, and the effects of activation conditions on the prepared carbon materials in terms of the characteristics and behavior of CO2 adsorption were investigated. Textural properties, such as specific surface area and total pore volume, linearly increased with the KOH/C ratio, attributed to the development of pores and enlargement of pores within carbon. The highest CO2 adsorption capacities of 5.70 mol kg-1 at 0 °C and 3.48 mol kg-1 at 25 °C were obtained for MCC activated with a KOH/C ratio of 3 (MCC-K3). In addition, CO2 adsorption uptake was significantly dependent on the volume of narrow micropores with a pore size of less than 0.8 nm rather than the volume of larger pores or surface area. MCC-K3 also exhibited excellent cyclic stability, facile regeneration, and rapid adsorption kinetics. As compared to the pseudo-first-order model, the pseudo-second-order kinetic model described the experimental adsorption data methodically.
Akbari, Ali; Ghoshal, Subhasis
2015-12-15
We evaluated the role of soil aggregate pore size on biodegradation of essentially insoluble petroleum hydrocarbons that are biodegraded primarily at the oil-water interface. The size and spatial distribution of pores in aggregates sampled from biodegradation experiments of a clayey, aggregated, hydrocarbon-contaminated soil with relatively high bioremediation end point were characterized by image analyses of X-ray micro-CT scans and N2 adsorption. To determine the bioaccessible pore sizes, we performed separate experiments to assess the ability of hydrocarbon degrading bacteria isolated from the soil to pass through membranes with specific sized pores and to access hexadecane (model insoluble hydrocarbon). Hexadecane biodegradation occurred only when pores were 5 μm or larger, and did not occur when pores were 3 μm and smaller. In clayey aggregates, ∼ 25% of the aggregate volume was attributed to pores larger than 4 μm, which was comparable to that in aggregates from a sandy, hydrocarbon-contaminated soil (~23%) scanned for comparison. The ratio of volumes of inaccessible pores (<4 μm) to bioaccessible pores (>4 μm) in the clayey aggregates was 0.32, whereas in the sandy aggregates it was approximately 10 times lower. The role of soil microstructure on attainable bioremediation end points could be qualitatively assessed in various soils by the aggregate characterization approach outlined herein.
Life and death of a single catalytic cracking particle
Meirer, Florian; Kalirai, Sam; Morris, Darius; Soparawalla, Santosh; Liu, Yijin; Mesu, Gerbrand; Andrews, Joy C.; Weckhuysen, Bert M.
2015-01-01
Fluid catalytic cracking (FCC) particles account for 40 to 45% of worldwide gasoline production. The hierarchical complex particle pore structure allows access of long-chain feedstock molecules into active catalyst domains where they are cracked into smaller, more valuable hydrocarbon products (for example, gasoline). In this process, metal deposition and intrusion is a major cause for irreversible catalyst deactivation and shifts in product distribution. We used x-ray nanotomography of industrial FCC particles at differing degrees of deactivation to quantify changes in single-particle macroporosity and pore connectivity, correlated to iron and nickel deposition. Our study reveals that these metals are incorporated almost exclusively in near-surface regions, severely limiting macropore accessibility as metal concentrations increase. Because macropore channels are “highways” of the pore network, blocking them prevents feedstock molecules from reaching the catalytically active domains. Consequently, metal deposition reduces conversion with time on stream because the internal pore volume, although itself unobstructed, becomes largely inaccessible. PMID:26601160
Pore size distribution of OPC and SRPC mortars in presence of chlorides
DOE Office of Scientific and Technical Information (OSTI.GOV)
Suryavanshi, A.K.; Scantlebury, J.D.; Lyon, S.B.
1995-07-01
The pore structure of chloride-free ordinary portland cement (OPC) and sulphate resistant portland cement (SRPC) mortars are compared with the corresponding mortars with NaCl and CaCl{sub 2} added during mixing. In both OPC and SRPC mortars the addition of chlorides reduced the total accessible pore volumes compared to the corresponding chloride-free mortars. Also, in the presence of chlorides, the number of coarse pores were increased. These changes in the pore structure are believed to be due to dense calcium silicate hydrate (C-S-H) gel morphology formed in the presence of chlorides. The SRPC showed greater changes in pore structures than themore » OPC with equivalent amounts of chlorides added. This may be due to the lower chloride binding capacity of the SRPC and hence the higher availability of free chlorides to modify the gel morphology.« less
CO2 Capture in the Sustainable Wheat-Derived Activated Microporous Carbon Compartments
Hong, Seok-Min; Jang, Eunji; Dysart, Arthur D.; Pol, Vilas G.; Lee, Ki Bong
2016-01-01
Microporous carbon compartments (MCCs) were developed via controlled carbonization of wheat flour producing large cavities that allow CO2 gas molecules to access micropores and adsorb effectively. KOH activation of MCCs was conducted at 700 °C with varying mass ratios of KOH/C ranging from 1 to 5, and the effects of activation conditions on the prepared carbon materials in terms of the characteristics and behavior of CO2 adsorption were investigated. Textural properties, such as specific surface area and total pore volume, linearly increased with the KOH/C ratio, attributed to the development of pores and enlargement of pores within carbon. The highest CO2 adsorption capacities of 5.70 mol kg−1 at 0 °C and 3.48 mol kg−1 at 25 °C were obtained for MCC activated with a KOH/C ratio of 3 (MCC-K3). In addition, CO2 adsorption uptake was significantly dependent on the volume of narrow micropores with a pore size of less than 0.8 nm rather than the volume of larger pores or surface area. MCC-K3 also exhibited excellent cyclic stability, facile regeneration, and rapid adsorption kinetics. As compared to the pseudo-first-order model, the pseudo-second-order kinetic model described the experimental adsorption data methodically. PMID:27698448
Estimation and modeling of coal pore accessibility using small angle neutron scattering
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhang, Rui; Liu, Shimin; Bahadur, Jitendra
Gas diffusion in coal is controlled by nano-structure of the pores. The interconnectivity of pores not only determines the dynamics of gas transport in the coal matrix but also influences the mechanical strength. In this study, small angle neutron scattering (SANS) was employed to quantify pore accessibility for two coal samples, one of sub-bituminous rank and the other of anthracite rank. Moreover, a theoretical pore accessibility model was proposed based on scattering intensities under both vacuum and zero average contrast (ZAC) conditions. Our results show that scattering intensity decreases with increasing gas pressure using deuterated methane (CD 4) at lowmore » Q values for both coals. Pores smaller than 40 nm in radius are less accessible for anthracite than sub-bituminous coal. On the contrary, when the pore radius is larger than 40 nm, the pore accessibility of anthracite becomes larger than that of sub-bituminous coal. Only 20% of pores are accessible to CD 4 for anthracite and 37% for sub-bituminous coal, where the pore radius is 16 nm. For these two coals, pore accessibility and pore radius follows a power-law relationship.« less
Estimation and modeling of coal pore accessibility using small angle neutron scattering
Zhang, Rui; Liu, Shimin; Bahadur, Jitendra; ...
2015-09-04
Gas diffusion in coal is controlled by nano-structure of the pores. The interconnectivity of pores not only determines the dynamics of gas transport in the coal matrix but also influences the mechanical strength. In this study, small angle neutron scattering (SANS) was employed to quantify pore accessibility for two coal samples, one of sub-bituminous rank and the other of anthracite rank. Moreover, a theoretical pore accessibility model was proposed based on scattering intensities under both vacuum and zero average contrast (ZAC) conditions. Our results show that scattering intensity decreases with increasing gas pressure using deuterated methane (CD 4) at lowmore » Q values for both coals. Pores smaller than 40 nm in radius are less accessible for anthracite than sub-bituminous coal. On the contrary, when the pore radius is larger than 40 nm, the pore accessibility of anthracite becomes larger than that of sub-bituminous coal. Only 20% of pores are accessible to CD 4 for anthracite and 37% for sub-bituminous coal, where the pore radius is 16 nm. For these two coals, pore accessibility and pore radius follows a power-law relationship.« less
Modeling adsorption: Investigating adsorbate and adsorbent properties
NASA Astrophysics Data System (ADS)
Webster, Charles Edwin
1999-12-01
Surface catalyzed reactions play a major role in current chemical production technology. Currently, 90% of all chemicals are produced by heterogeneously catalyzed reactions. Most of these catalyzed reactions involve adsorption, concentrating the substrate(s) (the adsorbate) on the surface of the solid (the adsorbent). Pore volumes, accessible surface areas, and the thermodynamics of adsorption are essential in the understanding of solid surface characteristics fundamental to catalyst and adsorbent screening and selection. Molecular properties such as molecular volumes and projected molecular areas are needed in order to convert moles adsorbed to surface volumes and areas. Generally, these molecular properties have been estimated from bulk properties, but many assumptions are required. As a result, different literature values are employed for these essential molecular properties. Calculated molar volumes and excluded molecular areas are determined and tabulated for a variety of molecules. Molecular dimensions of molecules are important in the understanding of molecular exclusion as well as size and shape selectivity, diffusion, and adsorbent selection. Molecular dimensions can also be used in the determination of the effective catalytic pore size of a catalyst. Adsorption isotherms, on zeolites, (crystalline mineral oxides) and amorphous solids, can be analyzed with the Multiple Equilibrium Analysis (MEA) description of adsorption. The MEA produces equilibrium constants (Ki), capacities (ni), and thermodynamic parameters (enthalpies, ΔHi, and entropies, ΔSi) of adsorption for each process. Pore volumes and accessible surface areas are calculated from the process capacities. Adsorption isotherms can also be predicted for existing and new adsorbate-adsorbent systems with the MEA. The results show that MEA has the potential of becoming a standard characterization method for microporous solids that will lead to an increased understanding of their behavior in gas adsorption and catalysis. These studies are also applicable to environmental cleanup applications, such as waste stream purification and separation procedures as well as decontamination of chemical warfare agents.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Chojnicki, Kirsten; Cooper, Marcia A.; Guo, Shuyue
Pore-scale aperture effects on flow in pore networks was studied in the laboratory to provide a parameterization for use in transport models. Four cases were considered: regular and irregular pillar/pore alignment with and without an aperture. The velocity field of each case was measured and simulated, providing quantitatively comparable results. Two aperture effect parameterizations were considered: permeability and transmission. Permeability values varied by an order of magnitude between the cases with and without apertures. However, transmission did not correlate with permeability. Despite having much greater permeability the regular aperture case permitted less transmission than the regular case. Moreover, both irregularmore » cases had greater transmission than the regular cases, a difference not supported by the permeabilities. Overall, these findings suggest that pore-scale aperture effects on flow though a pore-network may not be adequately captured by properties such as permeability for applications that are interested in determining particle transport volume and timing.« less
NASA Astrophysics Data System (ADS)
Shapiro, Allen M.; Evans, Christopher E.; Hayes, Erin C.
2017-08-01
Characterizing properties of the rock matrix that control retention and release of chlorinated solvents is essential in evaluating the extent of contamination and the application of remediation technologies in fractured rock. Core samples from seven closely spaced boreholes in a mudstone subject to trichloroethene (TCE) contamination were analyzed using Mercury Intrusion Porosimetry to investigate porosity and pore size distribution as a function of mudstone characteristics, and depth and lateral extent in the aquifer; organic carbon content was also evaluated to identify the potential for adsorption. Porosity and retardation factor varied over two orders of magnitude, with the largest porosities and largest retardation factors associated with carbon-rich mudstone layers. Larger porosities were also measured in the shallow rock that has been subject to enhanced groundwater flow. Porosity also varied over more than an order of magnitude in spatially continuous mudstone layers. The analyses of the rock cores indicated that the largest pore diameters may be accessible to entry of the nonaqueous form of TCE. Although the porosity associated with the largest pore diameters is small ( 0.1%), that volume of TCE can significantly affect the total TCE that is retained in the rock matrix. The dimensions of the largest pore diameters may also be accessible to microbes responsible for reductive dechlorination; however, the small percentage of the pore space that can accommodate microbes may limit the extent of reductive dechlorination in the rock matrix.
Shapiro, Allen M.; Evans, Chrsitopher E.; Hayes, Erin C.
2017-01-01
Characterizing properties of the rock matrix that control retention and release of chlorinated solvents is essential in evaluating the extent of contamination and the application of remediation technologies in fractured rock. Core samples from seven closely spaced boreholes in a mudstone subject to trichloroethene (TCE) contamination were analyzed using Mercury Intrusion Porosimetry to investigate porosity and pore size distribution as a function of mudstone characteristics, and depth and lateral extent in the aquifer; organic carbon content was also evaluated to identify the potential for adsorption. Porosity and retardation factor varied over two orders of magnitude, with the largest porosities and largest retardation factors associated with carbon-rich mudstone layers. Larger porosities were also measured in the shallow rock that has been subject to enhanced groundwater flow. Porosity also varied over more than an order of magnitude in spatially continuous mudstone layers. The analyses of the rock cores indicated that the largest pore diameters may be accessible to entry of the nonaqueous form of TCE. Although the porosity associated with the largest pore diameters is small (~ 0.1%), that volume of TCE can significantly affect the total TCE that is retained in the rock matrix. The dimensions of the largest pore diameters may also be accessible to microbes responsible for reductive dechlorination; however, the small percentage of the pore space that can accommodate microbes may limit the extent of reductive dechlorination in the rock matrix.
Crowe, Jacob D; Zarger, Rachael A; Hodge, David B
2017-10-04
Simultaneous chemical modification and physical reorganization of plant cell walls via alkaline hydrogen peroxide or liquid hot water pretreatment can alter cell wall structural properties impacting nanoscale porosity. Nanoscale porosity was characterized using solute exclusion to assess accessible pore volumes, water retention value as a proxy for accessible water-cell walls surface area, and solute-induced cell wall swelling to measure cell wall rigidity. Key findings concluded that delignification by alkaline hydrogen peroxide pretreatment decreased cell wall rigidity and that the subsequent cell wall swelling resulted increased nanoscale porosity and improved enzyme binding and hydrolysis compared to limited swelling and increased accessible surface areas observed in liquid hot water pretreated biomass. The volume accessible to a 90 Å dextran probe within the cell wall was found to be correlated to both enzyme binding and glucose hydrolysis yields, indicating cell wall porosity is a key contributor to effective hydrolysis yields.
Porosity of the Marcellus Shale: A contrast matching small-angle neutron scattering study
Bahadur, Jitendra; Ruppert, Leslie F.; Pipich, Vitaliy; Sakurovs, Richard; Melnichenko, Yuri B.
2018-01-01
Neutron scattering techniques were used to determine the effect of mineral matter on the accessibility of water and toluene to pores in the Devonian Marcellus Shale. Three Marcellus Shale samples, representing quartz-rich, clay-rich, and carbonate-rich facies, were examined using contrast matching small-angle neutron scattering (CM-SANS) at ambient pressure and temperature. Contrast matching compositions of H2O, D2O and toluene, deuterated toluene were used to probe open and closed pores of these three shale samples. Results show that although the mean pore radius was approximately the same for all three samples, the fractal dimension of the quartz-rich sample was higher than for the clay-rich and carbonate-rich samples, indicating different pore size distributions among the samples. The number density of pores was highest in the clay-rich sample and lowest in the quartz-rich sample. Contrast matching with water and toluene mixtures shows that the accessibility of pores to water and toluene also varied among the samples. In general, water accessed approximately 70–80% of the larger pores (>80 nm radius) in all three samples. At smaller pore sizes (~5–80 nm radius), the fraction of accessible pores decreases. The lowest accessibility to both fluids is at pore throat size of ~25 nm radii with the quartz-rich sample exhibiting lower accessibility than the clay- and carbonate-rich samples. The mechanism for this behaviour is unclear, but because the mineralogy of the three samples varies, it is likely that the inaccessible pores in this size range are associated with organics and not a specific mineral within the samples. At even smaller pore sizes (~<2.5 nm radius), in all samples, the fraction of accessible pores to water increases again to approximately 70–80%. Accessibility to toluene generally follows that of water; however, in the smallest pores (~<2.5 nm radius), accessibility to toluene decreases, especially in the clay-rich sample which contains about 30% more closed pores than the quartz- and carbonate-rich samples. Results from this study show that mineralogy of producing intervals within a shale reservoir can affect accessibility of pores to water and toluene and these mineralogic differences may affect hydrocarbon storage and production and hydraulic fracturing characteristics
Song, Xueping; Jiang, Yan; Rong, Xianjian; Wei, Wei; Wang, Shuangfei; Nie, Shuangxi
2016-09-01
The surface characterization and chemical analysis of bamboo substrates by alkali hydrogen peroxide pretreatment (AHPP) were investigated in this study. The results tended to manifest that AHPP prior to enzymatic and chemical treatment was potential for improving accessibility and reactivity of bamboo substrates. The inorganic components, organic solvent extractives and acid-soluble lignin were effectively removed by AHPP. X-ray photoelectron spectroscopy (XPS) analysis indicated that the surface of bamboo chips had less lignin but more carbohydrate after pre-treatment. Fiber surfaces became etched and collapsed, and more pores and debris on the substrate surface were observed with Scanning Electron Microscopy (SEM). Brenauer-Emmett-Teller (BET) results showed that both of pore volume and surface area were increased after AHPP. Although XRD analysis showed that AHPP led to relatively higher crystallinity, pre-extraction could overall enhance the accessibility of enzymes and chemicals into the bamboo structure. Copyright © 2016. Published by Elsevier Ltd.
3D Analysis of Porosity in a Ceramic Coating Using X-ray Microscopy
NASA Astrophysics Data System (ADS)
Klement, Uta; Ekberg, Johanna; Kelly, Stephen T.
2017-02-01
Suspension plasma spraying (SPS) is a new, innovative plasma spray technique using a feedstock consisting of fine powder particles suspended in a liquid. Using SPS, ceramic coatings with columnar microstructures have been produced which are used as topcoats in thermal barrier coatings. The microstructure contains a wide pore size range consisting of inter-columnar spacings, micro-pores and nano-pores. Hence, determination of total porosity and pore size distribution is a challenge. Here, x-ray microscopy (XRM) has been applied for describing the complex pore space of the coatings because of its capability to image the (local) porosity within the coating in 3D at a resolution down to 50 nm. The possibility to quantitatively segment the analyzed volume allows analysis of both open and closed porosity. For an yttria-stabilized zirconia coating with feathery microstructure, both open and closed porosity were determined and it could be revealed that 11% of the pore volumes (1.4% of the total volume) are closed pores. The analyzed volume was reconstructed to illustrate the distribution of open and closed pores in 3D. Moreover, pore widths and pore volumes were determined. The results on the complex pore space obtained by XRM are discussed in connection with other porosimetry techniques.
Biotemplating pores with size and shape diversity for Li-oxygen Battery Cathodes.
Oh, Dahyun; Ozgit-Akgun, Cagla; Akca, Esin; Thompson, Leslie E; Tadesse, Loza F; Kim, Ho-Cheol; Demirci, Gökhan; Miller, Robert D; Maune, Hareem
2017-04-04
Synthetic porogens provide an easy way to create porous structures, but their usage is limited due to synthetic difficulties, process complexities and prohibitive costs. Here we investigate the use of bacteria, sustainable and naturally abundant materials, as a pore template. The bacteria require no chemical synthesis, come in variable sizes and shapes, degrade easier and are approximately a million times cheaper than conventional porogens. We fabricate free standing porous multiwalled carbon nanotube (MWCNT) films using cultured, harmless bacteria as porogens, and demonstrate substantial Li-oxygen battery performance improvement by porosity control. Pore volume as well as shape in the cathodes were easily tuned to improve oxygen evolution efficiency by 30% and double the full discharge capacity in repeated cycles compared to the compact MWCNT electrode films. The interconnected pores produced by the templates greatly improve the accessibility of reactants allowing the achievement of 4,942 W/kg (8,649 Wh/kg) at 2 A/g e (1.7 mA/cm 2 ).
Biotemplating pores with size and shape diversity for Li-oxygen Battery Cathodes
Oh, Dahyun; Ozgit-Akgun, Çagla; Akca, Esin; Thompson, Leslie E.; Tadesse, Loza F.; Kim, Ho-Cheol; Demirci, Gökhan; Miller, Robert D.; Maune, Hareem
2017-01-01
Synthetic porogens provide an easy way to create porous structures, but their usage is limited due to synthetic difficulties, process complexities and prohibitive costs. Here we investigate the use of bacteria, sustainable and naturally abundant materials, as a pore template. The bacteria require no chemical synthesis, come in variable sizes and shapes, degrade easier and are approximately a million times cheaper than conventional porogens. We fabricate free standing porous multiwalled carbon nanotube (MWCNT) films using cultured, harmless bacteria as porogens, and demonstrate substantial Li-oxygen battery performance improvement by porosity control. Pore volume as well as shape in the cathodes were easily tuned to improve oxygen evolution efficiency by 30% and double the full discharge capacity in repeated cycles compared to the compact MWCNT electrode films. The interconnected pores produced by the templates greatly improve the accessibility of reactants allowing the achievement of 4,942 W/kg (8,649 Wh/kg) at 2 A/ge (1.7 mA/cm2). PMID:28374862
A computational geometry approach to pore network construction for granular packings
NASA Astrophysics Data System (ADS)
van der Linden, Joost H.; Sufian, Adnan; Narsilio, Guillermo A.; Russell, Adrian R.; Tordesillas, Antoinette
2018-03-01
Pore network construction provides the ability to characterize and study the pore space of inhomogeneous and geometrically complex granular media in a range of scientific and engineering applications. Various approaches to the construction have been proposed, however subtle implementational details are frequently omitted, open access to source code is limited, and few studies compare multiple algorithms in the context of a specific application. This study presents, in detail, a new pore network construction algorithm, and provides a comprehensive comparison with two other, well-established Delaunay triangulation-based pore network construction methods. Source code is provided to encourage further development. The proposed algorithm avoids the expensive non-linear optimization procedure in existing Delaunay approaches, and is robust in the presence of polydispersity. Algorithms are compared in terms of structural, geometrical and advanced connectivity parameters, focusing on the application of fluid flow characteristics. Sensitivity of the various networks to permeability is assessed through network (Stokes) simulations and finite-element (Navier-Stokes) simulations. Results highlight strong dependencies of pore volume, pore connectivity, throat geometry and fluid conductance on the degree of tetrahedra merging and the specific characteristics of the throats targeted by the merging algorithm. The paper concludes with practical recommendations on the applicability of the three investigated algorithms.
NASA Astrophysics Data System (ADS)
Stańczak, Grażyna; Rembiś, Marek; Figarska-Warchoł, Beata; Toboła, Tomasz
The complex pore space considerably affects the unique properties of diatomite and its significant potential for many industrial applications. The pore network in the diatomite from the Lower Miocene strata of the Skole nappe (the Jawornik deposit, SE Poland) has been investigated using a fractal approach. The fractal dimension of the pore-space volume was calculated using the Menger sponge as a model of a porous body and the mercury porosimetry data in a pore-throat diameter range between 10,000 and 10 nm. Based on the digital analyses of the two-dimensional images from thin sections taken under a scanning electron microscope at the backscattered electron mode at different magnifications, the authors tried to quantify the pore spaces of the diatomites using the box counting method. The results derived from the analyses of the pore-throat diameter distribution using mercury porosimetry have revealed that the pore space of the diatomite has the bifractal structure in two separated ranges of the pore-throat diameters considerably smaller than the pore-throat sizes corresponding to threshold pressures. Assuming that the fractal dimensions identified for the ranges of the smaller pore-throat diameters characterize the overall pore-throat network in the Jawornik diatomite, we can set apart the distribution of the pore-throat volume (necks) and the pore volume from the distribution of the pore-space volume (pores and necks together).
Porosity control in nanoporous carbide-derived carbon by oxidation in air and carbon dioxide
DOE Office of Scientific and Technical Information (OSTI.GOV)
Osswald, S.; Portet, C.; Gogotsi, Y., E-mail: gogotsi@drexel.ed
2009-07-15
Carbide-derived carbons (CDC) allow a precise control over the pore size through the selection of the carbide precursor and varying of the synthesis conditions. However, their pore volume is limited by the carbide stoichiometry. While activation of carbons derived from various organic precursors has been widely studied, this process may similarly be able to increase the pore volume and specific surface area of CDC. Oxidation of carbide-derived carbon in air and CO{sub 2} at different temperatures and times allows for significant increase in pore volume and specific surface area as well as control over average pore size with subnanometer accuracy.more » The effect of activation and associated changes in the pore volume and surface area on the hydrogen uptake are also discussed. - Graphical abstract: Carbide-derived carbons (CDC) provide great potential for sorption of toxicants and gas storage applications. Activation of CDC in air and CO{sub 2} at different temperatures and times is applied in order to maximize pore volume and specific surface area, and control the average pore size with subnanometer accuracy.« less
Hoffmann, Claudia; Thieme, Sören; Brückner, Jan; Oschatz, Martin; Biemelt, Tim; Mondin, Giovanni; Althues, Holger; Kaskel, Stefan
2014-12-23
Silica nanospheres are used as templates for the generation of carbide-derived carbons with monodisperse spherical mesopores (d=20-40 nm) and microporous walls. The nanocasting approach with a polycarbosilane precursor and subsequent pyrolysis, followed by silica template removal and chlorine treatment, results in carbide-derived carbons DUT-86 (DUT=Dresden University of Technology) with remarkable textural characteristics, monodisperse, spherical mesopores tunable in diameter, and very high pore volumes up to 5.0 cm3 g(-1). Morphology replication allows these nanopores to be arranged in a nanostructured inverse opal-like structure. Specific surface areas are very high (2450 m2 g(-1)) due to the simultaneous presence of micropores. Testing DUT-86 samples as cathode materials in Li-S batteries reveals excellent performance, and tailoring of the pore size allows optimization of cell performance, especially the active center accessibility and sulfur utilization. The outstanding pore volumes allow sulfur loadings of 80 wt %, a value seldom achieved in composite cathodes, and initial capacities of 1165 mAh gsulfur(-1) are reached. After 100 cycle capacities of 860 mAh gsulfur(-1) are retained, rendering DUT-86 a high-performance sulfur host material.
Antera 3D capabilities for pore measurements.
Messaraa, C; Metois, A; Walsh, M; Flynn, J; Doyle, L; Robertson, N; Mansfield, A; O'Connor, C; Mavon, A
2018-04-29
The cause of enlarged pores remains obscure but still remains of concern for women. To complement subjective methods, bioengineered methods are needed for quantification of pores visibility following treatments. The study objective was to demonstrate the suitability of pore measurements from the Antera 3D. Pore measurements were collected on 22 female volunteers aged 18-65 years with the Antera 3D, the DermaTOP and image analysis on photographs. Additionally, 4 raters graded pore size on photographs on a scale 0-5. Repeatability of Antera 3D parameters was ascertained and the benefit of a pore minimizer product on the cheek was assessed on a sub panel of seven female volunteers. Pore parameters using the Antera were shown to depict pore severity similar to raters on photographs, except for Max Depth. Mean pore volume, mean pore area and count were moderately correlated with DermaTOP parameters (up to r = .50). No relationship was seen between the Antera 3D and pore visibility analysis on photographs. The most repeatable parameters were found to be mean pore volume, mean pore area and max depth, especially for the small and medium filters. The benefits of a pore minimizer product were the most striking for mean pore volume and mean pore area when using the small filter for analysis, rather than the medium/large ones. Pore measurements with the Antera 3D represent a reliable tool for efficacy and field studies, with an emphasis of the small filter for analysis for the mean pore volume/mean pore area parameters. © 2018 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.
A USANS/SANS study of the accessibility of pores in the Barnett Shale to methane and water
Ruppert, Leslie F.; Sakurovs, Richard; Blach, Tomasz P.; He, Lilin; Melnichenko, Yuri B.; Mildner, David F.; Alcantar-Lopez, Leo
2013-01-01
Shale is an increasingly important source of natural gas in the United States. The gas is held in fine pores that need to be accessed by horizontal drilling and hydrofracturing techniques. Understanding the nature of the pores may provide clues to making gas extraction more efficient. We have investigated two Mississippian Barnett Shale samples, combining small-angle neutron scattering (SANS) and ultrasmall-angle neutron scattering (USANS) to determine the pore size distribution of the shale over the size range 10 nm to 10 μm. By adding deuterated methane (CD4) and, separately, deuterated water (D2O) to the shale, we have identified the fraction of pores that are accessible to these compounds over this size range. The total pore size distribution is essentially identical for the two samples. At pore sizes >250 nm, >85% of the pores in both samples are accessible to both CD4 and D2O. However, differences in accessibility to CD4 are observed in the smaller pore sizes (~25 nm). In one sample, CD4 penetrated the smallest pores as effectively as it did the larger ones. In the other sample, less than 70% of the smallest pores (4, but they were still largely penetrable by water, suggesting that small-scale heterogeneities in methane accessibility occur in the shale samples even though the total porosity does not differ. An additional study investigating the dependence of scattered intensity with pressure of CD4 allows for an accurate estimation of the pressure at which the scattered intensity is at a minimum. This study provides information about the composition of the material immediately surrounding the pores. Most of the accessible (open) pores in the 25 nm size range can be associated with either mineral matter or high reflectance organic material. However, a complementary scanning electron microscopy investigation shows that most of the pores in these shale samples are contained in the organic components. The neutron scattering results indicate that the pores are not equally proportioned in the different constituents within the shale. There is some indication from the SANS results that the composition of the pore-containing material varies with pore size; the pore size distribution associated with mineral matter is different from that associated with organic phases.
Gas permeability of ice-templated, unidirectional porous ceramics
NASA Astrophysics Data System (ADS)
Seuba, Jordi; Deville, Sylvain; Guizard, Christian; Stevenson, Adam J.
2016-01-01
We investigate the gas flow behavior of unidirectional porous ceramics processed by ice-templating. The pore volume ranged between 54% and 72% and pore size between 2.9 ?m and 19.1 ?m. The maximum permeability (?? m?) was measured in samples with the highest total pore volume (72%) and pore size (19.1 ?m). However, we demonstrate that it is possible to achieve a similar permeability (?? m?) at 54% pore volume by modification of the pore shape. These results were compared with those reported and measured for isotropic porous materials processed by conventional techniques. In unidirectional porous materials tortuosity (?) is mainly controlled by pore size, unlike in isotropic porous structures where ? is linked to pore volume. Furthermore, we assessed the applicability of Ergun and capillary model in the prediction of permeability and we found that the capillary model accurately describes the gas flow behavior of unidirectional porous materials. Finally, we combined the permeability data obtained here with strength data for these materials to establish links between strength and permeability of ice-templated materials.
Fractal Dimensionality of Pore and Grain Volume of a Siliciclastic Marine Sand
NASA Astrophysics Data System (ADS)
Reed, A. H.; Pandey, R. B.; Lavoie, D. L.
Three-dimensional (3D) spatial distributions of pore and grain volumes were determined from high-resolution computer tomography (CT) images of resin-impregnated marine sands. Using a linear gradient extrapolation method, cubic three-dimensional samples were constructed from two-dimensional CT images. Image porosity (0.37) was found to be consistent with the estimate of porosity by water weight loss technique (0.36). Scaling of the pore volume (Vp) with the linear size (L), V~LD provides the fractal dimensionalities of the pore volume (D=2.74+/-0.02) and grain volume (D=2.90+/-0.02) typical for sedimentary materials.
Costantini, Marco; Colosi, Cristina; Jaroszewicz, Jakub; Tosato, Alessia; Święszkowski, Wojciech; Dentini, Mariella; Garstecki, Piotr; Barbetta, Andrea
2015-10-28
Ordered porous polymeric materials can be engineered to present highly ordered pore arrays and uniform and tunable pore size. These features prompted a number of applications in tissue engineering, generation of meta materials, and separation and purification of biomolecules and cells. Designing new and efficient vistas for the generation of ordered porous materials is an active area of research. Here we investigate the potential of microfluidic foaming within a flow-focusing (FF) geometry in producing 3D regular sponge-like polymeric matrices with tailored morphological and permeability properties. The challenge in using microfluidic systems for the generation of polymeric foams is in the high viscosity of the continuous phase. We demonstrate that as the viscosity of the aqueous solution increases, the accessible range of foam bubble fraction (Φb) and bubble diameter (Db) inside the microfluidic chip tend to narrow progressively. This effect limits the accessible range of geometric properties of the resulting materials. We further show that this problem can be rationally tackled by appropriate choice of the concentration of the polymer. We demonstrate that via such optimization, the microfluidic assisted synthesis of porous materials becomes a facile and versatile tool for generation of porous materials with a wide range of pore size and pore volume. Moreover, we demonstrate that the size of interconnects among pores-for a given value of the gas fraction-can be tailored through the variation of surfactant concentration. This, in turn, affects the permeability of the materials, a factor of key importance in flow-through applications and in tissue engineering.
Cell wall microstructure, pore size distribution and absolute density of hemp shiv
Lawrence, M.; Ansell, M. P.; Hussain, A.
2018-01-01
This paper, for the first time, fully characterizes the intrinsic physical parameters of hemp shiv including cell wall microstructure, pore size distribution and absolute density. Scanning electron microscopy revealed microstructural features similar to hardwoods. Confocal microscopy revealed three major layers in the cell wall: middle lamella, primary cell wall and secondary cell wall. Computed tomography improved the visualization of pore shape and pore connectivity in three dimensions. Mercury intrusion porosimetry (MIP) showed that the average accessible porosity was 76.67 ± 2.03% and pore size classes could be distinguished into micropores (3–10 nm) and macropores (0.1–1 µm and 20–80 µm). The absolute density was evaluated by helium pycnometry, MIP and Archimedes' methods. The results show that these methods can lead to misinterpretation of absolute density. The MIP method showed a realistic absolute density (1.45 g cm−3) consistent with the density of the known constituents, including lignin, cellulose and hemi-cellulose. However, helium pycnometry and Archimedes’ methods gave falsely low values owing to 10% of the volume being inaccessible pores, which require sample pretreatment in order to be filled by liquid or gas. This indicates that the determination of the cell wall density is strongly dependent on sample geometry and preparation. PMID:29765652
Cell wall microstructure, pore size distribution and absolute density of hemp shiv
NASA Astrophysics Data System (ADS)
Jiang, Y.; Lawrence, M.; Ansell, M. P.; Hussain, A.
2018-04-01
This paper, for the first time, fully characterizes the intrinsic physical parameters of hemp shiv including cell wall microstructure, pore size distribution and absolute density. Scanning electron microscopy revealed microstructural features similar to hardwoods. Confocal microscopy revealed three major layers in the cell wall: middle lamella, primary cell wall and secondary cell wall. Computed tomography improved the visualization of pore shape and pore connectivity in three dimensions. Mercury intrusion porosimetry (MIP) showed that the average accessible porosity was 76.67 ± 2.03% and pore size classes could be distinguished into micropores (3-10 nm) and macropores (0.1-1 µm and 20-80 µm). The absolute density was evaluated by helium pycnometry, MIP and Archimedes' methods. The results show that these methods can lead to misinterpretation of absolute density. The MIP method showed a realistic absolute density (1.45 g cm-3) consistent with the density of the known constituents, including lignin, cellulose and hemi-cellulose. However, helium pycnometry and Archimedes' methods gave falsely low values owing to 10% of the volume being inaccessible pores, which require sample pretreatment in order to be filled by liquid or gas. This indicates that the determination of the cell wall density is strongly dependent on sample geometry and preparation.
Micromechanics investigation of expansive reactions in chemoelastic concrete.
Lemarchand, Eric; Dormieux, Luc; Ulm, Franz-Josef
2005-11-15
Expansive reactions damage porous materials through the formation of reaction products of a volume in excess of the available space left by the reactants and the natural porosity of the material. This leads to pressurizing the pore space accessible to the reaction products, which differs when the chemical reaction is through-solution or topochemical or both in nature. This paper investigates expansive reactions from a micromechanical point of view, which allows bridging the scale from the local chemo-mechanical mechanisms to the macroscopically observable stress-free expansion. In particular, the study of the effect of morphology of the pore space, in which the chemical expansion occurs locally, on the macroscopically observable expansion is the main focus of this paper. The first part revisits the through-solution and the topochemical reaction mechanism within the framework of micro-macro-homogenization theories, and the effect of the microscopic geometry of pores and microcracks in the solid matrix on the macroscopic chemical expansion is examined. The second part deals with the transition from a topochemical to a through-solution-like mechanism that occurs in a solid matrix with inclusions (cracks, pores) of different morphology.
Yasaki, Hirotoshi; Yasui, Takao; Yanagida, Takeshi; Kaji, Noritada; Kanai, Masaki; Nagashima, Kazuki; Kawai, Tomoji; Baba, Yoshinobu
2017-10-11
Measuring ionic currents passing through nano- or micropores has shown great promise for the electrical discrimination of various biomolecules, cells, bacteria, and viruses. However, conventional measurements have shown there is an inherent limitation to the detectable particle volume (1% of the pore volume), which critically hinders applications to real mixtures of biomolecule samples with a wide size range of suspended particles. Here we propose a rational methodology that can detect samples with the detectable particle volume of 0.01% of the pore volume by measuring a transient current generated from the potential differences in a microfluidic bridge circuit. Our method substantially suppresses the background ionic current from the μA level to the pA level, which essentially lowers the detectable particle volume limit even for relatively large pore structures. Indeed, utilizing a microscale long pore structure (volume of 5.6 × 10 4 aL; height and width of 2.0 × 2.0 μm; length of 14 μm), we successfully detected various samples including polystyrene nanoparticles (volume: 4 aL), bacteria, cancer cells, and DNA molecules. Our method will expand the applicability of ionic current sensing systems for various mixed biomolecule samples with a wide size range, which have been difficult to measure by previously existing pore technologies.
AFM-porosimetry: density and pore volume measurements of particulate materials.
Sörensen, Malin H; Valle-Delgado, Juan J; Corkery, Robert W; Rutland, Mark W; Alberius, Peter C
2008-06-01
We introduced the novel technique of AFM-porosimetry and applied it to measure the total pore volume of porous particles with a spherical geometry. The methodology is based on using an atomic force microscope as a balance to measure masses of individual particles. Several particles within the same batch were measured, and by plotting particle mass versus particle volume, the bulk density of the sample can be extracted from the slope of the linear fit. The pore volume is then calculated from the densities of the bulk and matrix materials, respectively. In contrast to nitrogen sorption and mercury porosimetry, this method is capable of measuring the total pore volume regardless of pore size distribution and pore connectivity. In this study, three porous samples were investigated by AFM-porosimetry: one ordered mesoporous sample and two disordered foam structures. All samples were based on a matrix of amorphous silica templated by a block copolymer, Pluronic F127, swollen to various degrees with poly(propylene glycol). In addition, the density of silica spheres without a template was measured by two independent techniques: AFM and the Archimedes principle.
Gas permeability of ice-templated, unidirectional porous ceramics.
Seuba, Jordi; Deville, Sylvain; Guizard, Christian; Stevenson, Adam J
2016-01-01
We investigate the gas flow behavior of unidirectional porous ceramics processed by ice-templating. The pore volume ranged between 54% and 72% and pore size between 2.9 [Formula: see text]m and 19.1 [Formula: see text]m. The maximum permeability ([Formula: see text] [Formula: see text] m[Formula: see text]) was measured in samples with the highest total pore volume (72%) and pore size (19.1 [Formula: see text]m). However, we demonstrate that it is possible to achieve a similar permeability ([Formula: see text] [Formula: see text] m[Formula: see text]) at 54% pore volume by modification of the pore shape. These results were compared with those reported and measured for isotropic porous materials processed by conventional techniques. In unidirectional porous materials tortuosity ([Formula: see text]) is mainly controlled by pore size, unlike in isotropic porous structures where [Formula: see text] is linked to pore volume. Furthermore, we assessed the applicability of Ergun and capillary model in the prediction of permeability and we found that the capillary model accurately describes the gas flow behavior of unidirectional porous materials. Finally, we combined the permeability data obtained here with strength data for these materials to establish links between strength and permeability of ice-templated materials.
Pastrama, Maria-Ioana; Scheiner, Stefan; Pivonka, Peter; Hellmich, Christian
2018-02-01
While bone tissue is a hierarchically organized material, mathematical formulations of bone remodeling are often defined on the level of a millimeter-sized representative volume element (RVE), "smeared" over all types of bone microstructures seen at lower observation scales. Thus, there is no explicit consideration of the fact that the biological cells and biochemical factors driving bone remodeling are actually located in differently sized pore spaces: active osteoblasts and osteoclasts can be found in the vascular pores, whereas the lacunar pores host osteocytes - bone cells originating from former osteoblasts which were then "buried" in newly deposited extracellular bone matrix. We here propose a mathematical description which considers size and shape of the pore spaces where the biological and biochemical events take place. In particular, a previously published systems biology formulation, accounting for biochemical regulatory mechanisms such as the rank-rankl-opg pathway, is cast into a multiscale framework coupled to a poromicromechanical model. The latter gives access to the vascular and lacunar pore pressures arising from macroscopic loading. Extensive experimental data on the biological consequences of this loading strongly suggest that the aforementioned pore pressures, together with the loading frequency, are essential drivers of bone remodeling. The novel approach presented here allows for satisfactory simulation of the evolution of bone tissue under various loading conditions, and for different species; including scenarios such as mechanical dis- and overuse of murine and human bone, or in osteocyte-free bone. Copyright © 2017 Elsevier Inc. All rights reserved.
Pore-scale supercritical CO 2 dissolution and mass transfer under drainage conditions
Chang, Chun; Zhou, Quanlin; Oostrom, Mart; ...
2016-12-05
Recently, both core- and pore-scale imbibition experiments have shown non-equilibrium dissolution of supercritical CO 2 (scCO 2) and a prolonged depletion of residual scCO 2. In this paper, pore-scale scCO 2 dissolution and mass transfer under drainage conditions were investigated using a two-dimensional heterogeneous micromodel and a novel fluorescent water dye with a sensitive pH range between 3.7 and 6.5. Drainage experiments were conducted at 9 MPa and 40 °C by injecting scCO 2 into the sandstone-analogue pore network initially saturated by water without dissolved CO 2 (dsCO 2). During the experiments, time-lapse images of dye intensity, reflecting water pH,more » were obtained. These images show non-uniform pH in individual pores and pore clusters, with average pH levels gradually decreasing with time. Further analysis on selected pores and pore clusters shows that (1) rate-limited mass transfer prevails with slowly decreasing pH over time when the scCO 2-water interface area is low with respect to the volume of water-filled pores and pore clusters, (2) fast scCO 2 dissolution and phase equilibrium occurs when scCO 2 bubbles invade into water-filled pores, significantly enhancing the area-to-volume ratio, and (3) a transition from rate-limited to diffusion-limited mass transfer occurs in a single pore when a medium area-to-volume ratio is prevalent. The analysis also shows that two fundamental processes – scCO 2 dissolution at phase interfaces and diffusion of dsCO 2 at the pore scale (10–100 µm) observed after scCO 2 bubble invasion into water-filled pores without pore throat constraints – are relatively fast. The overall slow dissolution of scCO 2 in the millimeter-scale micromodel can be attributed to the small area-to-volume ratios that represent pore-throat configurations and characteristics of phase interfaces. Finally, this finding is applicable for the behavior of dissolution at pore, core, and field scales when water-filled pores and pore clusters of varying size are surrounded by scCO 2 at narrow pore throats.« less
Pore-scale supercritical CO 2 dissolution and mass transfer under drainage conditions
DOE Office of Scientific and Technical Information (OSTI.GOV)
Chang, Chun; Zhou, Quanlin; Oostrom, Mart
Recently, both core- and pore-scale imbibition experiments have shown non-equilibrium dissolution of supercritical CO 2 (scCO 2) and a prolonged depletion of residual scCO 2. In this paper, pore-scale scCO 2 dissolution and mass transfer under drainage conditions were investigated using a two-dimensional heterogeneous micromodel and a novel fluorescent water dye with a sensitive pH range between 3.7 and 6.5. Drainage experiments were conducted at 9 MPa and 40 °C by injecting scCO 2 into the sandstone-analogue pore network initially saturated by water without dissolved CO 2 (dsCO 2). During the experiments, time-lapse images of dye intensity, reflecting water pH,more » were obtained. These images show non-uniform pH in individual pores and pore clusters, with average pH levels gradually decreasing with time. Further analysis on selected pores and pore clusters shows that (1) rate-limited mass transfer prevails with slowly decreasing pH over time when the scCO 2-water interface area is low with respect to the volume of water-filled pores and pore clusters, (2) fast scCO 2 dissolution and phase equilibrium occurs when scCO 2 bubbles invade into water-filled pores, significantly enhancing the area-to-volume ratio, and (3) a transition from rate-limited to diffusion-limited mass transfer occurs in a single pore when a medium area-to-volume ratio is prevalent. The analysis also shows that two fundamental processes – scCO 2 dissolution at phase interfaces and diffusion of dsCO 2 at the pore scale (10–100 µm) observed after scCO 2 bubble invasion into water-filled pores without pore throat constraints – are relatively fast. The overall slow dissolution of scCO 2 in the millimeter-scale micromodel can be attributed to the small area-to-volume ratios that represent pore-throat configurations and characteristics of phase interfaces. Finally, this finding is applicable for the behavior of dissolution at pore, core, and field scales when water-filled pores and pore clusters of varying size are surrounded by scCO 2 at narrow pore throats.« less
Pore-scale supercritical CO 2 dissolution and mass transfer under drainage conditions
DOE Office of Scientific and Technical Information (OSTI.GOV)
Chang, Chun; Zhou, Quanlin; Oostrom, Mart
Abstract: Recently, both core- and pore-scale imbibition experiments have shown non-equilibrium dissolution of supercritical CO 2 (scCO 2) and a prolonged depletion of residual scCO 2. In this study, pore-scale scCO 2 dissolution and mass transfer under drainage conditions were investigated using a two-dimensional heterogeneous micromodel and a novel fluorescent water dye with a sensitive pH range between 3.7 and 6.5. Drainage experiments were conducted at 9 MPa and 40 °C by injecting scCO 2 into the sandstone-analogue pore network initially saturated by water without dissolved CO 2 (dsCO 2). During the experiments, time-lapse images of dye intensity, reflecting watermore » pH, were obtained. These images show non-uniform pH in individual pores and pore clusters, with average pH levels gradually decreasing with time. Further analysis on selected pores and pore clusters shows that (1) rate-limited mass transfer prevails with slowly decreasing pH over time when the scCO 2-water interface area is low with respect to the volume of water-filled pores and pore clusters, (2) fast scCO 2 dissolution and phase equilibrium occurs when scCO 2 bubbles invade into water-filled pores, significantly enhancing the area-to-volume ratio, and (3) a transition from rate-limited to diffusion-limited mass transfer occurs in a single pore when a medium area-to-volume ratio is prevalent. The analysis also shows that two fundamental processes – scCO 2 dissolution at phase interfaces and diffusion of dsCO 2 at the pore scale (10-100 µm) observed after scCO 2 bubble invasion into water-filled pores without pore throat constraints – are relatively fast. The overall slow dissolution of scCO 2 in the millimeter-scale micromodel can be attributed to the small area-to-volume ratios that represent pore-throat configurations and characteristics of phase interfaces. This finding is applicable for the behavior of dissolution at pore, core, and field scales when water-filled pores and pore clusters of varying size are surrounded by scCO 2 at narrow pore throats.« less
Nanometer-Scale Pore Characteristics of Lacustrine Shale, Songliao Basin, NE China
Wang, Min; Yang, Jinxiu; Wang, Zhiwei; Lu, Shuangfang
2015-01-01
In shale, liquid hydrocarbons are accumulated mainly in nanometer-scale pores or fractures, so the pore types and PSDs (pore size distributions) play a major role in the shale oil occurrence (free or absorbed state), amount of oil, and flow features. The pore types and PSDs of marine shale have been well studied; however, research on lacustrine shale is rare, especially for shale in the oil generation window, although lacustrine shale is deposited widely around the world. To investigate the relationship between nanometer-scale pores and oil occurrence in the lacustrine shale, 10 lacustrine shale core samples from Songliao Basin, NE China were analyzed. Analyses of these samples included geochemical measurements, SEM (scanning electron microscope) observations, low pressure CO2 and N2 adsorption, and high-pressure mercury injection experiments. Analysis results indicate that: (1) Pore types in the lacustrine shale include inter-matrix pores, intergranular pores, organic matter pores, and dissolution pores, and these pores are dominated by mesopores and micropores; (2) There is no apparent correlation between pore volumes and clay content, however, a weak negative correlation is present between total pore volume and carbonate content; (3) Pores in lacustrine shale are well developed when the organic matter maturity (Ro) is >1.0% and the pore volume is positively correlated with the TOC (total organic carbon) content. The statistical results suggest that oil in lacustrine shale mainly occurs in pores with diameters larger than 40 nm. However, more research is needed to determine whether this minimum pore diameter for oil occurrence in lacustrine shale is widely applicable. PMID:26285123
Nanometer-Scale Pore Characteristics of Lacustrine Shale, Songliao Basin, NE China.
Wang, Min; Yang, Jinxiu; Wang, Zhiwei; Lu, Shuangfang
2015-01-01
In shale, liquid hydrocarbons are accumulated mainly in nanometer-scale pores or fractures, so the pore types and PSDs (pore size distributions) play a major role in the shale oil occurrence (free or absorbed state), amount of oil, and flow features. The pore types and PSDs of marine shale have been well studied; however, research on lacustrine shale is rare, especially for shale in the oil generation window, although lacustrine shale is deposited widely around the world. To investigate the relationship between nanometer-scale pores and oil occurrence in the lacustrine shale, 10 lacustrine shale core samples from Songliao Basin, NE China were analyzed. Analyses of these samples included geochemical measurements, SEM (scanning electron microscope) observations, low pressure CO2 and N2 adsorption, and high-pressure mercury injection experiments. Analysis results indicate that: (1) Pore types in the lacustrine shale include inter-matrix pores, intergranular pores, organic matter pores, and dissolution pores, and these pores are dominated by mesopores and micropores; (2) There is no apparent correlation between pore volumes and clay content, however, a weak negative correlation is present between total pore volume and carbonate content; (3) Pores in lacustrine shale are well developed when the organic matter maturity (Ro) is >1.0% and the pore volume is positively correlated with the TOC (total organic carbon) content. The statistical results suggest that oil in lacustrine shale mainly occurs in pores with diameters larger than 40 nm. However, more research is needed to determine whether this minimum pore diameter for oil occurrence in lacustrine shale is widely applicable.
NASA Astrophysics Data System (ADS)
Zhang, Chuan; Luo, Wenjun; Wen, Xin; Guan, Zhongjie; Zou, Zhigang
2017-11-01
P-type Cu(In,Ga)S2 semiconductors are promising candidates to be used as photocathodes for solar water splitting. Porous structures have been widely used to improve the performances of photoelectrodes due to good minority carrier transport. However, a porous photoelectrode has longer transport distance of majority carriers, which limits its performance. Controlling pore volume of a photoelectrode can balance minority and majority carrier transport and improve the performance. Here, a porous Cu(In,Ga)S2 film is prepared by facile spin-coating method. The pore volume of Cu(In,Ga)S2 film is controlled by adjusting relative humidity (RH) of air during spin-coating process. Further studies suggest that polyvinyl acetate (PVAc) in precursor solution is a humidity sensitive polymer and plays a key role to form different pore volume. The 40% RH sample has the best performance due to its optimum pore volume. After further coated with CdS surface passivation layer and Pt electrocatalyst on the surface, a 40% RH Cu(In,Ga)S2 photocathode indicates a photocurrent density of 8.6 mA cm-2 at 0 V RHE, which is one of the highest photocurrents of Cu(In,Ga)S2 photocathodes. This new strategy for adjusting pore volume is also suitable to prepare other solution-processed inorganic materials.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bradley, R.H.; Rand, B.
The physical adsorption of nonpolar and polar vapors by active carbons is discussed in relation to pore structure and pore wall chemistry. For nonpolar vapors the Dubinin-Radushkevich equation is used to derive micropore volumes (W[sub 0]), average adsorption energies (E[sub 0]), and micropore widths (L) for a number of systems. These parameters are used to interpret the adsorption behavior of nitrogen which, because it is a relatively small molecule, is frequently used at 77 K to probe porosity and surface area. Results are presented for three carbons from differing precursors, namely, coal, coconut shells, and polyvinylidene chloride (PVDC) to illustratemore » the applicability of the technique. For the latter carbon increases in micropore size, induced by activation in carbon dioxide, and reductions in accessible pore volume caused by heat treatment in argon are also characterized and related to structural changes. The approach is then extended to the adsorption of larger hydrogen vapors, where the resulting W[sub 0] values may require correction for molecular packing effects which occur in the lower relative pressure regions of the isotherms, i.e., during the filling of ultramicropores. These packing effects are shown to limit the use of the Polanyi characteristic curve for correlating isotherm data for several vapors, of differing molecular size, by one adsorbent. Data for the adsorption of water, which is a strongly polar liquid, have been interpreted using the Dubinin-Serpinsky equation.« less
Effect of degassing temperature on specific surface area and pore volume measurements of biochar
NASA Astrophysics Data System (ADS)
Sigmund, Gabriel; Hüffer, Thorsten; Kah, Melanie; Hofmann, Thilo
2017-04-01
Specific surface area, pore volume, and pore size distribution are key biochar properties that have been related to water and nutrient cycling, microbial activity as well as sorption potential for organic compounds. Specific surface area and pore volume are commonly determined by measurement of physisorption of N2 and/or CO2. The measurement requires prior degassing of the samples, which may change the structure of the materials. Information on degassing temperature is rarely reported in literature, and recommendations differ considerably between existing guidelines for biochar characterization. Therefore, the influence of degassing temperature on N2 and CO2physisorption measurements was investigated by systematically degassing a range of materials, including four biochars, Al2O3 and carbon nanotubes at different temperatures (105 ˚ C, 150 ˚ C, 200 ˚ C, 250 ˚ C and 300 ˚ C for ≥ 14 h each). Measured specific surface area and pore volume increased with increasing degassing temperature for all biochars. Additional surface area and pore volume may have become available as components in biochars volatilized during the degassing phase. The results of our study showed that (i) degassing conditions change material properties, and influence physisorption measurements for biochar (ii) comparison between parameters derived from different degassing protocols may not be appropriate, and (iii) degassing protocols should be harmonized in the biochar community [1]. [1] Sigmund, et al. (2016), "Biochar total surface area and total pore volume determined by N2 and CO2 physisorption are strongly influenced by degassing temperature", STOTEN, doi: http://dx.doi.org/10.1016/j.scitotenv.2016.12.023.
Catalyst for coal liquefaction process
Huibers, Derk T. A.; Kang, Chia-Chen C.
1984-01-01
An improved catalyst for a coal liquefaction process; e.g., the H-Coal Process, for converting coal into liquid fuels, and where the conversion is carried out in an ebullated-catalyst-bed reactor wherein the coal contacts catalyst particles and is converted, in addition to liquid fuels, to gas and residual oil which includes preasphaltenes and asphaltenes. The improvement comprises a catalyst selected from the group consisting of the oxides of nickel molybdenum, cobalt molybdenum, cobalt tungsten, and nickel tungsten on a carrier of alumina, silica, or a combination of alumina and silica. The catalyst has a total pore volume of about 0.500 to about 0.900 cc/g and the pore volume comprises micropores, intermediate pores and macropores, the surface of the intermediate pores being sufficiently large to convert the preasphaltenes to asphaltenes and lighter molecules. The conversion of the asphaltenes takes place on the surface of micropores. The macropores are for metal deposition and to prevent catalyst agglomeration. The micropores have diameters between about 50 and about 200 angstroms (.ANG.) and comprise from about 50 to about 80% of the pore volume, whereas the intermediate pores have diameters between about 200 and 2000 angstroms (.ANG.) and comprise from about 10 to about 25% of the pore volume, and the macropores have diameters between about 2000 and about 10,000 angstroms (.ANG.) and comprise from about 10 to about 25% of the pore volume. The catalysts are further improved where they contain promoters. Such promoters include the oxides of vanadium, tungsten, copper, iron and barium, tin chloride, tin fluoride and rare earth metals.
Publications - GMC 120 | Alaska Division of Geological & Geophysical
DGGS GMC 120 Publication Details Title: Porosity, permeability, density, and pore volume Reference Unknown, 1989, Porosity, permeability, density, and pore volume compressibility data of core from
Gritti, Fabrice; Guiochon, Georges
2007-12-28
The adsorption isotherms of phenol, caffeine, insulin, and lysozyme were measured on two C(18)-bonded silica columns. The first one was packed with classical totally porous particles (3 microm Luna(2)-C(18)from Phenomenex, Torrance, CA, USA), the second one with shell particles (2.7 microm Halo-C(18) from Advanced Materials Technology, Wilmington, DE, USA). The measurements were made at room temperature (T=295+/-1K), using mainly frontal analysis (FA) and also elution by characteristic points (FACP) when necessary. The adsorption energy distributions (AEDs) were estimated by the iterative numerical expectation-maximization (EM) procedure and served to justify the choice of the best adsorption isotherm model for each compound. The best isotherm parameters were derived from either the best fit of the experimental data to a multi-Langmuir isotherm model (MLRA) or from the AED results (equilibrium constants and saturation capacities), when the convergence of the EM program was achieved. The experiments show than the loading capacity of the Luna column is more than twice that of the Halo column for low-molecular-weight compounds. This result was expected; it is in good agreement with the values of the accessible surface area of these two materials, which were calculated from the pore size volume distributions. The pore size volume distributions are validated by the excellent agreement between the calculated and measured exclusion volumes of polystyrene standards by inverse size exclusion chromatography (ISEC). In contrast, the loading capacity ratio of the two columns is 1.5 or less with insulin and lysozyme. This is due to a significant exclusion of these two proteins from the internal pore volumes of the two packing materials. This result raises the problem of the determination of the effective surface area of the packing material, particularly in the case of proteins. This area is about 40 and 30% of the total surface area for insulin and for lysozyme, respectively, based on the pore size volume distribution validated by the ISEC method. The ISEC experiments showed that the largest and the smallest mesopores have rather a cylindrical and a spherical shape, respectively, for both packing materials.
NASA Astrophysics Data System (ADS)
Zhang, Jie; Li, Fan; Sun, Qian
2018-05-01
Organic dye pollutants become a big headache due to their toxic nature to the environment, and it should be one of the best solutions if we can remove and separate them. Here, a metal-organic framework (MOF) (denoted as Zn-MOF) with carbonyl group based on fluorenone-2,7-dicarboxylate ligand, was directly synthesized without post-synthesis method and applied to selectively absorb cationic dyes such as MB, CV, RhB from aqueous solution, while anionic or neutral dyes were excluded. Characterization of the Zn-MOF was achieved by X-ray diffraction, scanning electron microscope, Fourier transform infrared spectrometry and elemental analysis. The Zn-MOF mainly possesses open pore channels, high surface area, big pore volume, and most important, the pore surface is furnished with carbonyl groups arising from the ligand and pointing toward the centers of the large chambers of the framework, which are benefit for the adsorption of the cationic dyes. The MB maximum adsorption capacities can attain 326 mg g-1, which is probably due to the suitable pore size, higher solvent-accessible void, and the prominent adsorption capacity of the mesoporous material. The dye adsorption process for the material is proven to be charge-selective and size-selective, and the adsorption isotherms, as well as kinetics characteristic of dye adsorption onto the Zn-MOF were also investigated.
Effects of Pore Distributions on Ductility of Thin-Walled High Pressure Die-Cast Magnesium
DOE Office of Scientific and Technical Information (OSTI.GOV)
Choi, Kyoo Sil; Li, Dongsheng; Sun, Xin
2013-06-01
In this paper, a microstructure-based three-dimensional (3D) finite element modeling method is adopted to investigate the effects of porosity in thin-walled high pressure die-cast (HPDC) Magnesium alloys on their ductility. For this purpose, the cross-sections of AM60 casting samples are first examined using optical microscope and X-ray tomography to obtain the general information on the pore distribution features. The experimentally observed pore distribution features are then used to generate a series of synthetic microstructure-based 3D finite element models with different pore volume fractions and pore distribution features. Shear and ductile damage models are adopted in the finite element analyses tomore » induce the fracture by element removal, leading to the prediction of ductility. The results in this study show that the ductility monotonically decreases as the pore volume fraction increases and that the effect of ‘skin region’ on the ductility is noticeable under the condition of same local pore volume fraction in the center region of the sample and its existence can be beneficial for the improvement of ductility. The further synthetic microstructure-based 3D finite element analyses are planned to investigate the effects of pore size and pore size distribution.« less
NASA Astrophysics Data System (ADS)
Sobina, E.; Zimathis, A.; Prinz, C.; Emmerling, F.; Unger, W.; de Santis Neves, R.; Galhardo, C. E.; De Robertis, E.; Wang, H.; Mizuno, K.; Kurokawa, A.
2016-01-01
CCQM key comparison K-136 Measurement of porosity properties (specific adsorption, BET specific surface area, specific pore volume and pore diameter) of nanoporous Al2O3 has been performed by the Surface Analysis Working Group (SAWG) of the Consultative Committee for Amount of Substance (CCQM). The objective of this key comparison is to compare the equivalency of the National Metrology Institutes (NMIs) and Designated Institutes (DIs) for the measurement of specific adsorption, BET specific surface area, specific pore volume and pore diameter) of nanoporous substances (sorbents, catalytic agents, cross-linkers, zeolites, etc) used in advanced technology. In this key comparison, a commercial sorbent (aluminum oxide) was supplied as a sample. Five NMIs participated in this key comparison. All participants used a gas adsorption method, here nitrogen adsorption at 77.3 K, for analysis according to the international standards ISO 15901-2 and 9277. In this key comparison, the degrees of equivalence uncertainties for specific adsorption, BET specific surface area, specific pore volume and pore diameter was established. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).
Effective Thermal Conductivity of an Aluminum Foam + Water Two Phase System
NASA Technical Reports Server (NTRS)
Moskito, John
1996-01-01
This study examined the effect of volume fraction and pore size on the effective thermal conductivity of an aluminum foam and water system. Nine specimens of aluminum foam representing a matrix of three volume fractions (4-8% by vol.) and three pore sizes (2-4 mm) were tested with water to determine relationships to the effective thermal conductivity. It was determined that increases in volume fraction of the aluminum phase were correlated to increases in the effective thermal conductivity. It was not statistically possible to prove that changes in pore size of the aluminum foam correlated to changes in the effective thermal conductivity. However, interaction effects between the volume fraction and pore size of the foam were statistically significant. Ten theoretical models were selected from the published literature to compare against the experimental data. Models by Asaad, Hadley, and de Vries provided effective thermal conductivity predictions within a 95% confidence interval.
Huang, Xiaoxi; Tao, Zhimin; Praskavich, John C; Goswami, Anandarup; Al-Sharab, Jafar F; Minko, Tamara; Polshettiwar, Vivek; Asefa, Tewodros
2014-09-16
The pore size and pore structure of nanoporous materials can affect the materials' physical properties, as well as potential applications in different areas, including catalysis, drug delivery, and biomolecular therapeutics. KCC-1, one of the newest members of silica nanomaterials, possesses fibrous, large pore, dendritic pore networks with wide pore entrances, large pore size distribution, spacious pore volume and large surface area--structural features that are conducive for adsorption and release of large guest molecules and biomacromolecules (e.g., proteins and DNAs). Here, we report the results of our comparative studies of adsorption of salmon DNA in a series of KCC-1-based nanomaterials that are functionalized with different organoamine groups on different parts of their surfaces (channel walls, external surfaces or both). For comparison the results of our studies of adsorption of salmon DNA in similarly functionalized, MCM-41 mesoporous silica nanomaterials with cylindrical pores, some of the most studied silica nanomaterials for drug/gene delivery, are also included. Our results indicate that, despite their relatively lower specific surface area, the KCC-1-based nanomaterials show high adsorption capacity for DNA than the corresponding MCM-41-based nanomaterials, most likely because of KCC-1's large pores, wide pore mouths, fibrous pore network, and thereby more accessible and amenable structure for DNA molecules to diffuse through. Conversely, the MCM-41-based nanomaterials adsorb much less DNA, presumably because their outer surfaces/cylindrical channel pore entrances can get blocked by the DNA molecules, making the inner parts of the materials inaccessible. Moreover, experiments involving fluorescent dye-tagged DNAs suggest that the amine-grafted KCC-1 materials are better suited for delivering the DNAs adsorbed on their surfaces into cellular environments than their MCM-41 counterparts. Finally, cellular toxicity tests show that the KCC-1-based materials are biocompatible. On the basis of these results, the fibrous and porous KCC-1-based nanomaterials can be said to be more suitable to carry, transport, and deliver DNAs and genes than cylindrical porous nanomaterials such as MCM-41.
NASA Astrophysics Data System (ADS)
Milleret, R.; Le Bayon, R.-C.; Lamy, F.; Gobat, J.-M.; Boivin, P.
2009-07-01
SummarySoil biota such as earthworms, arbuscular mycorrhizal fungi (AMF) and plant roots are known to play a major role in engineering the belowground part of the terrestrial ecosystems, thus strongly influencing the water budget and quality on earth. However, the effect of soil organisms and their interactions on the numerous soil physical properties to be considered are still poorly understood. Shrinkage analysis allows quantifying a large spectrum of soil properties in a single experiment, with small standard errors. The objectives of the present study were, therefore, to assess the ability of the method to quantify changes in soil properties as induced by single or combined effects of leek roots ( Allium porrum), AMF ( Glomus intraradices) and earthworms ( Allolobophora chlorotica). The study was performed on homogenised soil microcosms and the experiments lasted 35 weeks. The volume of the root network and the external fungal hyphae was measured at the end, and undisturbed soil cores were collected. Shrinkage analysis allowed calculating the changes in soil hydro-structural stability, soil plasma and structural pore volumes, soil bulk density and plant available water, and structural pore size distributions. Data analysis revealed different impacts of the experimented soil biota on the soil physical properties. At any water content, the presence of A. chlorotica resulted in a decrease of the specific bulk volume and the hydro-structural stability around 25%, and in a significant increase in the bulk soil density. These changes went with a decrease of the structural pore volumes at any pore size, a disappearing of the thinnest structural pores, a decrease in plant available water, and a hardening of the plasma. On the contrary, leek roots decreased the bulk soil density up to 1.23 g cm -3 despite an initial bulk density of 1.15 g cm -3. This increase in volume was accompanied with a enhanced hydro-structural stability, a larger structural pore volume at any pore size, smaller structural pore radii and an increase in plant available water. Interestingly, a synergistic effect of leek roots and AMF in the absence of the earthworms was highlighted, and this synergistic effect was not observed in presence of earthworms. The structural pore volume generated by root and AMF growth was several orders of magnitude larger than the volume of the organisms. Root exudates as well as other AMF secretion have served as carbon source for bacteria that in turn would enhance soil aggregation and porosity, thus supporting the idea of a self-organization of the soil-plant-microbe complex previously described.
Pore size distribution and accessible pore size distribution in bituminous coals
DOE Office of Scientific and Technical Information (OSTI.GOV)
Sakurovs, Richard; He, Lilin; Melnichenko, Yuri B
2012-01-01
The porosity and pore size distribution of coals determine many of their properties, from gas release to their behavior on carbonization, and yet most methods of determining pore size distribution can only examine a restricted size range. Even then, only accessible pores can be investigated with these methods. Small-angle neutron scattering (SANS) and ultra small-angle neutron scattering (USANS) are increasingly used to characterize the size distribution of all of the pores non-destructively. Here we have used USANS/SANS to examine 24 well-characterized bituminous and subbituminous coals: three from the eastern US, two from Poland, one from New Zealand and the restmore » from the Sydney and Bowen Basins in Eastern Australia, and determined the relationships of the scattering intensity corresponding to different pore sizes with other coal properties. The range of pore radii examinable with these techniques is 2.5 nm to 7 {micro}m. We confirm that there is a wide range of pore sizes in coal. The pore size distribution was found to be strongly affected by both rank and type (expressed as either hydrogen or vitrinite content) in the size range 250 nm to 7 {micro}m and 5 to 10 nm, but weakly in intermediate regions. The results suggest that different mechanisms control coal porosity on different scales. Contrast-matching USANS and SANS were also used to determine the size distribution of the fraction of the pores in these coals that are inaccessible to deuterated methane, CD{sub 4}, at ambient temperature. In some coals most of the small ({approx} 10 nm) pores were found to be inaccessible to CD{sub 4} on the time scale of the measurement ({approx} 30 min - 16 h). This inaccessibility suggests that in these coals a considerable fraction of inherent methane may be trapped for extended periods of time, thus reducing the effectiveness of methane release from (or sorption by) these coals. Although the number of small pores was less in higher rank coals, the fraction of total pores that was inaccessible was not rank dependent. In the Australian coals, at the 10 nm to 50 nm size scales the pores in inertinites appeared to be completely accessible to CD{sub 4}, whereas the pores in the vitrinite were about 75% inaccessible. Unlike the results for total porosity that showed no regional effects on relationships between porosity and coal properties, clear regional differences in the relationships between fraction of closed porosity and coal properties were found. The 10 to 50 nm-sized pores of inertinites of the US and Polish coals examined appeared less accessible to methane than those of the inertinites of Australian coals. This difference in pore accessibility in inertinites may explain why empirical relationships between fluidity and coking properties developed using Carboniferous coals do not apply to Australian coals.« less
NASA Astrophysics Data System (ADS)
Holzner, M.; Morales, V.; Willmann, M.; Jerjen, I.; Kaufmann, R.; Dentz, M.
2016-12-01
Continuum models of porous media are based on the validity of the Darcy equation for fluid and Fick's law for scalar fluxes on a representative elementary volume. Fluctuations of pore-scale flow and scalar transport are averaged out and represented in terms of effective parameters such as hydrodynamic dispersion. However, the intermittent behavior of pore-scale flow impacts on the nature of particle and scalar transport, and it determines the way dissolved substances mix and react. The understanding of the origin of these processes is of both fundamental and practical importance in applications ranging from reactive transport in groundwater flow to diffusion in fuel cells or biological systems. A central issue in porous medium flow is therefore to relate intermittent behavior of Lagrangian velocity at pore scale imposed by the complex pore network geometry to transport properties at larger scales. Lagrangian measurements in porous systems are nonetheless scarce and most experimental techniques do not provide access to all three velocity components. In this contribution we report 3D measurements of Lagrangian velocity in soil-like porous media. We complement these measurements with detailed X-ray scans of the pore network. We find sharp velocity transitions close to pore throats, and low flow variability in the pore bodies, which gives rise to stretched exponential Lagrangian velocity and acceleration distributions characterized by a sharp peak at low velocity and a superlinear evolution of particle dispersion. We demonstrate that porosity and pore size distribution alone cannot explain the observed features of the flow. Rather, anomalous transport is better interpreted in terms of how pores of various geometries are interconnected. We reproduce the main observations using a continuous-time random walk (CTRW) model revealing the main features that control the system and showing the potential of this simple model to capture transport in complex geometries.
Neusser, G; Eppler, S; Bowen, J; Allender, C J; Walther, P; Mizaikoff, B; Kranz, C
2017-10-05
We present combined focused ion beam/scanning electron beam (FIB/SEM) tomography as innovative method for differentiating and visualizing the distribution and connectivity of pores within molecularly imprinted polymers (MIPs) and non-imprinted control polymers (NIPs). FIB/SEM tomography is used in cell biology for elucidating three-dimensional structures such as organelles, but has not yet been extensively applied for visualizing the heterogeneity of nanoscopic pore networks, interconnectivity, and tortuosity in polymers. To our best knowledge, the present study is the first application of this strategy for analyzing the nanoscale porosity of MIPs. MIPs imprinted for propranolol - and the corresponding NIPs - were investigated establishing FIB/SEM tomography as a viable future strategy complementing conventional isotherm studies. For visualizing and understanding the properties of pore networks in detail, polymer particles were stained with osmium tetroxide (OsO 4 ) vapor, and embedded in epoxy resin. Staining with OsO 4 provides excellent contrast during high-resolution SEM imaging. After optimizing the threshold to discriminate between the stained polymer matrix, and pores filled with epoxy resin, a 3D model of the sampled volume may be established for deriving not only the pore volume and pore surface area, but also to visualize the interconnectivity and tortuosity of the pores within the sampled polymer volume. Detailed studies using different types of cross-linkers and the effect of hydrolysis on the resulting polymer properties have been investigated. In comparison of MIP and NIP, it could be unambiguously shown that the interconnectivity of the visualized pores in MIPs is significantly higher vs. the non-imprinted polymer, and that the pore volume and pore area is 34% and approx. 35% higher within the MIP matrix. This confirms that the templating process not only induces selective binding sites, but indeed also affects the physical properties of such polymers down to the nanoscale, and that additional chemical modification, e.g., via hydrolysis clearly affects that nature of the polymer.
NASA Astrophysics Data System (ADS)
Mizuki, Hidenobu; Ito, Yudai; Harada, Hisashi; Uezu, Kazuya
Zr(IV) surface-immobilized resins for removal of fluoride ion were prepared by surface template polymerization using polystyrene as a porogen. At polymerization, polystyrene was added in order to increase mesopores (2-50 nm) and macropore (>50 nm) with large macropores (around 300 nm) formed with internal aqueous phase of W⁄O emulsion. The pore structure of Zr(IV) surface-immobilized resins was evaluated by measuring specific surface area, pore volume, and pore size distribution with volumetric adsorption measurement instrument and mercury porosimeter. The adsorption isotherms were well fitted by Langmuir equation. The removal of fluoride was also carried out with column method. Zr(IV) surface-immobilized resins, using 10 g⁄L polystyrene in toluene at polymerization, possessed higher volume of not only mesopores and macropores but also large macropores. Furethermore, by adding the polystyrene with smaller molecular size, the pore volume of mesopores, macropores and large macropores was significantly increased, and the fluoride ion adsorption capacity and the column utilization also increased.
The role of mesopores in MTBE removal with granular activated carbon.
Redding, Adam M; Cannon, Fred S
2014-06-01
This activated carbon research appraised how pore size and empty-bed contact time influenced the removal of methyl tert-butyl ether (MTBE) at part-per-billion (ppb) concentrations when MTBE was the sole organic impurity. The study compared six granular activated carbons (GACs) from three parent sources; these GACs contained a range of pore volume distributions and had uniform slurry pHs of 9.7-10.4 (i.e. the carbons' bulk surface chemistries were basic). Several of these activated carbons had been specifically tailored for enhanced sorption of trace organic compounds. In these tests, MTBE was spiked into deionized-distilled water (∼pH 7); MTBE loading was measured by isotherms and by rapid small-scale column tests (RSSCTs) that simulated full-scale empty-bed contact times of 7, 14, and 28 min. The results showed that both ultra-fine micropores and small-diameter mesopores were important for MTBE adsorption. Specifically, full MTBE loading during RSSCTs bore a strong correlation (R(2) = 0.94) to the product (mL/g × mL/g) of pore volume ≤4.06 Å wide and pore volume between ∼22 Å and ∼59 Å wide. This correlation was greater than for the product of any other pore volume combinations. Also, this product exhibited a stronger correlation than for just one or the other of these two pore ranges. This multiplicative relationship implied that both of these pore sizes were important for the optimum GAC performance of these six carbons (i.e. favorable mass transfer coupled with favorable sorption). The authors also compared MTBE mass loading during RSSCTs (μg MTBE/g GAC) to isotherm capacity (μg MTBE/g GAC). This RSSCT loading "efficiency" ranged from 28% to 96% for the six GACs; this efficiency correlated most strongly to pores that were 14-200 Å wide (R(2) = 0.94). This correlation indicated that only those carbons with a sufficient volume of 14-200 Å pores could adsorb MTBE to the extent that would be predicted from isotherm data. Copyright © 2014 Elsevier Ltd. All rights reserved.
Prodanović, M; Lindquist, W B; Seright, R S
2006-06-01
Using oil-wet polyethylene core models, we present the development of robust throat finding techniques for the extraction, from X-ray microtomographic images, of a pore network description of porous media having porosity up to 50%. Measurements of volume, surface area, shape factor, and principal diameters are extracted for pores and area, shape factor and principal diameters for throats. We also present results on the partitioning of wetting and non-wetting phases in the pore space at fixed volume increments of the injected fluid during a complete cycle of drainage and imbibition. We compare these results with fixed fractional flow injection, where wetting and non-wetting phase are simultaneously injected at fixed volume ratio. Finally we demonstrate the ability to differentiate three fluid phases (oil, water, air) in the pore space.
Metastable Prepores in Tension-Free Lipid Bilayers
NASA Astrophysics Data System (ADS)
Ting, Christina L.; Awasthi, Neha; Müller, Marcus; Hub, Jochen S.
2018-03-01
The formation and closure of aqueous pores in lipid bilayers is a key step in various biophysical processes. Large pores are well described by classical nucleation theory, but the free-energy landscape of small, biologically relevant pores has remained largely unexplored. The existence of small and metastable "prepores" was hypothesized decades ago from electroporation experiments, but resolving metastable prepores from theoretical models remained challenging. Using two complementary methods—atomistic simulations and self-consistent field theory of a minimal lipid model—we determine the parameters for which metastable prepores occur in lipid membranes. Both methods consistently suggest that pore metastability depends on the relative volume ratio between the lipid head group and lipid tails: lipids with a larger head-group volume fraction (or shorter saturated tails) form metastable prepores, whereas lipids with a smaller head-group volume fraction (or longer unsaturated tails) form unstable prepores.
NASA Astrophysics Data System (ADS)
Udawatta, Ranjith P.; Gantzer, Clark J.; Anderson, Stephen H.; Assouline, Shmuel
2016-05-01
Soil compaction degrades soil structure and affects water, heat, and gas exchange as well as root penetration and crop production. The objective of this study was to use X-ray computed microtomography (CMT) techniques to compare differences in geometrical soil pore parameters as influenced by compaction of two different aggregate size classes. Sieved (diameter < 2 mm and < 0.5 mm) and repacked (1.51 and 1.72 Mg m-3) Hamra soil cores of 5 by 5 mm (average porosities were 0.44 and 0.35) were imaged at 9.6 μm resolution at the Argonne Advanced Photon Source (synchrotron facility) using X-ray CMT. Images of 58.9 mm3 volume were analyzed using 3-Dimensional Medial Axis (3-DMA) software. Geometrical characteristics of the spatial distributions of pore structures (pore radii, volume, connectivity, path length, and tortuosity) were numerically investigated. Results show that the coordination number (CN) distribution and path length (PL) measured from the medial axis were reasonably fit by exponential relationships P(CN) = 10-CN/Co and P(PL) = 10-PL/PLo, respectively, where Co and PLo are the corresponding characteristic constants. Compaction reduced porosity, average pore size, number of pores, and characteristic constants. The average pore radii (63.7 and 61 µm; p < 0.04), largest pore volume (1.58 and 0.58 mm3; p = 0.06), number of pores (55 and 50; p = 0.09), and characteristic coordination number (3.74 and 3.94; p = 0.02) were significantly different between the low-density than the high-density treatment. Aggregate size also influenced measured geometrical pore parameters. This analytical technique provides a tool for assessing changes in soil pores that affect hydraulic properties and thereby provides information to assist in assessment of soil management systems.
Jahandar Lashaki, Masoud; Atkinson, John D; Hashisho, Zaher; Phillips, John H; Anderson, James E; Nichols, Mark
2016-09-05
The effect of activated carbon's pore size distribution (PSD) on heel formation during adsorption of organic vapors was investigated. Five commercially available beaded activated carbons (BAC) with varying PSDs (30-88% microporous) were investigated. Virgin samples had similar elemental compositions but different PSDs, which allowed for isolating the contribution of carbon's microporosity to heel formation. Heel formation was linearly correlated (R(2)=0.91) with BAC micropore volume; heel for the BAC with the lowest micropore volume was 20% lower than the BAC with the highest micropore volume. Meanwhile, first cycle adsorption capacities and breakthrough times correlated linearly (R(2)=0.87 and 0.93, respectively) with BAC total pore volume. Micropore volume reduction for all BACs confirmed that heel accumulation takes place in the highest energy pores. Overall, these results show that a greater portion of adsorbed species are converted into heel on highly microporous adsorbents due to higher share of high energy adsorption sites in their structure. This differs from mesoporous adsorbents (low microporosity) in which large pores contribute to adsorption but not to heel formation, resulting in longer adsorbent lifetime. Thus, activated carbon with high adsorption capacity and high mesopore fraction is particularly desirable for organic vapor application involving extended adsorption/regeneration cycling. Copyright © 2016 Elsevier B.V. All rights reserved.
Alrwashdeh, Saad S; Manke, Ingo; Markötter, Henning; Klages, Merle; Göbel, Martin; Haußmann, Jan; Scholta, Joachim; Banhart, John
2017-06-27
Understanding the function of nanoporous materials employed in polymer electrolyte membrane fuel cells (PEMFCs) is crucial to improve their performance, durability, and cost efficiency. Up to now, the water distribution in the nm-sized pore structures was hardly accessible during operation of the cells. Here we demonstrate that phase contrast synchrotron X-ray tomography allows for an in operando quantification of the three-dimensional water distribution within the nm-sized pores of carbon-based microporous layers (MPLs). For this purpose, a fuel cell design optimized for tomographic phase contrast measurements was realized. Water in the pores of the entire MPL was detected and quantified. We found an inhomogeneous distribution of the local water saturation and a sharp boundary between mostly filled MPL and almost empty areas. We attribute the latter observation to the two-phase boundary created because condensation takes place predominantly on one side of the boundary. Furthermore, high water saturation in large areas hints at gas diffusion or transport along preferred three-dimensional paths through the material, therefore bypassing most of the MPL volume. Our approach may contribute significantly to future investigations of nanoporous fuel cell materials under realistic operating conditions.
High surface area carbon and process for its production
Romanos, Jimmy; Burress, Jacob; Pfeifer, Peter; Rash, Tyler; Shah, Parag; Suppes, Galen
2016-12-13
Activated carbon materials and methods of producing and using activated carbon materials are provided. In particular, biomass-derived activated carbon materials and processes of producing the activated carbon materials with prespecified surface areas and pore size distributions are provided. Activated carbon materials with preselected high specific surface areas, porosities, sub-nm (<1 nm) pore volumes, and supra-nm (1-5 nm) pore volumes may be achieved by controlling the degree of carbon consumption and metallic potassium intercalation into the carbon lattice during the activation process.
Pore architecture of nanoporous gold and titania by hydrogen thermoporometry
Johnston, L. T.; Biener, M. M.; Ye, J. C.; ...
2015-07-10
Nanoporous gold (NPG) and materials derived from it by templating have complex pore architecture that determines their technologically relevant physical properties. Here, we apply high-resolution hydrogen thermoporometry to study the pore structure of NPG and NPG-derived titania nanofoam (TNF). Results reveal complex multimodal pore size distributions for NPG and TNF. The freezing–melting hysteresis is pronounced, with freezing and melting scans having entirely different shapes. Experiments involving partial freeze–melt cycles reveal the lack of direct correlation between individual freezing and melting peaks, pointing to phenomena that are beyond the Gibbs-Thomson formalism. The depression of the average freezing temperature scales linearly withmore » the ratio of the internal surface area (measured by gas sorption) and the total pore volume derived from the density of monoliths. In conclusion, thermoporometry yields total pore volumes in good agreement with those derived from monolith densities for both NPG and TNF.« less
Pore size engineering applied to starved electrochemical cells and batteries
NASA Technical Reports Server (NTRS)
Abbey, K. M.; Thaller, L. H.
1982-01-01
To maximize performance in starved, multiplate cells, the cell design should rely on techniques which widen the volume tolerance characteristics. These involve engineering capillary pressure differences between the components of an electrochemical cell and using these forces to promote redistribution of electrolyte to the desired optimum values. This can be implemented in practice by prescribing pore size distributions for porous back-up plates, reservoirs, and electrodes. In addition, electrolyte volume management can be controlled by incorporating different pore size distributions into the separator. In a nickel/hydrogen cell, the separator must contain pores similar in size to the small pores of both the nickel and hydrogen electrodes in order to maintain an optimum conductive path for the electrolyte. The pore size distributions of all components should overlap in such a way as to prevent drying of the separator and/or flooding of the hydrogen electrode.
Pore architecture of nanoporous gold and titania by hydrogen thermoporometry
DOE Office of Scientific and Technical Information (OSTI.GOV)
Johnston, L. T.; Biener, M. M.; Ye, J. C.
Nanoporous gold (NPG) and materials derived from it by templating have complex pore architecture that determines their technologically relevant physical properties. Here, we apply high-resolution hydrogen thermoporometry to study the pore structure of NPG and NPG-derived titania nanofoam (TNF). Results reveal complex multimodal pore size distributions for NPG and TNF. The freezing–melting hysteresis is pronounced, with freezing and melting scans having entirely different shapes. Experiments involving partial freeze–melt cycles reveal the lack of direct correlation between individual freezing and melting peaks, pointing to phenomena that are beyond the Gibbs-Thomson formalism. The depression of the average freezing temperature scales linearly withmore » the ratio of the internal surface area (measured by gas sorption) and the total pore volume derived from the density of monoliths. In conclusion, thermoporometry yields total pore volumes in good agreement with those derived from monolith densities for both NPG and TNF.« less
Evolution of Micro-Pores in a Single-Crystal Nickel-Based Superalloy During Solution Heat Treatment
NASA Astrophysics Data System (ADS)
Li, Xiangwei; Wang, Li; Dong, Jiasheng; Lou, Langhong; Zhang, Jian
2017-06-01
Evolution of micro-pores in a third-generation single-crystal nickel-based superalloy during solution heat treatment at 1603 K (1330 °C) was investigated by X-ray computed tomography. 3D information including morphology, size, number, and volume fraction of micro-pores formed during solidification (S-pores) and solution (H-pores) was analyzed. The growth behaviors of both S-pores and H-pores can be related to the vacancy formation and diffusion during heat treatment.
Root induced changes of effective 1D hydraulic properties in a soil column.
Scholl, P; Leitner, D; Kammerer, G; Loiskandl, W; Kaul, H-P; Bodner, G
Roots are essential drivers of soil structure and pore formation. This study aimed at quantifying root induced changes of the pore size distribution (PSD). The focus was on the extent of clogging vs. formation of pores during active root growth. Parameters of Kosugi's lognormal PSD model were determined by inverse estimation in a column experiment with two cover crops (mustard, rye) and an unplanted control. Pore dynamics were described using a convection-dispersion like pore evolution model. Rooted treatments showed a wider range of pore radii with increasing volumes of large macropores >500 μm and micropores <2.5 μm, while fine macropores, mesopores and larger micropores decreased. The non-rooted control showed narrowing of the PSD and reduced porosity over all radius classes. The pore evolution model accurately described root induced changes, while structure degradation in the non-rooted control was not captured properly. Our study demonstrated significant short term root effects with heterogenization of the pore system as dominant process of root induced structure formation. Pore clogging is suggested as a partial cause for reduced pore volume. The important change in micro- and large macropores however indicates that multiple mechanic and biochemical processes are involved in root-pore interactions.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Renteria, A. Flores; Saruhan-Brings, B.; Ilavsky, J.
2008-03-03
Thermal barrier coatings (TBCs) deposited by Electron-beam physical deposition (EB-PVD) protect the turbine blades situated at the high pressure sector of the aircraft and stationary turbines. It is an important task to uphold low thermal conductivity in TBCs during long-term service at elevated temperatures. One of the most promising methods to fulfil this task is to optimize the properties of PYSZ-based TBC by tailoring its microstructure. Thermal conductivity of the EB-PVD produced PYSZ TBCs is influenced mainly by the size, shape, orientation and volume of the various types of porosity present in the coatings. These pores can be classified asmore » open (inter-columnar and between feather arms gaps) and closed (intra-columnar pores). Since such pores are located within the three-dimensionally deposited columns and enclose large differences in their sizes, shapes, distribution and anisotropy, the accessibility for their characterization is very complex and requires the use of sophisticated methods. In this work, three different EB-PVD TBC microstructures were manufactured by varying the process parameters, yielding various characteristics of their pores. The corresponding thermal conductivities in as-coated state and after ageing at 11000C/1h and 100h were measured via Laser Flash Analysis Method (LFA). The pore characteristics and their individual effect on the thermal conductivity are analysed by USAXS which is supported by subsequent modelling and LFA methods, respectively. Evident differences in the thermal conductivity values of each microstructure were found in as-coated and aged conditions. In summary, broader columns introduce higher values in thermal conductivity. In general, thermal conductivity increases after ageing for all three investigated microstructures, although those with initial smaller pore surface area show smaller changes.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Renteria, A. F.; Saruhan, B.; Ilavsky, J.
2007-01-01
Thermal barrier coatings (TBCs) deposited by Electron-beam physical deposition (EB-PVD) protect the turbine blades situated at the high pressure sector of the aircraft and stationary turbines. It is an important task to uphold low thermal conductivity in TBCs during long-term service at elevated temperatures. One of the most promising methods to fulfil this task is to optimize the properties of PYSZ-based ,TBC by tailoring its microstructure. Thermal conductivity of the EB-PVD produced PYSZ TBCs is influenced mainly by the size, shape, orientation and volume of the various types of porosity present in the coatings. These pores can be classified asmore » open (inter-columnar and between feather arms gaps) and closed (intra-columnar pores). Since such pores are located within the three-dimensionally deposited columns and enclose large differences in their sizes, shapes, distribution and anisotropy, the accessibility for their characterization is very complex and requires the use of sophisticated methods. In this work, three different EB-PVD TBC microstructures were manufactured by varying the process parameters, yielding various characteristics of their pores. The corresponding thermal conductivities in as-coated state and after ageing at 1100C/1h and 100h were measured via Laser Flash Analysis Method (LFA). The pore characteristics and their individual effect on the thermal conductivity are analysed by USAXS which is supported by subsequent modelling and LFA methods, respectively. Evident differences in the thermal conductivity values of each microstructure were found in as-coated and aged conditions. In summary, broader columns introduce higher values in thermal conductivity. In general, thermal conductivity increases after ageing for all three investigated microstructures, although those with initial smaller pore surface area show smaller changes.« less
Metastable Prepores in Tension-Free Lipid Bilayers
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ting, Christina L.; Awasthi, Neha; Muller, Marcus
The formation and closure of aqueous pores in lipid bilayers is a key step in various biophysical processes. Large pores are well described by classical nucleation theory, but the free-energy landscape of small, biologically relevant pores has remained largely unexplored. The existence of small and metastable “prepores” was hypothesized decades ago from electroporation experiments, but resolving metastable prepores from theoretical models remained challenging. Using two complementary methods—atomistic simulations and self-consistent field theory of a minimal lipid model—we determine the parameters for which metastable prepores occur in lipid membranes. Here, both methods consistently suggest that pore metastability depends on the relativemore » volume ratio between the lipid head group and lipid tails: lipids with a larger head-group volume fraction (or shorter saturated tails) form metastable prepores, whereas lipids with a smaller head-group volume fraction (or longer unsaturated tails) form unstable prepores.« less
Metastable Prepores in Tension-Free Lipid Bilayers
Ting, Christina L.; Awasthi, Neha; Muller, Marcus; ...
2018-03-23
The formation and closure of aqueous pores in lipid bilayers is a key step in various biophysical processes. Large pores are well described by classical nucleation theory, but the free-energy landscape of small, biologically relevant pores has remained largely unexplored. The existence of small and metastable “prepores” was hypothesized decades ago from electroporation experiments, but resolving metastable prepores from theoretical models remained challenging. Using two complementary methods—atomistic simulations and self-consistent field theory of a minimal lipid model—we determine the parameters for which metastable prepores occur in lipid membranes. Here, both methods consistently suggest that pore metastability depends on the relativemore » volume ratio between the lipid head group and lipid tails: lipids with a larger head-group volume fraction (or shorter saturated tails) form metastable prepores, whereas lipids with a smaller head-group volume fraction (or longer unsaturated tails) form unstable prepores.« less
Mechanical properties and failure behavior of unidirectional porous ceramics
NASA Astrophysics Data System (ADS)
Seuba, Jordi; Deville, Sylvain; Guizard, Christian; Stevenson, Adam J.
2016-04-01
We show that the honeycomb out-of-plane model derived by Gibson and Ashby can be applied to describe the compressive behavior of unidirectional porous materials. Ice-templating allowed us to process samples with accurate control over pore volume, size, and morphology. These samples allowed us to evaluate the effect of this microstructural variations on the compressive strength in a porosity range of 45-80%. The maximum strength of 286 MPa was achieved in the least porous ice-templated sample (P(%) = 49.9), with the smallest pore size (3 μm). We found that the out-of-plane model only holds when buckling is the dominant failure mode, as should be expected. Furthermore, we controlled total pore volume by adjusting solids loading and sintering temperature. This strategy allows us to independently control macroporosity and densification of walls, and the compressive strength of ice-templated materials is exclusively dependent on total pore volume.
Mechanical properties and failure behavior of unidirectional porous ceramics.
Seuba, Jordi; Deville, Sylvain; Guizard, Christian; Stevenson, Adam J
2016-04-14
We show that the honeycomb out-of-plane model derived by Gibson and Ashby can be applied to describe the compressive behavior of unidirectional porous materials. Ice-templating allowed us to process samples with accurate control over pore volume, size, and morphology. These samples allowed us to evaluate the effect of this microstructural variations on the compressive strength in a porosity range of 45-80%. The maximum strength of 286 MPa was achieved in the least porous ice-templated sample (P(%) = 49.9), with the smallest pore size (3 μm). We found that the out-of-plane model only holds when buckling is the dominant failure mode, as should be expected. Furthermore, we controlled total pore volume by adjusting solids loading and sintering temperature. This strategy allows us to independently control macroporosity and densification of walls, and the compressive strength of ice-templated materials is exclusively dependent on total pore volume.
Prediction of Hydraulic Conductivity as Related to Pore Size Distribution in Unsaturated Soils
USDA-ARS?s Scientific Manuscript database
Soil pore volume as well as pore size, shape, type (i.e. biopore versus crack), continuity, and distribution in soil affect soil water and gas exchange. Vertical and lateral drainage of water by gravitational forces occurs through large, non-capillary soil pores, but redistribution and upward moveme...
NASA Astrophysics Data System (ADS)
Moebius, Franziska; Or, Dani
2014-05-01
The macroscopically smooth and regular motion of fluid fronts in porous media is composed of numerous rapid pore-scale interfacial jumps and pressure bursts that involve intense interfacial energy release in the form of acoustic emissions. The characteristics of these pore scale events affect residual phase entrapment and transport properties behind the front. We present experimental studies using acoustic emission technique (AE), rapid imaging, and liquid pressure measurements to characterize these processes during drainage and imbibition in simple porous media. Imbibition and drainage produce different AE signatures (AE amplitudes obey a power law). For rapid drainage, AE signals persist long after cessation of front motion reflecting fluid redistribution and interfacial relaxation. Imaging revealed that the velocity of interfacial jumps often exceeds front velocity by more than 50 fold and is highly inertial component (Re>1000). Pore invasion volumes reduced deduced from pressure fluctuations waiting times (for constant withdrawal rates) show remarkable agreement with geometrically-deduced pore volumes. Discrepancies between invaded volumes and geometrical pores increase with increasing capillary numbers due to constraints on evacuation opportunity times and simultaneous invasion events. A mechanistic model for interfacial motions in a pore-throat network was developed to investigate interfacial dynamics focusing on the role of inertia. Results suggest that while pore scale dynamics were sensitive to variations in pore geometry and boundary conditions, inertia exerted only a minor effect on phase entrapment. The study on pore scale invasion events paints a complex picture of rapid and inertial motions and provides new insights on mechanisms at displacement fronts that are essential for improved macroscopic description of multiphase flows in porous media.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Patton, J.T.; Holbrook, S.T.
1990-01-01
The selection of the optimum foaming agent (surfactant) for enhancing oil production by carbon dioxide flooding is based on foamability and adsorption. Measurement of adsorption on carbonate cores from New Mexico reservoirs showed large adsorption differences between three commercial, high-foaming surfactants. An ethoxylated alcohol structure was least adsorbed, 0.64 mg/cc pore volume; an ethoxylated alcohol sulfate was next, 0.74 mg/cc pore volume; the highest adsorbed was a glyceryl sulfonate, 2.30 mg/cc pore volume. Commercial application of the foaming additive involves injecting alternate slugs of surfactant solution and carbon dioxide. Surfactant concentration should be determined to allow for the adsorption above.
Porosity of Self-Compacting Concrete (SCC) incorporating high volume fly ash
NASA Astrophysics Data System (ADS)
Kristiawan, S. A.; Sunarmasto; Murti, G. Y.
2017-02-01
Degradation of concrete could be triggered by the presence of aggressive agents from the environment into the body of concrete. The penetration of these agents is influenced by the pore characteristics of the concrete. Incorporating a pozzolanic material such as fly ash could modify the pore characteristic of the concrete. This research aims to investigate the influence of incorporating fly ash at high volume level on the porosity of Self-Compacting Concrete (SCC). Laboratory investigations were carried out following the ASTM C642 for measuring density and volume of permeable pores (voids) of the SCC with varying fly ash contents (50-70% by weight of total binder). In addition, a measurement of permeable voids by saturation method was carried out to obtain an additional volume of voids that could not be measured by the immersion and boiling method of ASTM C642. The results show that the influence of fly ash content on the porosity appears to be dependent on age of SCC. At age less than 56 d, fly ash tends to cause an increase of voids but at 90 d of age it reduces the pores. The additional pores that can be penetrated by vacuum saturation method counts about 50% of the total voids.
NASA Astrophysics Data System (ADS)
Bendz, David; Tüchsen, Peter L.; Christensen, Thomas H.
2007-12-01
Leaching and tracer experiments in batches at L/S 20 were performed with 3-month-old MSWI bottom ash separated into eight different particle sizes. The time-dependent leaching of major elements (Ca 2+, K +, Na +, Cl - and SO 4- 2 ) was monitored for up to 747 h. Physical properties of the particles, the specific surface (BET), pore volume and pore volume distribution over pore sizes (BJH) were determined for all particle classes by N 2 adsorption/desorption experiments. Some common features of physical pore structure for all particles were revealed. The specific surface and the particle pore volume were found to be negatively correlated with particle size, ranging from 3.2 m 2/g to 25.7 m 2/g for the surface area and from 0.0086 cm 3/g to 0.091 cm 3/g for the pore volume. Not surprisingly, the specific surface area was found to be the major material parameter that governed the leaching behavior for all elements (Ca 2+, K +, Na +, Cl - and SO 4- 2 ) and particle sizes. The diffusion resistance was determined independently by separate tracer (tritium) experiments. Diffusion gave a significant contribution to the apparent leaching kinetics for all elements during the first 10-40 h (depending on the particle size) of leaching and surface reaction was the overall rate controlling mechanism at late times for all particle sizes. For Ca 2+ and SO 4- 2 , the coupled effect of diffusion resistance and the degree of undersaturation in the intra particle pore volume was found to be a major rate limiting dissolution mechanism for both early and late times. The solubility control in the intra particulate porosity may undermine any attempt to treat bottom ash by washing out the sulfate. Even for high liquid/solid ratios, the solubility in the intra-particular porosity will limit the release rate.
NASA Astrophysics Data System (ADS)
Patil, Vishal; Liburdy, James
2012-11-01
Turbulent porous media flows are encountered in catalytic bed reactors and heat exchangers. Dispersion and mixing properties of these flows play an essential role in efficiency and performance. In an effort to understand these flows, pore scale time resolved PIV measurements in a refractive index matched porous bed were made. Pore Reynolds numbers, based on hydraulic diameter and pore average velocity, were varied from 400-4000. Jet-like flows and recirculation regions associated with large scale structures were found to exist. Coherent vortical structures which convect at approximately 0.8 times the pore average velocity were identified. These different flow regions exhibited different turbulent characteristics and hence contributed unequally to global transport properties of the bed. The heterogeneity present within a pore and also from pore to pore can be accounted for in estimating transport properties using the method of volume averaging. Eddy viscosity maps and mean velocity field maps, both obtained from PIV measurements, along with the method of volume averaging were used to predict the dispersion tensor versus Reynolds number. Asymptotic values of dispersion compare well to existing correlations. The role of molecular diffusion was explored by varying the Schmidt number and molecular diffusion was found to play an important role in tracer transport, especially in recirculation regions. Funding by NSF grant 0933857, Particulate and Multiphase Processing.
USDA-ARS?s Scientific Manuscript database
Characterization of biochars usually includes surface area and pore volume determination by nitrogen adsorption. In this study, we show that there is a substantial pore volume in biochars created via slow pyrolysis from low- and high-ash almond shells that cannot be characterized in this fashion due...
Effects of pore volume-transmissivity correlation on transport phenomena.
Lunati, Ivan; Kinzelbach, Wolfgang; Sørensen, Ivan
2003-12-01
The relevant velocity that describes transport phenomena in a porous medium is the pore velocity. For this reason, one needs not only to describe the variability of transmissivity, which fully determines the Darcy velocity field for given source terms and boundary conditions, but also any variability of the pore volume. We demonstrate that hydraulically equivalent media with exactly the same transmissivity field can produce dramatic differences in the displacement of a solute if they have different pore volume distributions. In particular, we demonstrate that correlation between pore volume and transmissivity leads to a much smoother and more homogeneous solute distribution. This was observed in a laboratory experiment performed in artificial fractures made of two plexiglass plates into which a space-dependent aperture distribution was milled. Using visualization by a light transmission technique, we observe that the solute behaviour is much smoother and more regular after the fractures are filled with glass powder, which plays the role of a homogeneous fault gouge material. This is due to a perfect correlation between pore volume and transmissivity that causes pore velocity to be not directly dependent on the transmissivity, but only indirectly through the hydraulic gradient, which is a much smoother function due to the diffusive behaviour of the flow equation acting as a filter. This smoothing property of the pore volume-transmissivity correlation is also supported by numerical simulations of tracer tests in a dipole flow field. Three different conceptual models are used: an empty fracture, a rough-walled fracture filled with a homogeneous material and a parallel-plate fracture with a heterogeneous fault gouge. All three models are hydraulically equivalent, yet they have a different pore volume distribution. Even if piezometric heads and specific flow rates are exactly the same at any point of the domain, the transport process differs dramatically. These differences make it important to discriminate in situ among different conceptual models in order to simulate correctly the transport phenomena. For this reason, we study the solute breakthrough and recovery curves at the extraction wells. Our numerical case studies show that discrimination on the basis of such data might be impossible except under very favourable conditions, i.e. the integral scale of the transmissivity field has to be known and small compared to the dipole size. If the latter conditions are satisfied, discrimination between the rough-walled fracture filled with a homogeneous material and the other two models becomes possible, whereas the parallel-plate fracture with a heterogeneous fault gouge and the empty fracture still show identifiability problems. The latter may be solved by inspection of aperture and pressure testing.
Adsorption of SO2 onto oxidized and heat-treated activated carbon fibers (ACFs)
Daley, M.A.; Mangun, C.L.; DeBarr, J.A.; Riha, S.; Lizzio, A.A.; Donnals, G.L.; Economy, J.
1997-01-01
Oxidation of the ACFs, using an aqueous oxidant, decreased their adsorption capacity for SO2 from flue gas due to a decrease in pore volume and repulsion of the SO2 from acidic surface groups. If these samples were heat-treated to desorb the oxygen containing function groups, the amount of SO2 adsorption increased. This increase in adsorption capacity was directly correlated to the amount of CO2 evolved during heat-treatment of the oxidized ACFs. The amount of SO2 adsorbed for these samples was related to the pore size, pore surface chemistry and pore volume. This analysis is explained in more detail in this paper.
Zhao, Cunyu; Liu, Lianjun; Zhao, Huilei; Krall, Andy; Wen, Zhenhai; Chen, Junhong; Hurley, Patrick; Jiang, Junwei; Li, Ying
2014-01-21
Sulfur has received increasing attention as a cathode material for lithium-sulfur (Li-S) batteries due to its high theoretical specific capacity. However, the commercialization of Li-S batteries is limited by the challenges of poor electrical conductivity of sulfur, dissolution of the polysulfide intermediates into the electrolyte, and volume expansion of sulfur during cycling. Herein, we report the fabrication of novel-structured porous carbon microspheres with a controllable multi-modal pore size distribution, i.e., a combination of interconnected micropores, mesopores and macropores. Cathodes made of sulfur infiltrated in such a hierarchical carbon framework provide several advantages: (1) a continuous and high surface area carbon network for enhanced electrical conductivity and high sulfur loading; (2) macropores and large mesopores bridged by small mesopores to provide good electrolyte accessibility and fast Li ion transport and to accommodate volume expansion of sulfur; and (3) small mesopores and micropores to improve carbon/sulfur interaction and to help trap polysulfides. An initial discharge capacity at 1278 mA h g(-1) and capacity retention at 70.7% (904 mA h g(-1)) after 100 cycles at a high rate (1 C) were achieved. The material fabrication process is relatively simple and easily scalable.
George, David L.; Iverson, Richard M.
2011-01-01
Pore-fluid pressure plays a crucial role in debris flows because it counteracts normal stresses at grain contacts and thereby reduces intergranular friction. Pore-pressure feedback accompanying debris deformation is particularly important during the onset of debrisflow motion, when it can dramatically influence the balance of forces governing downslope acceleration. We consider further effects of this feedback by formulating a new, depth-averaged mathematical model that simulates coupled evolution of granular dilatancy, solid and fluid volume fractions, pore-fluid pressure, and flow depth and velocity during all stages of debris-flow motion. To illustrate implications of the model, we use a finite-volume method to compute one-dimensional motion of a debris flow descending a rigid, uniformly inclined slope, and we compare model predictions with data obtained in large-scale experiments at the USGS debris-flow flume. Predictions for the first 1 s of motion show that increasing pore pressures (due to debris contraction) cause liquefaction that enhances flow acceleration. As acceleration continues, however, debris dilation causes dissipation of pore pressures, and this dissipation helps stabilize debris-flow motion. Our numerical predictions of this process match experimental data reasonably well, but predictions might be improved by accounting for the effects of grain-size segregation.
NASA Astrophysics Data System (ADS)
Udawatta, Ranjith; Gantzer, Clark; Anderson, Stephen; Assouline, Shmuel
2015-04-01
Soil compaction degrades soil structure and affects water, heat, and gas exchange as well as root penetration and crop production. The objective of this study was to use X-ray computed microtomography (CMT) techniques to compare differences in geometrical soil pore parameters as influenced by compaction of two different aggregate size classes. Sieved (diam. < 2mm and < 0.5mm) and repacked (1.51 and 1.72 Mg m-3) Hamra soil cores of 5- by 5-mm (average porosities were 0.44 and 0.35) were imaged at 9.6-micrometer resolution at the Argonne Advanced Photon Source (synchrotron facility) using X-ray computed microtomography. Images of 58.9 mm3 volume were analyzed using 3-Dimensional Medial Axis (3DMA) software. Geometrical characteristics of the spatial distributions of pore structures (pore radii, volume, connectivity, path length, and tortuosity) were numerically investigated. Results show that the coordination number (CN) distribution and path length (PL) measured from the medial axis were reasonably fit by exponential relationships P(CN)=10-CN/Co and P(PL)=10-PL/PLo, respectively, where Co and PLo are the corresponding characteristic constants. Compaction reduced porosity, average pore size, number of pores, and characteristic constants. The average pore radii (64 and 61 μm; p<0.04), largest pore volume (1.6 and 0.6 mm3; p=0.06), number of pores (55 and 50; p=0.09), characteristic coordination number (6.3 and 6.0; p=0.09), and characteristic path length number (116 and 105; p=0.001) were significantly greater in the low density than the high density treatment. Aggregate size also influenced measured geometrical pore parameters. This analytical technique provides a tool for assessing changes in soil pores that affect hydraulic properties and thereby provides information to assist in assessment of soil management systems.
NASA Astrophysics Data System (ADS)
Udawatta, R. P.; Gantzer, C. J.; Anderson, S. H.; Assouline, S.
2015-07-01
Soil compaction degrades soil structure and affects water, heat, and gas exchange as well as root penetration and crop production. The objective of this study was to use X-ray computed microtomography (CMT) techniques to compare differences in geometrical soil pore parameters as influenced by compaction of two different aggregate size classes. Sieved (diam. < 2 mm and < 0.5 mm) and repacked (1.51 and 1.72 Mg m-3) Hamra soil cores of 5- by 5 mm (average porosities were 0.44 and 0.35) were imaged at 9.6-micrometer resolution at the Argonne Advanced Photon Source (synchrotron facility) using X-ray computed microtomography. Images of 58.9 mm3 volume were analyzed using 3-Dimensional Medial Axis (3DMA) software. Geometrical characteristics of the spatial distributions of pore structures (pore radii, volume, connectivity, path length, and tortuosity) were numerically investigated. Results show that the coordination number (CN) distribution and path length (PL) measured from the medial axis were reasonably fit by exponential relationships P(CN) = 10-CN/Co and P(PL) = 10-PL/PLo, respectively, where Co and PLo are the corresponding characteristic constants. Compaction reduced porosity, average pore size, number of pores, and characteristic constants. The average pore radii (63.7 and 61 μm; p < 0.04), largest pore volume (1.58 and 0.58 mm3; p = 0.06), number of pores (55 and 50; p = 0.09), characteristic coordination number (6.32 and 5.94; p = 0.09), and characteristic path length number (116 and 105; p = 0.001) were significantly greater in the low density than the high density treatment. Aggregate size also influenced measured geometrical pore parameters. This analytical technique provides a tool for assessing changes in soil pores that affect hydraulic properties and thereby provides information to assist in assessment of soil management systems.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Tanju Karanfil; Seyed A. Dastgheib; Dina Mauldin
2006-02-15
Adsorption of trichloroethylene (TCE) by two activated carbon fibers ACF10 and ACF20H and two granular activated carbons, coal-based F400 and Macro preloaded with hydrophobic and transphilic fractions of natural organic matter (NOM) was examined. ACF10, the most microporous activated carbon used in this study, had over 90% of its pore volume in pores smaller than 10 {angstrom}. It also had the highest volume in pores 5-8 {angstrom}, which is the optimum pore size region for TCE adsorption, among the four activated carbons. Adsorption of NOM fractions by ACF10 was, in general, negligible. Therefore, ACF10, functioning as a molecular sieve duringmore » preloading, exhibited the least NOM uptake for each fraction, and subsequently the highest TCE adsorption. The other three sorbents had wider pore size distributions, including high volumes in pores larger than 10 {angstrom}, where NOM molecules can adsorb. As a result, they showed a higher degree of uptake for all NOM fractions, and subsequently lower adsorption capacities for TCE, as compared to ACF10. The results obtained in this study showed that understanding the interplay between the optimum pore size region for the adsorption of target synthetic organic contaminant (SOC) and the pore size region for the adsorption of NOM molecules is important for controlling NOM-SOC competitions. Experiments with different NOM fractions indicated that the degree of NOM loading is important in terms of preloading effects; however the way that the carbon pores are filled and loaded by different NOM fractions can be different and may create an additional negative impact on TCE adsorption. 40 refs., 3 figs., 2 tabs.« less
NASA Astrophysics Data System (ADS)
Xu, Jiandong; Gao, Qiuming; Zhang, Yunlu; Tan, Yanli; Tian, Weiqian; Zhu, Lihua; Jiang, Lei
2014-07-01
Two-dimensional (2D) porous carbon AC-SPN-3 possessing of amazing high micropore volume ratio of 83% and large surface area of about 1069 m2 g-1 is high-yield obtained by pyrolysis of natural waste Pistachio nutshells with KOH activation. The AC-SPN-3 has a curved 2D lamellar morphology with the thickness of each slice about 200 nm. The porous carbon is consists of highly interconnected uniform pores with the median pore diameter of about 0.76 nm, which could potentially improve the performance by maximizing the electrode surface area accessible to the typical electrolyte ions (such as TEA+, diameter = ~0.68 nm). Electrochemical analyses show that AC-SPN-3 has significantly large areal capacitance of 29.3/20.1 μF cm-2 and high energy density of 10/39 Wh kg-1 at power of 52/286 kW kg-1 in 6 M KOH aqueous electrolyte and 1 M TEABF4 in EC-DEC (1:1) organic electrolyte system, respectively.
Liu, Yijin; Meirer, Florian; Krest, Courtney M.; ...
2016-08-30
To understand how hierarchically structured functional materials operate, analytical tools are needed that can reveal small structural and chemical details in large sample volumes. Often, a single method alone is not sufficient to get a complete picture of processes happening at multiple length scales. Here we present a correlative approach combining three-dimensional X-ray imaging techniques at different length scales for the analysis of metal poisoning of an individual catalyst particle. The correlative nature of the data allowed establishing a macro-pore network model that interprets metal accumulations as a resistance to mass transport and can, by tuning the effect of metalmore » deposition, simulate the response of the network to a virtual ageing of the catalyst particle. In conclusion, the developed approach is generally applicable and provides an unprecedented view on dynamic changes in a material’s pore space, which is an essential factor in the rational design of functional porous materials.« less
Adsorption properties of carbon dioxide enchanced oil recovery additives
DOE Office of Scientific and Technical Information (OSTI.GOV)
Patton, J.T.; Holbrook, S.T.
1990-01-01
The selection of the optimum foaming agent (surfactant) for enhancing oil production by carbon dioxide flooding is based on foamability and adsorption. Measurements of adsorption on carbonate cores from New Mexico reservoirs showed large adsorption differences between three commercial, high-foaming surfactants. An ethoxylated alcohol structure was at least adsorbed, 0.64 mg/cc pore volume; an ethoxylated alcohol sulfate was next, 0.74 mg/cc pore volume; the highest adsorbed was a glyceryl sulfonate, 2.30 mg/cc pore volume. Commercial application of the foaming additive involves injecting alternate slugs of surfactant solution and carbon dioxide. Surfactant concentration should be determined to allow for the adsorptionmore » above. 9 refs., 27 figs., 6 tabs.« less
Wang, Xianfeng; Sun, Peipei; Han, Ningxu; Xing, Feng
2017-01-01
Encapsulation of healing agents embedded in a material matrix has become one of the major approaches for achieving self-healing function in cementitious materials in recent years. A novel type of microcapsules based self-healing cementitious composite was developed in Guangdong Provincial Key Laboratory of Durability for Marine Civil Engineering, Shenzhen University. In this study, both macro performance and the microstructure of the composite are investigated. The macro performance was evaluated by employing the compressive strength and the dynamic modulus, whereas the microstructure was represented by the pore structure parameters such as porosity, cumulative-pore volume, and average-pore diameter, which are significantly correlated to the pore-size distribution and the compressive strength. The results showed that both the compressive strength and the dynamic modulus, as well as the pore structure parameters such as porosity, cumulative-pore volume, and average-pore diameter of the specimen decrease to some extent with the amount of microcapsules. However, the self-healing rate and the recovery rate of the specimen performance and the pore-structure parameters increase with the amount of microcapsules. The results should confirm the self-healing function of microcapsules in the cementitious composite from macroscopic and microscopic viewpoints.
Wang, Xianfeng; Sun, Peipei; Han, Ningxu; Xing, Feng
2017-01-01
Encapsulation of healing agents embedded in a material matrix has become one of the major approaches for achieving self-healing function in cementitious materials in recent years. A novel type of microcapsules based self-healing cementitious composite was developed in Guangdong Provincial Key Laboratory of Durability for Marine Civil Engineering, Shenzhen University. In this study, both macro performance and the microstructure of the composite are investigated. The macro performance was evaluated by employing the compressive strength and the dynamic modulus, whereas the microstructure was represented by the pore structure parameters such as porosity, cumulative-pore volume, and average-pore diameter, which are significantly correlated to the pore-size distribution and the compressive strength. The results showed that both the compressive strength and the dynamic modulus, as well as the pore structure parameters such as porosity, cumulative-pore volume, and average-pore diameter of the specimen decrease to some extent with the amount of microcapsules. However, the self-healing rate and the recovery rate of the specimen performance and the pore-structure parameters increase with the amount of microcapsules. The results should confirm the self-healing function of microcapsules in the cementitious composite from macroscopic and microscopic viewpoints. PMID:28772382
NASA Astrophysics Data System (ADS)
Beckingham, Lauren E.; Steefel, Carl I.; Swift, Alexander M.; Voltolini, Marco; Yang, Li; Anovitz, Lawrence M.; Sheets, Julia M.; Cole, David R.; Kneafsey, Timothy J.; Mitnick, Elizabeth H.; Zhang, Shuo; Landrot, Gautier; Ajo-Franklin, Jonathan B.; DePaolo, Donald J.; Mito, Saeko; Xue, Ziqiu
2017-05-01
The rates of mineral dissolution reactions in porous media are difficult to predict, in part because of a lack of understanding of mineral reactive surface area in natural porous media. Common estimates of mineral reactive surface area used in reactive transport models for porous media are typically ad hoc and often based on average grain size, increased to account for surface roughness or decreased by several orders of magnitude to account for reduced surface reactivity of field as opposed to laboratory samples. In this study, accessible mineral surface areas are determined for a sample from the reservoir formation at the Nagaoka pilot CO2 injection site (Japan) using a multi-scale image analysis based on synchrotron X-ray microCT, SEM QEMSCAN, XRD, SANS, and FIB-SEM. This analysis not only accounts for accessibility of mineral surfaces to macro-pores, but also accessibility through connected micro-pores in smectite, the most abundant clay mineral in this sample. While the imaging analysis reveals that most of the micro- and macro-pores are well connected, some pore regions are unconnected and thus inaccessible to fluid flow and diffusion. To evaluate whether mineral accessible surface area accurately reflects reactive surface area a flow-through core experiment is performed and modeled at the continuum scale. The core experiment is performed under conditions replicating the pilot site and the evolution of effluent solutes in the aqueous phase is tracked. Various reactive surface area models are evaluated for their ability to capture the observed effluent chemistry, beginning with parameter values determined as a best fit to a disaggregated sediment experiment (Beckingham et al., 2016) described previously. Simulations that assume that all mineral surfaces are accessible (as in the disaggregated sediment experiment) over-predict the observed mineral reaction rates, suggesting that a reduction of RSA by a factor of 10-20 is required to match the core flood experimental data. While the fit of the effluent chemistry (and inferred mineral dissolution rates) greatly improve when the pore-accessible mineral surface areas are used, it was also necessary to include highly reactive glass phases to match the experimental observations, in agreement with conclusions from the disaggregated sediment experiment. It is hypothesized here that the 10-20 reduction in reactive surface areas based on the limited pore accessibility of reactive phases in core flood experiment may be reasonable for poorly sorted and cemented sediments like those at the Nagaoka site, although this reflects pore rather than larger scale heterogeneity.
NASA Astrophysics Data System (ADS)
Ngom, Ndèye Fatou; Monga, Olivier; Ould Mohamed, Mohamed Mahmoud; Garnier, Patricia
2012-02-01
This paper focuses on the modeling of soil microstructures using generalized cylinders, with a specific application to pore space. The geometric modeling of these microstructures is a recent area of study, made possible by the improved performance of computed tomography techniques. X-scanners provide very-high-resolution 3D volume images ( 3-5μm) of soil samples in which pore spaces can be extracted by thresholding. However, in most cases, the pore space defines a complex volume shape that cannot be approximated using simple analytical functions. We propose representing this shape using a compact, stable, and robust piecewise approximation by means of generalized cylinders. This intrinsic shape representation conserves its topological and geometric properties. Our algorithm includes three main processing stages. The first stage consists in describing the volume shape using a minimum number of balls included within the shape, such that their union recovers the shape skeleton. The second stage involves the optimum extraction of simply connected chains of balls. The final stage copes with the approximation of each simply optimal chain using generalized cylinders: circular generalized cylinders, tori, cylinders, and truncated cones. This technique was applied to several data sets formed by real volume computed tomography soil samples. It was possible to demonstrate that our geometric representation supplied a good approximation of the pore space. We also stress the compactness and robustness of this method with respect to any changes affecting the initial data, as well as its coherence with the intuitive notion of pores. During future studies, this geometric pore space representation will be used to simulate biological dynamics.
Adsorption of polypropylene from dilute solutions on a zeolite column packing.
Macko, Tibor; Pasch, Harald; Denayer, Joeri F
2005-01-01
Faujasite type zeolite CBV-780 was tested as adsorbent for isotactic polypropylene by liquid chromatography. When cyclohexane, cyclohexanol, n-decanol, n-dodecanol, diphenylmethane, or methylcyclohexane was used as mobile phase, polypropylene was fully or partially retained within the column packing. This is the first series of sorbent-solvent systems to show a pronounced retention of isotactic polypropylene. According to the hydrodynamic volumes of polypropylene in solution, macromolecules of polypropylene should be fully excluded from the pore volume of the sorbent. Sizes of polypropylene macromolecules in linear conformations, however, correlate with the pore size of the column packing used. It is presumed that the polypropylene chains partially penetrate into the pores and are retained due to the high adsorption potential in the narrow pores.
Catalyst for hydrotreating carbonaceous liquids
Berg, Lloyd; McCandless, Frank P.; Ramer, Ronald J.
1982-01-01
A catalyst for denitrogenating and desulfurating carbonaceous liquid such as solvent refined coal includes catalytic metal oxides impregnated within a porous base of mostly alumina with relatively large pore diameters, surface area and pore volume. The base material includes pore volumes of 0.7-0.85 ml/g, surface areas of 200-350 m.sup.2 /g and pore diameters of 85-200 Angstroms. The catalytic metals impregnated into these base materials include the oxides of Group VI metals, molybdenum and tungsten, and the oxides of Group VIII metals, nickel and cobalt, in various combinations. These catalysts and bases in combination have effectively promoted the removal of chemically combined sulfur and nitrogen within a continuous flowing mixture of carbonaceous liquid and hydrogen gas.
Liquid Photonic Crystals for Mesopore Detection.
Zhu, Biting; Fu, Qianqian; Chen, Ke; Ge, Jianping
2018-01-02
Nitrogen adsorption-desorption for mesopore characterization requires the using of expensive instrumentation, time-consuming processes, and the consumption of liquid nitrogen. Herein, a new method is developed to measure the pore parameters through mixing a mesoporous substance with a supersaturated SiO 2 colloidal solution at different temperatures, and subsequent rapid measurement of reflection changes of the precipitated liquid photonic crystals. The pore volumes and diameters of mesoporous silica were measured according to the positive correlation between unit mass reflection change (Δλ/m) and pore volume (V), and the negative correlation between average absorption temperature (T) and pore diameter (D). This new approach may provide an alternative method for fast, convenient and economical characterization of mesoporous materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Effect of nitric acid treatment on activated carbon derived from oil palm shell
NASA Astrophysics Data System (ADS)
Allwar, Allwar; Hartati, Retno; Fatimah, Is
2017-03-01
The primary object of this work is to study the effect of nitric acid on the porous and morphology structure of activated carbon. Production of activated carbon from oil palm shell was prepared with pyrolysis process at temperature 900°C and by introduction of 10 M nitric acid. Determination of surface area, pore volume and pore size distribution of activated carbon was conducted by the N2 adsorption-desorption isotherm at 77 K. Morphology structure and elemental micro-analysis of activated carbon were estimated by Scanning Electron Microscopy (SEM) and energy dispersive X-ray (EDX), respectively. The result shows that activated carbon after treating with nitric acid proved an increasing porous characteristics involving surface area, pore volume and pore size distribution. It also could remove the contaminants including metals and exhibit an increasing of pores and crevices all over the surface.
Elements of an improved model of debris-flow motion
Iverson, R.M.
2009-01-01
A new depth-averaged model of debris-flow motion describes simultaneous evolution of flow velocity and depth, solid and fluid volume fractions, and pore-fluid pressure. Non-hydrostatic pore-fluid pressure is produced by dilatancy, a state-dependent property that links the depth-averaged shear rate and volumetric strain rate of the granular phase. Pore-pressure changes caused by shearing allow the model to exhibit rate-dependent flow resistance, despite the fact that the basal shear traction involves only rate-independent Coulomb friction. An analytical solution of simplified model equations shows that the onset of downslope motion can be accelerated or retarded by pore-pressure change, contingent on whether dilatancy is positive or negative. A different analytical solution shows that such effects will likely be muted if downslope motion continues long enough, because dilatancy then evolves toward zero, and volume fractions and pore pressure concurrently evolve toward steady states. ?? 2009 American Institute of Physics.
Water storage capacities of soil under four different land uses in Hawaii
Teruo Yamamoto; Paul Duffy
1963-01-01
Soil pore volume and pore size were correlated with land use or vegetation cover type. The top foot of forest soils had more large pores and higher water-holding capacities than that of soils under cultivation, in pasture land, or in idle grassland.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Yanping Guo; Abhishek Yadav; Tanju Karanfil
Adsorption of trichloroethylene (TCE) and atrazine, two synthetic organic contaminants (SOCs) having different optimum adsorption pore regions, by four activated carbons and an activated carbon fiber (ACF) was examined. Adsorbents included two coconut-shell based granular activated carbons (GACs), two coal-based GACs (F400 and HD4000) and a phenol formaldehyde-based activated carbon fiber. The selected adsorbents had a wide range of pore size distributions but similar surface acidity and hydrophobicity. Single solute and preloading (with a dissolved organic matter (DOM)) isotherms were performed. Single solute adsorption results showed that (i) the adsorbents having higher amounts of pores with sizes about the dimensionsmore » of the adsorbate molecules exhibited higher uptakes, (ii) there were some pore structure characteristics, which were not completely captured by pore size distribution analysis, that also affected the adsorption, and (iii) the BET surface area and total pore volume were not the primary factors controlling the adsorption of SOCs. The preloading isotherm results showed that for TCE adsorbing primarily in pores <10 {angstrom}, the highly microporous ACF and GACs, acting like molecular sieves, exhibited the highest uptakes. For atrazine with an optimum adsorption pore region of 10-20 {angstrom}, which overlaps with the adsorption region of some DOM components, the GACs with a broad pore size distribution and high pore volumes in the 10-20 {angstrom} region had the least impact of DOM on the adsorption. 25 refs., 3 figs., 3 tabs.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Barin, G; Krungleviciute, V; Gutov, O
2014-07-07
We successfully demonstrate an approach based on linker fragmentation to create defects and tune the pore volumes and surface areas of two metal-organic frameworks, NU-125 and HKUST-1, both of which feature copper paddlewheel nodes. Depending on the linker fragment composition, the defect can be either a vacant site or a functional group that the original linker does not have. In the first case, we show that both surface area and pore volume increase, while in the second case they decrease. The effect of defects on the high-pressure gas uptake is also studied over a large temperature and pressure range formore » different gases. We found that despite an increase in pore volume and surface area in structures with vacant sites, the absolute adsorption for methane decreases for HKUST-1 and slightly increases for NU-125. However, the working capacity (deliverable amount between 65 and 5 bar) in both cases remains similar to parent frameworks due to lower uptakes at low pressures. In the case of NU-125, the effect of defects became more pronounced at lower temperatures, reflecting the greater surface areas and pore volumes of the altered forms.« less
Li, Duo; Han, Fei; Wang, Shuai; Cheng, Fei; Sun, Qiang; Li, Wen-Cui
2013-03-01
Porous carbon materials with large pore volume are crucial in loading insulated sulfur with the purpose of achieving high performance for lithium-sulfur batteries. In our study, peapodlike mesoporous carbon with interconnected pore channels and large pore volume (4.69 cm(3) g(-1)) was synthesized and used as the matrix to fabricate carbon/sulfur (C/S) composite which served as attractive cathodes for lithium-sulfur batteries. Systematic investigation of the C/S composite reveals that the carbon matrix can hold a high but suitable sulfur loading of 84 wt %, which is beneficial for improving the bulk density in practical application. Such controllable sulfur-filling also effectively allows the volume expansion of active sulfur during Li(+) insertion. Moreover, the thin carbon walls (3-4 nm) of carbon matrix not only are able to shorten the pathway of Li(+) transfer and conduct electron to overcome the poor kinetics of sulfur cathode, but also are flexible to warrant structure stability. Importantly, the peapodlike carbon shell is beneficial to increase the electrical contact for improving electronic conductivity of active sulfur. Meanwhile, polymer modification with polypyrrole coating layer further restrains polysulfides dissolution and improves the cycle stability of carbon/sulfur composites.
Kravchenko, Alexandra; Falconer, Ruth E; Grinev, Dmitri; Otten, Wilfred
2011-06-01
Despite the importance of fungi in soil functioning they have received comparatively little attention, and our understanding of fungal interactions and communities is lacking. This study aims to combine a physiologically based model of fungal growth with digitized images of internal pore volume of samples of undisturbed soil from contrasting management practices to determine the effect of physical structure on fungal growth dynamics. We quantified pore geometries of the undisturbed-soil samples from two contrasting agricultural practices, conventionally plowed (chisel plow) (CT) and no till (NT), and from native-species vegetation land use on land that was taken out of production in 1989 (NS). Then we modeled invasion of a fungal species within the soil samples and evaluated the role of soil structure on the progress of fungal colonization of the soil pore space. The size of the studied pores was > or =110 microm. The dynamics of fungal invasion was quantified through parameters of a mathematical model fitted to the fungal invasion curves. Results indicated that NT had substantially lower porosity and connectivity than CT and NS soils. For example, the largest connected pore volume occupied 79% and 88% of pore space in CT and NS treatments, respectively, while it only occupied 45% in NT. Likewise, the proportion of pore space available to fungal colonization was much greater in NS and CT than in NT treatment, and the dynamics of the fungal invasion differed among the treatments. The relative rate of fungal invasion at the onset of simulation was higher in NT samples, while the invasion followed a more sigmoidal pattern with relatively slow invasion rates at the initial time steps in NS and CT samples. Simulations allowed us to elucidate the contribution of physical structure to the rates and magnitudes of fungal invasion processes. It appeared that fragmented pore space disadvantaged fungal invasion in soils under long-term no-till, while large connected pores in soils under native vegetation or in tilled agriculture promoted the invasion.
High-pressure synthesis of mesoporous stishovite: potential applications in mineral physics
NASA Astrophysics Data System (ADS)
Stagno, Vincenzo; Mandal, Manik; Landskron, Kai; Fei, Yingwei
2015-06-01
Recently, we have described a successful synthesis route to obtain mesoporous quartz and its high-pressure polymorph coesite by nanocasting at high pressure using periodic mesostructured precursors, such as SBA-16 and FDU-12/carbon composite as starting materials. Periodic mesoporous high-pressure silica polymorphs are of particular interest as they combine transport properties and physical properties such as hardness that potentially enable the industrial use of these materials. In addition, synthesis of mesoporous crystalline silica phases can allow more detailed geology-related studies such as water/mineral interaction, dissolution/crystallization rate and the surface contribution to the associated thermodynamic stability (free energy and enthalpy) of the various polymorphs and their crossover. Here, we present results of synthesis of mesoporous stishovite from cubic large-pore periodic mesoporous silica LP-FDU-12/C composite as precursor with an fcc lattice. We describe the synthesis procedure using multi-anvil apparatus at 9 GPa (about 90,000 atm) and temperature of 500 °C. The synthetic mesoporous stishovite is, then, characterized by wide and small-angle X-ray diffraction, scanning/transmission electron microscopy and gas adsorption. Results show that this new material is characterized by accessible mesopores with wide pore size distribution, surface area of ~45 m2/g and volume of pores of ~0.15 cm3/g. Results from gas adsorption indicate that both porosity and permeability are retained at the high pressures of synthesis but with weak periodic order of the pores.
NASA Astrophysics Data System (ADS)
Tembely, Moussa; Alsumaiti, Ali M.; Jouini, Mohamed S.; Rahimov, Khurshed; Dolatabadi, Ali
2017-11-01
Most of the digital rock physics (DRP) simulations focus on Newtonian fluids and overlook the detailed description of rock-fluid interaction. A better understanding of multiphase non-Newtonian fluid flow at pore-scale is crucial for optimizing enhanced oil recovery (EOR). The Darcy scale properties of reservoir rocks such as the capillary pressure curves and the relative permeability are controlled by the pore-scale behavior of the multiphase flow. In the present work, a volume of fluid (VOF) method coupled with an adaptive meshing technique is used to perform the pore-scale simulation on a 3D X-ray micro-tomography (CT) images of rock samples. The numerical model is based on the resolution of the Navier-Stokes equations along with a phase fraction equation incorporating the dynamics contact model. The simulations of a single phase flow for the absolute permeability showed a good agreement with the literature benchmark. Subsequently, the code is used to simulate a two-phase flow consisting of a polymer solution, displaying a shear-thinning power law viscosity. The simulations enable to access the impact of the consistency factor (K), the behavior index (n), along with the two contact angles (advancing and receding) on the relative permeability.
Wang, Yusen; Wang, Xiaoxia; Feng, Xiaolan; Ye, Xiao; Fu, Jie
2018-01-01
Layered double hydroxides (LDHs) have been widely used as an important subset of solid base catalysts. However, developing low-cost, small-sized LDH nanoparticles with enhanced surface catalytic sites remains a challenge. In this work, silica aerogel (SA)-supported, small-sized Mg–Al LDH nanosheets were successfully prepared by one-pot coprecipitation of Mg and Al ions in an alkaline suspension of crushed silica aerogel. The supported LDH nanosheets were uniformly dispersed in the SA substrate with the smallest average radial diameter of 19.2 nm and the thinnest average thickness of 3.2 nm, both dimensions being significantly less than those of the vast majority of LDH nanoparticles reported. The SA/LDH composites also showed large pore volume (up to 1.3 cm3·g) and pore diameter (>9 nm), and therefore allow efficient access of reactants to the edge catalytic sites of LDH nanosheets. In a base-catalyzed Henry reaction of benzaldehyde with nitromethane, the SA/LDH catalysts showed high reactant conversions and favorable stability in 6 successive cycles of reactions. The low cost of the SA carrier and LDH precursors, easy preparation method, and excellent catalytic properties make these SA/LDH composites a competitive example of solid-base catalysts. PMID:29462941
Wang, Lijun; Wang, Yusen; Wang, Xiaoxia; Feng, Xiaolan; Ye, Xiao; Fu, Jie
2018-02-16
Layered double hydroxides (LDHs) have been widely used as an important subset of solid base catalysts. However, developing low-cost, small-sized LDH nanoparticles with enhanced surface catalytic sites remains a challenge. In this work, silica aerogel (SA)-supported, small-sized Mg-Al LDH nanosheets were successfully prepared by one-pot coprecipitation of Mg and Al ions in an alkaline suspension of crushed silica aerogel. The supported LDH nanosheets were uniformly dispersed in the SA substrate with the smallest average radial diameter of 19.2 nm and the thinnest average thickness of 3.2 nm, both dimensions being significantly less than those of the vast majority of LDH nanoparticles reported. The SA/LDH composites also showed large pore volume (up to 1.3 cm3·g) and pore diameter (>9 nm), and therefore allow efficient access of reactants to the edge catalytic sites of LDH nanosheets. In a base-catalyzed Henry reaction of benzaldehyde with nitromethane, the SA/LDH catalysts showed high reactant conversions and favorable stability in 6 successive cycles of reactions. The low cost of the SA carrier and LDH precursors, easy preparation method, and excellent catalytic properties make these SA/LDH composites a competitive example of solid-base catalysts.
Reddy, M.M.; Claassen, H.C.; Rutherford, D.W.; Chiou, C.T.
1994-01-01
Porosity of welded tuff from Snowshoe Mountain, Colorado, was characterized by mercury intrusion porosimetry (MIP), nitrogen sorption porosimetry, ethylene glycol monoethyl ether (EGME) gas phase sorption and epifluorescence optical microscopy. Crushed tuff of two particle-size fractions (1-0.3 mm and less than 0.212 mm), sawed sections of whole rock and crushed tuff that had been reacted with 0.1 N hydrochloric acid were examined. Average MIP pore diameter values were in the range of 0.01-0.02??m. Intrusion volume was greatest for tuff reacted with 0.1 N hydrochloric acid and least for sawed tuff. Cut rock had the smallest porosity (4.72%) and crushed tuff reacted in hydrochloric acid had the largest porosity (6.56%). Mean pore diameters from nitrogen sorption measurements were 0.0075-0.0187 ??m. Nitrogen adsorption pore volumes (from 0.005 to 0.013 cm3/g) and porosity values (from 1.34 to 3.21%) were less than the corresponding values obtained by MIP. More than half of the total tuff pore volume was associated with pore diameters < 0.05??m. Vapor sorption of EGME demonstrated that tuff pores contain a clay-like material. Epifluorescence microscopy indicated that connected porosity is heterogeneously distributed within the tuff matix; mineral grains had little porosity. Tuff porosity may have important consequences for contaminant disposal in this host rock. ?? 1994.
Assessing the utility of FIB-SEM images for shale digital rock physics
NASA Astrophysics Data System (ADS)
Kelly, Shaina; El-Sobky, Hesham; Torres-Verdín, Carlos; Balhoff, Matthew T.
2016-09-01
Shales and other unconventional or low permeability (tight) reservoirs house vast quantities of hydrocarbons, often demonstrate considerable water uptake, and are potential repositories for fluid sequestration. The pore-scale topology and fluid transport mechanisms within these nanoporous sedimentary rocks remain to be fully understood. Image-informed pore-scale models are useful tools for studying porous media: a debated question in shale pore-scale petrophysics is whether there is a representative elementary volume (REV) for shale models? Furthermore, if an REV exists, how does it differ among petrophysical properties? We obtain three dimensional (3D) models of the topology of microscale shale volumes from image analysis of focused ion beam-scanning electron microscope (FIB-SEM) image stacks and investigate the utility of these models as a potential REV for shale. The scope of data used in this work includes multiple local groups of neighboring FIB-SEM images of different microscale sizes, corresponding core-scale (milli- and centimeters) laboratory data, and, for comparison, series of two-dimensional (2D) cross sections from broad ion beam SEM images (BIB-SEM), which capture a larger microscale field of view than the FIB-SEM images; this array of data is larger than the majority of investigations with FIB-SEM-derived microscale models of shale. Properties such as porosity, organic matter content, and pore connectivity are extracted from each model. Assessments of permeability with single phase, pressure-driven flow simulations are performed in the connected pore space of the models using the lattice-Boltzmann method. Calculated petrophysical properties are compared to those of neighboring FIB-SEM images and to core-scale measurements of the sample associated with the FIB-SEM sites. Results indicate that FIB-SEM images below ∼5000 μm3 volume (the largest volume analyzed) are not a suitable REV for shale permeability and pore-scale networks; i.e. field of view is compromised at the expense of detailed, but often unconnected, nanopore morphology. Further, we find that it is necessary to acquire several local FIB-SEM or BIB-SEM images and correlate their extracted geometric properties to improve the likelihood of achieving representative values of porosity and organic matter volume. Our work indicates that FIB-SEM images of microscale volumes of shale are a qualitative tool for petrophysical and transport analysis. Finally, we offer alternatives for quantitative pore-scale assessments of shale.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wang, Hsiu-Wen; Anovitz, Lawrence; Burg, Avihu
Backscattered scanning electron micrograph and ultra small- and small-angle neutron scattering data have been combined to provide statistically meaningful data on the pore/grain structure and pore evolution of combustion metamorphic complexes from the Hatrurim basin, Israel. Three processes, anti-sintering roughening, alteration of protolith (dehydration, decarbonation, and oxidation) and crystallization of high-temperature minerals, occurred simultaneously, leading to significant changes in observed pore/grain structures. Pore structures in the protoliths, and in lowand high-grade metamorphic rocks show surface (Ds) and mass (Dm) pore fractal geometries with gradual increases in both Ds and Dm values as a function of metamorphic grade. This suggests thatmore » increases in pore volume and formation of less branching pore networks are accompanied by a roughening of pore/grain interfaces. Additionally, pore evolution during combustion metamorphism is also characterized by reduced contributions from small-scale pores to the cumulative porosity in the high-grade rocks. At high temperatures, small-scale pores may be preferentially closed by the formation of high-temperature minerals, producing a rougher morphology with increasing temperature. Alternatively, large-scale pores may develop at the expense of small-scale pores. These observations (pore fractal geometry and cumulative porosity) indicate that the evolution of pore/grain structures is correlated with the growth of high-temperature phases and is a consequence of the energy balance between pore/grain surface energy and energy arising from heterogeneous phase contacts. The apparent pore volume density further suggests that the localized time/temperature development of the high-grade Hatrurim rocks is not simply an extension of that of the low-grade rocks. The former likely represents the "hot spots (burning foci)" in the overall metamorphic terrain while the latter may represent contact aureoles.« less
Column Testing and 1D Reactive Transport Modeling to Evaluate Uranium Plume Persistence Processes
NASA Astrophysics Data System (ADS)
Johnson, R. H.; Morrison, S.; Morris, S.; Tigar, A.; Dam, W. L.; Dayvault, J.
2015-12-01
At many U.S. Department of Energy Office of Legacy Management sites, 100 year natural flushing was selected as a remedial option for groundwater uranium plumes. However, current data indicate that natural flushing is not occurring as quickly as expected and solid-phase and aqueous uranium concentrations are persistent. At the Grand Junction, Colorado office site, column testing was completed on core collected below an area where uranium mill tailings have been removed. The total uranium concentration in this core was 13.2 mg/kg and the column was flushed with laboratory-created water with no uranium and chemistry similar to the nearby Gunnison River. The core was flushed for a total of 91 pore volumes producing a maximum effluent uranium concentration of 6,110 μg/L at 2.1 pore volumes and a minimum uranium concentration of 36.2 μg/L at the final pore volume. These results indicate complex geochemical reactions at small pore volumes and a long tailing affect at greater pore volumes. Stop flow data indicate the occurrence of non-equilibrium processes that create uranium concentration rebound. These data confirm the potential for plume persistence, which is occurring at the field scale. 1D reactive transport modeling was completed using PHREEQC (geochemical model) and calibrated to the column test data manually and using PEST (inverse modeling calibration routine). Processes of sorption, dual porosity with diffusion, mineral dissolution, dispersion, and cation exchange were evaluated separately and in combination. The calibration results indicate that sorption and dual porosity are major processes in explaining the column test data. These processes are also supported by fission track photographs that show solid-phase uranium residing in less mobile pore spaces. These procedures provide valuable information on plume persistence and secondary source processes that may be used to better inform and evaluate remedial strategies, including natural flushing.
Daniele Tonina; Alberto Bellin
2008-01-01
Pore-scale dispersion (PSD), aquifer heterogeneity, sampling volume, and source size influence solute concentrations of conservative tracers transported in heterogeneous porous formations. In this work, we developed a new set of analytical solutions for the concentration ensemble mean, variance, and coefficient of variation (CV), which consider the effects of all these...
NASA Astrophysics Data System (ADS)
Wang, Lu; Yu, Qingchun
2016-11-01
This study investigated the effects of moisture on high-pressure methane adsorption in carboniferous shales from the Qaidam Basin, China. The shale characteristics, including the organic/inorganic compositions and pore structure (volume and surface) distribution, were obtained using various techniques. Gibbs adsorption measurements were performed over a pressure range up to 6 MPa and temperatures of 308.15 K on dry samples and moisture-equilibrated samples to analyze the correlations between organic/inorganic matter, pore structure, and moisture content on the methane sorption capacity. Compared to dry samples, the sorption capacity of wet samples (0.44-2.52% of water content) is reduced from 19.7 ± 5.3% to 36.1% ± 6.1%. Langmuir fitting is conducted to investigate moisture-dependent variations of adsorbed methane density, Langmuir pressure, and volume. By combining the pore volume and surface distribution analyses, our observations suggested that the main competition sites for CH4-H2O covered pores of approximately 2-7 nm, whereas the effective sites for methane and water were predominantly distributed within smaller (<4 nm) and larger pores (>10 nm), respectively. Regarding the compositional correlations, the impact of moisture on the amount of adsorbed methane shows a roughly linearly decreasing trend with increasing TOC content ranging from 0.62 to 2.88%, whereas the correlation between the moisture effect and various inorganic components is more complicated. Further fitting results indicate that illite/smectite mixed formations are closely related to the methane capacity, whereas the illite content show an evident connection to the pore structural (volume and surface) variations in the presence of moisture.
NASA Astrophysics Data System (ADS)
Nguyen, B. V.; Challagulla, K. S.; Venkatesh, T. A.; Hadjiloizi, D. A.; Georgiades, A. V.
2016-12-01
Unit-cell based finite element models are developed to completely characterize the role of porosity distribution and porosity volume fraction in determining the elastic, dielectric and piezoelectric properties as well as relevant figures of merit of 3-3 type piezoelectric foam structures. Eight classes of foam structures which represent structures with different types and degrees of uniformity of porosity distribution are identified; a Base structure (Class I), two H-type foam structures (Classes II, and III), a Cross-type foam structure (Class IV) and four Line-type foam structures (Classes V, VI, VII, and VIII). Three geometric factors that influence the electromechanical properties are identified: (i) the number of pores per face, pore size and the distance between the pores; (ii) pore orientation with respect to poling direction; (iii) the overall symmetry of the pore distribution with respect to the center of the face of the unit cell. To assess the suitability of these structures for such applications as hydrophones, bone implants, medical imaging and diagnostic devices, five figures of merit are determined via the developed finite element model; the piezoelectric coupling constant (K t ), the acoustic impedance (Z), the piezoelectric charge coefficient (d h ), the hydrostatic voltage coefficient (g h ), and the hydrostatic figure of merit (d h g h ). At high material volume fractions, foams with non-uniform Line-type porosity (Classes V and VII) where the pores are preferentially distributed perpendicular to poling direction, are found to exhibit the best combination of desirable piezoelectric figures of merit. For example, at about 50% volume fraction, the d h , g h , and d h g h figures of merit are 55%, 1600% and 2500% higher, respectively, for Classes V and VII of Line-like foam structures compared with the Base structure.
NASA Astrophysics Data System (ADS)
Masoum Raman, S. N.; Ismail, N. A.; Jamari, S. S.
2017-06-01
Development of effective materials for carbon dioxide (CO2) capture technology is a fundamental importance to reduce CO2 emissions. This work establishes the addition of amine functional group on the surface of activated carbon to further improve the adsorption capacity of CO2. Rice husks activated carbon were modified using wet impregnation method by introducing piperazine onto the activated carbon surfaces at different concentrations and mixture ratios. These modified activated carbons were characterized by using X-Ray Diffraction (XRD), Brunauer, Emmett and Teller (BET), Fourier Transform Infrared Spectroscopy (FTIR) and Field Emission Scanning Electron Microscopy (FESEM). The results from XRD analysis show the presence of polyethylene butane at diffraction angles of 21.8° and 36.2° for modified activated carbon with increasing intensity corresponding to increase in piperazine concentration. BET results found the surface area and pore volume of non-impregnated activated carbon to be 126.69 m2/g and 0.081 cm3/g respectively, while the modified activated carbons with 4M of piperazine have lower surface area and pore volume which is 6.77 m2/g and 0.015 cm3/g respectively. At 10M concentration, the surface area and pore volume are the lowest which is 4.48 m2/g and 0.0065 cm3/g respectively. These results indicate the piperazine being filled inside the activated carbon pores thus, lowering the surface area and pore volume of the activated carbon. From the FTIR analysis, the presence of peaks at 3312 cm-1 and 1636 cm-1 proved the existence of reaction between carboxyl groups on the activated carbon surfaces with piperazine. The surface morphology of activated carbon can be clearly seen through FESEM analysis. The modified activated carbon contains fewer pores than non-modified activated carbon as the pores have been covered with piperazine.
Hay, M.B.; Stoliker, D.L.; Davis, J.A.; Zachara, J.M.
2011-01-01
Although "intragranular" pore space within grain aggregates, grain fractures, and mineral surface coatings may contain a relatively small fraction of the total porosity within a porous medium, it often contains a significant fraction of the reactive surface area, and can thus strongly affect the transport of sorbing solutes. In this work, we demonstrate a batch experiment procedure using tritiated water as a high-resolution diffusive tracer to characterize the intragranular pore space. The method was tested using uranium-contaminated sediments from the vadose and capillary fringe zones beneath the former 300A process ponds at the Hanford site (Washington). Sediments were contacted with tracers in artificial groundwater, followed by a replacement of bulk solution with tracer-free groundwater and the monitoring of tracer release. From these data, intragranular pore volumes were calculated and mass transfer rates were quantified using a multirate first-order mass transfer model. Tritium-hydrogen exchange on surface hydroxyls was accounted for by conducting additional tracer experiments on sediment that was vacuum dried after reaction. The complementary ("wet" and "dry") techniques allowed for the simultaneous determination of intragranular porosity and surface area using tritium. The Hanford 300A samples exhibited intragranular pore volumes of ???1% of the solid volume and intragranular surface areas of ???20%-35% of the total surface area. Analogous experiments using bromide ion as a tracer yielded very different results, suggesting very little penetration of bromide into the intragranular porosity. Copyright 2011 by the American Geophysical Union.
Hay, Michael B.; Stoliker, Deborah L.; Davis, James A.; Zachara, John M.
2011-01-01
Although "intragranular" pore space within grain aggregates, grain fractures, and mineral surface coatings may contain a relatively small fraction of the total porosity within a porous medium, it often contains a significant fraction of the reactive surface area, and can thus strongly affect the transport of sorbing solutes. In this work, we demonstrate a batch experiment procedure using tritiated water as a high-resolution diffusive tracer to characterize the intragranular pore space. The method was tested using uranium-contaminated sediments from the vadose and capillary fringe zones beneath the former 300A process ponds at the Hanford site (Washington). Sediments were contacted with tracers in artificial groundwater, followed by a replacement of bulk solution with tracer-free groundwater and the monitoring of tracer release. From these data, intragranular pore volumes were calculated and mass transfer rates were quantified using a multirate first-order mass transfer model. Tritium-hydrogen exchange on surface hydroxyls was accounted for by conducting additional tracer experiments on sediment that was vacuum dried after reaction. The complementary ("wet" and "dry") techniques allowed for the simultaneous determination of intragranular porosity and surface area using tritium. The Hanford 300A samples exhibited intragranular pore volumes of ~1% of the solid volume and intragranular surface areas of ~20%–35% of the total surface area. Analogous experiments using bromide ion as a tracer yielded very different results, suggesting very little penetration of bromide into the intragranular porosity.
Min, Kyungmin; Choi, Woosung; Choi, Minkee
2017-06-09
Poly(ethyleneimine) (PEI)/silica has been widely studied as a solid adsorbent for post-combustion CO 2 capture. In this work, a highly macroporous silica (MacS), synthesized by secondary sintering of fumed silica, is compared with various mesoporous silicas with different pore structures as a support for PEI. The silicas with large pore diameter and volume enabled high CO 2 adsorption kinetics and capacity, because pore occlusion by the supported PEI was minimized. The steam stability of the silica structures increased with the silica wall thickness owing to suppressed framework ripening. The silicas with low steam stability showed rapid leaching of PEI, which indicated that the PEI squeezed out of the collapsed silica pores leached more readily. Consequently, MacS that had an extra-large pore volume (1.80 cm 3 g -1 ) and pore diameter (56.0 nm), and a thick wall (>10 nm), showed the most promising CO 2 adsorption kinetics and capacity as well as steam stability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Estevez, Luis; Prabhakaran, Venkateshkumar; Garcia, Adam L.
Developing hierarchical porous carbon (HPC) materials with competing textural characteristics such as surface area and pore volume in one material is difficult to accomplish—particulalry for an atomically ordered (graphitic) carbon. Herein we describe a synthesis strategy to engineer tunable hierarchically porous carbon (HPC) materials across micro- meso- and macroporous length scales, allowing the fabrication of a graphitic HPC with both very high surface area (> 2500 m2/g) and pore volume (>10 cm3/g), the combination of which has not been seen previously. The mesopore volume alone for these materials is up to 7.91 cm3/g, the highest ever reported. The unique materialmore » was explored for use as a supercapaictor electrode and for oil adsorption; two applications that require textural properties that are typicaly exclusive to one another. This design scheme for HPCs can be utilized in broad applications, including electrochemical systems such as batteries and supercapacitors, sorbents, and catalyst supports.« less
Meng, Xianzhi; Wells, Tyrone; Sun, Qining; ...
2015-06-19
Pretreatment is known to render biomass more reactive to cellulase by altering the chemical compositions as well as physical structures of biomass. Simons stain technique along with mercury porosimetry were applied on the acid, neutral, and alkaline pretreated materials to measure the accessible surface area of cellulose and pore size distribution of Populus. Results indicated that acid pretreatment is much more effective than water and alkaline pretreatment in terms of cellulose accessibility increase. Further investigation suggests that lignin does not dictate cellulose accessibility to the extent that hemicellulose does, but it does restrict xylan accessibility which in turn controls themore » access of cellulase to cellulose. The most interesting finding is that severe acid pretreatment significantly decreases the average pore size, i.e., 90% average size decrease could be observed after 60 min dilute acid pretreatment at 160 °C; moreover, the nano-pore space formed between coated microfibrils is increased after pretreatment, especially for the acid pretreatment, suggesting this particular type of biomass porosity is probably the most fundamental barrier to effective enzymatic hydrolysis.« less
Li, Xiaoshi; Hou, Quanlin; Li, Zhuo; Wei, Mingming
2014-01-01
The enrichment of coalbed methane (CBM) and the outburst of gas in a coal mine are closely related to the nanopore structure of coal. The evolutionary characteristics of 12 coal nanopore structures under different natural deformational mechanisms (brittle and ductile deformation) are studied using a scanning electron microscope (SEM) and low-temperature nitrogen adsorption. The results indicate that there are mainly submicropores (2~5 nm) and supermicropores (<2 nm) in ductile deformed coal and mesopores (10~100 nm) and micropores (5~10 nm) in brittle deformed coal. The cumulative pore volume (V) and surface area (S) in brittle deformed coal are smaller than those in ductile deformed coal which indicates more adsorption space for gas. The coal with the smaller pores exhibits a large surface area, and coal with the larger pores exhibits a large volume for a given pore volume. We also found that the relationship between S and V turns from a positive correlation to a negative correlation when S > 4 m2/g, with pore sizes <5 nm in ductile deformed coal. The nanopore structure (<100 nm) and its distribution could be affected by macromolecular structure in two ways. Interconversion will occur among the different size nanopores especially in ductile deformed coal. PMID:25126601
Disorder-induced stiffness degradation of highly disordered porous materials
NASA Astrophysics Data System (ADS)
Laubie, Hadrien; Monfared, Siavash; Radjaï, Farhang; Pellenq, Roland; Ulm, Franz-Josef
2017-09-01
The effective mechanical behavior of multiphase solid materials is generally modeled by means of homogenization techniques that account for phase volume fractions and elastic moduli without considering the spatial distribution of the different phases. By means of extensive numerical simulations of randomly generated porous materials using the lattice element method, the role of local textural properties on the effective elastic properties of disordered porous materials is investigated and compared with different continuum micromechanics-based models. It is found that the pronounced disorder-induced stiffness degradation originates from stress concentrations around pore clusters in highly disordered porous materials. We identify a single disorder parameter, φsa, which combines a measure of the spatial disorder of pores (the clustering index, sa) with the pore volume fraction (the porosity, φ) to scale the disorder-induced stiffness degradation. Thus, we conclude that the classical continuum micromechanics models with one spherical pore phase, due to their underlying homogeneity assumption fall short of addressing the clustering effect, unless additional texture information is introduced, e.g. in form of the shift of the percolation threshold with disorder, or other functional relations between volume fractions and spatial disorder; as illustrated herein for a differential scheme model representative of a two-phase (solid-pore) composite model material.
NASA Astrophysics Data System (ADS)
Latifi, Fatemeh; Talebi, Zahra; Khalili, Haleh; Zarrebini, Mohammad
2018-05-01
This work investigates the influence of processing parameters and aerogel pore structure on the physical properties and hydrophobicity of aerogel blankets. Aerogel blankets were produced by in situ synthesis of nanostructured silica aerogel on a polyester nonwoven substrate. Nitrogen adsorption-desorption analysis, contact angle test and FE-SEM images were used to characterize both the aerogel particles and the blankets. The results showed that the weight and thickness of the blanket were reduced when the low amount of catalyst was used. A decrease in the aerogel pore size from 22 to 11 nm increased the weight and thickness of the blankets. The xerogel particles with high density and pore size of 5 nm reduced the blanket weight. Also, the blanket weight and thickness were increased due to increasing the sol volume. It was found that the hydrophobicity of aerogel blankets is not influenced by sol volume and pore structure of silica aerogel.
Synthesis and characterization of binary titania-silica mixed oxides
NASA Astrophysics Data System (ADS)
Budhi, Sridhar
A series of binary titania-silica mixed oxides were synthesized by the sol-gel method at room temperature. The mixed oxides were prepared that involved the hydrolysis of titanium isopropoxide and tetraethylorthosilicate (TEOS) by co-solvent induced gelation usually in acidic media. The resulting gels were dried, calcined and then characterized by powder X-ray diffractometric studies, nitrogen sorption studies (at 77K), diffuse reflectance spectroscopy, Raman microscopy and transmission electron microscopic studies. The nitrogen sorption studies indicate that the specific surface areas, pore volume, pore diameter and pore size distribution of the mixed oxides were substantially enhanced when non-polar solvents such as toluene, p-xylene or mesitylene were added as co-solvents to the synthesis gel. Transmission electron microscopic (TEM) studies confirm the results obtained from the nitrogen sorption studies. Our results indicate that we can obtain binary metal oxides possessing high surface area and large pore volumes with tunable pore size distribution at room temperature. Photocatalytic evaluation of the mixed oxides is currently in progress.
Porosity of different dental luting cements.
Milutinović-Nikolić, Aleksandra D; Medić, Vesna B; Vuković, Zorica M
2007-06-01
The aim of this in vitro study was to compare open porosity and pore size distribution of different types of luting cements (zinc phosphate and polycarboxylate produced by Harvard Cement, Great Britain, glass-ionomer product GC Fuji I, GC Corporation, Japan, and Panavia F, resin based composite cement, Kurraray Co. Ltd. Japan) using mercury intrusion porosimetry and use it as an additional parameter for ranging the quality of cements used in prosthetics. Samples were hand mixed in accordance with the manufacturer's instructions and formed in cylindrical test specimens. Density of samples was determined using a pycnometer while porous structure was estimated using high pressure mercury intrusion porosimeter enabling estimation of pore diameters in interval 7.5-15,000 nm. The polycarboxylate cement posses the highest porosity and specific pore volume among investigated cements. By comparison of the results obtained for zinc phosphate and glass-ionomer cement, it can be observed that according to some textural properties zinc phosphate cement is better choice (smaller specific pore volume and absence of macropores larger than 1 microm) while according to other textural properties the glass-ionomer has advantage (smaller porosity). The resin based composite cement poses the most desired porous structure for prosthetic application among the investigated cements (the lowest porosity and specific pore volume and all identified pores are smaller than 20 nm). Based on results of this study, it is possible to estimate the efficiency of luting cements to protect the interior of tooth from penetration of oral fluids, bacteria and bacterial toxins into unprotected dentine.
Modeling Stokes flow in real pore geometries derived by high resolution micro CT imaging
NASA Astrophysics Data System (ADS)
Halisch, M.; Müller, C.
2012-04-01
Meanwhile, numerical modeling of rock properties forms an important part of modern petrophysics. Substantially, equivalent rock models are used to describe and assess specific properties and phenomena, like fluid transport or complex electrical properties. In recent years, non-destructive computed X-ray tomography got more and more important - not only to take a quick and three dimensional look into rock samples but also to get access to in-situ sample information for highly accurate modeling purposes. Due to - by now - very high resolution of the 3D CT data sets (micron- to submicron range) also very small structures and sample features - e.g. micro porosity - can be visualized and used for numerical models of very high accuracy. Special demands even arise before numerical modeling can take place. Inappropriate filter applications (e.g. improper type of filter, wrong kernel, etc.) may lead to a significant corruption of spatial sample structure and / or even sample or void space volume. Because of these difficulties, especially small scale mineral- and pore space textures are very often lost and valuable in-situ information is erased. Segmentation of important sample features - porosity as well as rock matrix - based upon grayscale values strongly depends upon the scan quality and upon the experience of the application engineer, respectively. If the threshold for matrix-porosity separation is set too low, porosity can be quickly (and even more, due to restrictions of scanning resolution) underestimated. Contrary to this, a too high threshold over-determines porosity and small void space features as well as interfaces are changed and falsified. Image based phase separation in close combination with "conventional" analytics, as scanning electron microscopy or thin sectioning, greatly increase the reliability of this preliminary work. For segmentation and quantification purposes, a special CT imaging and processing software (Avizo Fire) has been used. By using this tool, 3D rock data can be assessed and interpreted by petrophysical means. Furthermore, pore structures can be directly segmented and hence could be used for so called image based modeling approach. The special XLabHydro module grants a finite volume solver for the direct assessment of Stokes flow (incompressible fluid, constant dynamic viscosity, stationary conditions and laminar flow) in real pore geometries. Nevertheless, also pore network extraction and numerical modeling with standard FE or lattice Boltzmann solvers is possible. By using the achieved voxel resolution as smallest node distance, fluid flow properties can be analyzed even in very small sample structures and hence with very high accuracy, especially with interaction to bigger parts of the pore network. The so derived results in combination with a direct 3D visualization within the structures offer great new insights and understanding in range of meso- and microscopic pore space phenomena.
Tomographic Image of a Seismically Active Volcano: Mammoth Mountain, California
NASA Astrophysics Data System (ADS)
Dawson, P. B.; Chouet, B. A.; Pitt, A. M.
2015-12-01
High-resolution tomographic P wave, S wave, and VP /VS velocity structure models are derived for Mammoth Mountain, California using phase data from the Northern California Seismic Network and a temporary deployment of broadband seismometers. An anomalous volume (˜50 km3) of low P and low S wave velocities is imaged beneath Mammoth Mountain, extending from near the surface to a depth of ˜2 km below sea level. We infer that the reduction in seismic wave velocities is primarily due to the presence of CO2 distributed in oblate-spheroid pores with mean aspect ratio α ˜8 x 10-4 (crack-like pores) and gas volume fraction φ ˜4 x 10-4. The pore density parameter κ = 3φ / (4πα) = na3 = 0.12, where n is the number of pores per cubic meter and a is the mean pore equatorial radius. The total mass of CO2 is estimated to range up to ˜1.6 x 1010 kg if the pores exclusively contain CO2, although he presence of an aqueous phase may lower this estimate by up to one order of magnitude. The local geological structure indicates that the CO2 contained in the pores is delivered to the surface through fractures controlled by faults and remnant foliation of the bedrock beneath Mammoth Mountain. The total volume of CO2 contained in the reservoir suggests that given an emission rate of 5 x 105 kg day-1, the reservoir could supply the emission of CO2 for ˜8 to ˜90 years before depletion. Continued supply of CO2 from an underlying magmatic system would significantly prolong the existence of the reservoir.
The effects of pore structure on the behavior of water in lignite coal and activated carbon.
Nwaka, Daniel; Tahmasebi, Arash; Tian, Lu; Yu, Jianglong
2016-09-01
The effects of physical structure (pore structure) on behavior of water in lignite coal and activated carbon (AC) samples were investigated by using Differential Scanning Calorimetry (DSC) and low-temperature X-ray diffraction (XRD) techniques. AC samples with different pore structures were prepared at 800°C in steam and the results were compared with that of parent lignite coal. The DSC results confirmed the presence of two types of freezable water that freeze at -8°C (free water) and -42°C (freezable bound water). A shift in peak position of free water (FW) towards lower temperature was observed in AC samples compared to the lignite coal with decreasing water loading. The amount of free water (FW) increased with increasing gasification conversion. The amounts of free and freezable bound water (FBW) in AC samples were calculated and correlated to pore volume and average pore size. The amount of FW in AC samples is well correlated to the pore volume and average pore size of the samples, while an opposite trend was observed for FBW. The low-temperature XRD analysis confirmed the existence of non-freezable water (NFW) in coal and AC with the boundary between the freezable and non-freezable water (NFW) determined. Copyright © 2016 Elsevier Inc. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Qu Fengyu; Chemistry and Pharmaceutical College, Jiamusi University, Jiamusi 154007; Zhu Guangshan
2006-07-15
A series of mesoporous silica materials with similar pore sizes, different morphologies and variable pore geometries were prepared systematically. In order to control drug release, ibuprofen was employed as a model drug and the influence of morphology and pore geometry of mesoporous silica on drug release profiles was extensively studied. The mesoporous silica and drug-loaded samples were characterized by X-ray diffraction, Fourier transform IR spectroscopy, N{sub 2} adsorption and desorption, scanning electron microscopy, and transmission electron microscopy. It was found that the drug-loading amount was directly correlated to the Brunauer-Emmett-Teller surface area, pore geometry, and pore volume; while the drugmore » release profiles could be controlled by tailoring the morphologies of mesoporous silica carriers. - Graphical abstract: The release of ibuprofen is controlled by tailoring the morphologies of mesoporous silica. The mesoporous silica and drug-loaded samples are characterized by powder X-ray diffraction, Fourier transform IR spectroscopy, N{sub 2} adsorption and desorption, scanning electron microscopy, and transmission electron microscopy. The drug-loading amount is directly correlated to the Brunauer-Emmett-Teller surface area, pore geometry, and pore volume; while the drug release profiles can be controlled by tailoring the morphologies of mesoporous silica carriers.« less
Generalized network modeling of capillary-dominated two-phase flow
NASA Astrophysics Data System (ADS)
Raeini, Ali Q.; Bijeljic, Branko; Blunt, Martin J.
2018-02-01
We present a generalized network model for simulating capillary-dominated two-phase flow through porous media at the pore scale. Three-dimensional images of the pore space are discretized using a generalized network—described in a companion paper [A. Q. Raeini, B. Bijeljic, and M. J. Blunt, Phys. Rev. E 96, 013312 (2017), 10.1103/PhysRevE.96.013312]—which comprises pores that are divided into smaller elements called half-throats and subsequently into corners. Half-throats define the connectivity of the network at the coarsest level, connecting each pore to half-throats of its neighboring pores from their narrower ends, while corners define the connectivity of pore crevices. The corners are discretized at different levels for accurate calculation of entry pressures, fluid volumes, and flow conductivities that are obtained using direct simulation of flow on the underlying image. This paper discusses the two-phase flow model that is used to compute the averaged flow properties of the generalized network, including relative permeability and capillary pressure. We validate the model using direct finite-volume two-phase flow simulations on synthetic geometries, and then present a comparison of the model predictions with a conventional pore-network model and experimental measurements of relative permeability in the literature.
Wood decay by brown-rot fungi : changes in pore structure and cell wall volume
Douglas S. Flournoy; T. Kent Kirk; T.L. Highley
1991-01-01
Sweetgum (Liquidambar styraciflua L.) wood blocks were decayed by Postia (= Poria) placenta in soilblock cultures. Decay was terminated at various weight losses, and the pore volumes available to four low molecular weight molecules, (water, 4 Ã ,; glucose, 8 Ã ,; maltose, 10 Ã ; and raffinose, 128,) and three dextrans (Mr 6,000, 38 Ã ; 11,200, 51 Ã ; nd 17,500, 61 Ã ) were...
Catalytic two-stage coal liquefaction process having improved nitrogen removal
Comolli, Alfred G.
1991-01-01
A process for catalytic multi-stage hydrogenation and liquefaction of coal to produce high yields of low-boiling hydrocarbon liquids containing low concentrations of nitogen compounds. First stage catalytic reaction conditions are 700.degree.-800.degree. F. temperature, 1500-3500 psig hydrogen partial pressure, with the space velocity maintained in a critical range of 10-40 lb coal/hr ft.sup.3 catalyst settled volume. The first stage catalyst has 0.3-1.2 cc/gm total pore volume with at least 25% of the pore volume in pores having diameters of 200-2000 Angstroms. Second stage reaction conditions are 760.degree.-870.degree. F. temperature with space velocity exceeding that in the first stage reactor, so as to achieve increased hydrogenation yield of low-boiling hydrocarbon liquid products having at least 75% removal of nitrogen compounds from the coal-derived liquid products.
NASA Astrophysics Data System (ADS)
Zhao, Cunyu; Liu, Lianjun; Zhao, Huilei; Krall, Andy; Wen, Zhenhai; Chen, Junhong; Hurley, Patrick; Jiang, Junwei; Li, Ying
2013-12-01
Sulfur has received increasing attention as a cathode material for lithium-sulfur (Li-S) batteries due to its high theoretical specific capacity. However, the commercialization of Li-S batteries is limited by the challenges of poor electrical conductivity of sulfur, dissolution of the polysulfide intermediates into the electrolyte, and volume expansion of sulfur during cycling. Herein, we report the fabrication of novel-structured porous carbon microspheres with a controllable multi-modal pore size distribution, i.e., a combination of interconnected micropores, mesopores and macropores. Cathodes made of sulfur infiltrated in such a hierarchical carbon framework provide several advantages: (1) a continuous and high surface area carbon network for enhanced electrical conductivity and high sulfur loading; (2) macropores and large mesopores bridged by small mesopores to provide good electrolyte accessibility and fast Li ion transport and to accommodate volume expansion of sulfur; and (3) small mesopores and micropores to improve carbon/sulfur interaction and to help trap polysulfides. An initial discharge capacity at 1278 mA h g-1 and capacity retention at 70.7% (904 mA h g-1) after 100 cycles at a high rate (1 C) were achieved. The material fabrication process is relatively simple and easily scalable.Sulfur has received increasing attention as a cathode material for lithium-sulfur (Li-S) batteries due to its high theoretical specific capacity. However, the commercialization of Li-S batteries is limited by the challenges of poor electrical conductivity of sulfur, dissolution of the polysulfide intermediates into the electrolyte, and volume expansion of sulfur during cycling. Herein, we report the fabrication of novel-structured porous carbon microspheres with a controllable multi-modal pore size distribution, i.e., a combination of interconnected micropores, mesopores and macropores. Cathodes made of sulfur infiltrated in such a hierarchical carbon framework provide several advantages: (1) a continuous and high surface area carbon network for enhanced electrical conductivity and high sulfur loading; (2) macropores and large mesopores bridged by small mesopores to provide good electrolyte accessibility and fast Li ion transport and to accommodate volume expansion of sulfur; and (3) small mesopores and micropores to improve carbon/sulfur interaction and to help trap polysulfides. An initial discharge capacity at 1278 mA h g-1 and capacity retention at 70.7% (904 mA h g-1) after 100 cycles at a high rate (1 C) were achieved. The material fabrication process is relatively simple and easily scalable. Electronic supplementary information (ESI) available: Preparation process scheme; X-ray mapping images and EDX analysis for the surface of PMC/S-40; X-ray mapping images for the cross-section of PMC/S-40; thermogravimetric analysis (TGA) of PMC/S samples; T-plot results for PMC sample; and electrochemical measurements of lithium-sulfur batteries using PMC/S as cathode materials. See DOI: 10.1039/c3nr04532c
NASA Astrophysics Data System (ADS)
Savina, Irina N.; Ingavle, Ganesh C.; Cundy, Andrew B.; Mikhalovsky, Sergey V.
2016-02-01
The development of bulk, three-dimensional (3D), macroporous polymers with high permeability, large surface area and large volume is highly desirable for a range of applications in the biomedical, biotechnological and environmental areas. The experimental techniques currently used are limited to the production of small size and volume cryogel material. In this work we propose a novel, versatile, simple and reproducible method for the synthesis of large volume porous polymer hydrogels by cryogelation. By controlling the freezing process of the reagent/polymer solution, large-scale 3D macroporous gels with wide interconnected pores (up to 200 μm in diameter) and large accessible surface area have been synthesized. For the first time, macroporous gels (of up to 400 ml bulk volume) with controlled porous structure were manufactured, with potential for scale up to much larger gel dimensions. This method can be used for production of novel 3D multi-component macroporous composite materials with a uniform distribution of embedded particles. The proposed method provides better control of freezing conditions and thus overcomes existing drawbacks limiting production of large gel-based devices and matrices. The proposed method could serve as a new design concept for functional 3D macroporous gels and composites preparation for biomedical, biotechnological and environmental applications.
Pore-expanded SBA-15 sulfonic acid silicas for biodiesel synthesis.
Dacquin, J P; Lee, A F; Pirez, C; Wilson, K
2012-01-07
Here we present the first application of pore-expanded SBA-15 in heterogeneous catalysis. Pore expansion over the range 6-14 nm confers a striking activity enhancement towards fatty acid methyl ester (FAME) synthesis from triglycerides (TAG), and free fatty acid (FFA), attributed to improved mass transport and acid site accessibility. This journal is © The Royal Society of Chemistry 2012
Meso- and micropore characteristics of coal lithotypes: Implications for CO2 adsorption
Mastalerz, Maria; Drobniak, A.; Rupp, J.
2008-01-01
Lithotypes (vitrain, clarain, and fusain) of high volatile bituminous Pennsylvanian coals (Ro of 0.56-0.62%) from Indiana (the Illinois Basin) have been studied with regard to meso- and micropore characteristics using low-pressure nitrogen and carbon dioxide adsorption techniques, respectively. High-pressure CO2 adsorption isotherms were obtained from lithotypes of the Lower Block Coal Member (the Brazil Formation) and the Springfield Coal Member (the Petersburg Formation), and after evacuation of CO2, the lithotypes were re-analyzed for meso- and micropore characteristics to investigate changes related to high-pressure CO2 adsorption. Coal lithotypes have differing Brunauer-Emmett-Teller (BET) surface areas and mesopore volumes, with significantly lower values in fusains than in vitrains or clarains. Fusains have very limited pore volume in the pore size width of 4-10 nm, and the volume, increases with an increase in pore size, in contrast to vitrain, for which a 4-10 nm range is the dominant pore'Wlidth. For clarain, both pores of 4-10 nm and pores larger than 20 nm contribute substantially to the mesoporosity. Micropore surface areas are the smallest for fusain (from 72.8 to 98.2 m2/g), largest for vitrain (from 125.0 to,158.4 m2 /g), and intermediate for clarain (from 110.5 to 124.4 m2/g). Similar relationships are noted for micropore volumes, and the lower values of these parameters in fusains are related to smaller volumes of all incremental micropore sizes. In the Springfield and the Lower Block Coal Members, among lithotypes studied, fusain has the lowest adsorption capacity. For the Lower Block, vitrain has significantly higher adsorption capacity than fusain and clarain, whereas for the Springfield, vitrain and clarain have comparable but still significantly higher adsorption capacities than fusain. The Lower Block vitrain and fusain have much higher adsorption capacities than those in the Springfield, whereas the clarains of the two coals are comparable. After exposure of coal to CO2 at high pressure, vitrains experienced the largest porosity changes among all lithotypes studied. These changes are dominantly manifested in the mesoporosity (decrease in mesopore volume) range; whereas little to no change occurred in the micropore size range. In other lithotypes (clarains, the dominant lithology in the coals studied, and sporadic fusains), the changes were minimal. ?? 2008 American Chemical Society.
Qian, Ken K; Suib, Steven L; Bogner, Robin H
2011-11-01
Amorphization of crystalline compounds using mesoporous media is a promising technique to improve the solubility and dissolution rate of poorly soluble compounds. The objective of this paper is to determine the capacity of amorphization and understand the mechanisms of phase transformation. Commercial grades of mesoporous silicon dioxide (SiO(2)) samples (5- to 30-nm mean pore diameters) with either constant surface area or constant pore volume were used. The amorphization capacity of naphthalene was not proportional to either the surface area or the pore volume measured using adsorption chambers. Instead, the amorphization capacity correlated with surface curvature, that is, the smaller the pore diameter and the higher the surface curvature, the greater the amorphization capacity. The change in surface chemistry due to a highly curved surface may be responsible for the enhanced amorphization capacity as well. The amorphization of crystalline compounds was facilitated through capillary condensation, with the decrease in pore volume as the direct experimental evidence. The amorphization capacity was also enhanced by the dipole-dipole or dipole-induced dipole interaction, promoted by the hydroxyl groups on the surface of SiO(2). The enthalpy of vapor-solid condensation of crystalline compounds was a useful indicator to predict the rank order of amorphization capacity. Copyright © 2011 Wiley-Liss, Inc.
Sulfonated mesoporous silica-carbon composites and their use as solid acid catalysts
NASA Astrophysics Data System (ADS)
Valle-Vigón, Patricia; Sevilla, Marta; Fuertes, Antonio B.
2012-11-01
The synthesis of highly functionalized porous silica-carbon composites made up of sulfonic groups attached to a carbon layer coating the pores of three types of mesostructured silica (i.e. SBA-15, KIT-6 and mesocellular silica) is presented. The synthesis procedure involves the following steps: (a) removal of the surfactant, (b) impregnation of the silica pores with a carbon precursor, (c) carbonization and (d) sulfonation. The resulting silica-carbon composites contain ˜30 wt % of carbonaceous matter with a high density of acidic groups attached to the deposited carbon (i.e.sbnd SO3H, sbnd COOH and sbnd OH). The structural characteristics of the parent silica are retained in the composite materials, which exhibit a high surface area, a large pore volume and a well-ordered porosity made up uniform mesopores. The high density of the sulfonic groups in combination with the mesoporous structure of the composites ensures that a large number of active sites are easily accessible to reactants. These sulfonated silica-carbon composites behave as eco-friendly, active, selective, water tolerant and recyclable solid acids. In this study we demonstrate the usefulness of these composites as solid acid catalysts for the esterification of maleic anhydride, succinic acid and oleic acid with ethanol. These composites exhibit a superior intrinsic catalytic activity to other commercial solid acids such as Amberlyst-15.
Ridgway, Cathy; Bawuah, Prince; Markl, Daniel; Zeitler, J Axel; Ketolainen, Jarkko; Peiponen, Kai-Erik; Gane, Patrick
2017-06-30
The physical properties and mechanical integrity of pharmaceutical tablets are of major importance when loading with active pharmaceutical ingredient(s) (API) in order to ensure ease of processing, control of dosage and stability during transportation and handling prior to patient consumption. The interaction between API and excipient, acting as functional extender and binder, however, is little understood in this context. The API indomethacin is combined in this study with microcrystalline cellulose (MCC) at increasing loading levels. Tablets from the defined API/MCC ratios are made under conditions of controlled porosity and tablet thickness, resulting from different compression conditions, and thus compaction levels. Mercury intrusion porosimetry is used to establish the accessible pore volume, pore size distribution and, adopting the observed region of elastic intrusion-extrusion at high pressure, an elastic bulk modulus of the skeletal material is recorded. Porosity values are compared to previously published values derived from terahertz (THz) refractive index data obtained from exactly the same tablet sample sets. It is shown that the elastic bulk modulus is dependent on API wt% loading under constant tablet preparation conditions delivering equal dimensions and porosity. The findings are considered of novel value in respect to establishing consistency of tablet production and optimisation of physical properties. Copyright © 2017 Elsevier B.V. All rights reserved.
Nguyen, Thanh H; Cho, Hyun-Hee; Poster, Dianne L; Ball, William P
2007-02-15
Sorption isotherms for five aromatic hydrocarbons were obtained with a natural wood char (NC1) and its residue after solvent extraction (ENC1). Substantial isotherm nonlinearity was observed in all cases. ENC1 showed higher BET surface area, higher nitrogen-accessible micropore volume, and lower mass of extractable organic chemicals, including quantifiable polycyclic aromatic hydrocarbons (PAHs),while the two chars showed identical surface oxygen/ carbon (O/C) ratio. For two chlorinated benzenes that normally condense as liquids at the temperatures used, sorption isotherms with NC1 and ENC1 were found to be statistically identical. For the solid-phase compounds (1,4-dichlorobenzene (1,4-DCB) and two PAHs), sorption was statistically higher with ENC1, thus demonstrating sorption effects due to both (1) authigenic organic content in the sorbentand (2)the sorbate's condensed state. Polanyi-based isotherm modeling, pore size measurements, and comparisons with activated carbon showthe relative importance of adsorptive pore filling and help explain results. With both chars, maximum sorption increased in the order of decreasing molecular diameter: phenanthrene < naphthalene < 1,2-dichlorobenzene/1,2,4-trichlorobenzene < 1,4-DCB. Comparison of 1,4- and 1,2-DCB shows that the critical molecular diameter was apparently more important than the condensed state, suggesting that 1,4-DCB sorbed in the liquid state for ENC1.
Wu, Ying; Chen, Huiyong; Liu, Defei; Xiao, Jing; Qian, Yu; Xi, Hongxia
2015-03-18
The adsorption and separation properties of benzene and toluene on the zirconium-based frameworks UiO-66, -67, -68, and their functional analogues UiO-Phe and UiO-Me2 were studied using grand canonical Monte Carlo simulations, density functional theory, and ideal adsorbed solution theory. Remarkable higher adsorption uptakes of benzene and toluene at low pressures on UiO-Phe and -Me2 were found compared to their parent framework UiO-67. It can be ascribed to the presence of functional groups (aromatic rings and methyl groups) that significantly intensified the adsorption, majorly by reducing the effective pore size and increasing the interaction strength with the adsorbates. At high pressures, the pore volumes and accessible surfaces of the frameworks turned out to be the dominant factors governing the adsorption. In the case of toluene/benzene separation, toluene selectivities of UiOs showed a two-stage separation behavior at the measured pressure range, resulting from the greater interaction affinities of toluene at low pressures and steric hindrance effects at high pressures. Additionally, the counterbalancing factors of enhanced π delocalization and suitable pore size of UiO-Phe gave rise to the highest toluene selectivity, suggesting the ligand functionalization strategy could reach both high adsorption capacity and separation selectivity from aromatic mixtures at low concentrations.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Han, Yosep; Choi, Junhyun; Tong, Meiping, E-mail: tongmeiping@iee.pku.edu.cn
2014-04-01
Millimeter-sized spherical silica foams (SSFs) with hierarchical multi-modal pore structure featuring high specific surface area and ordered mesoporous frameworks were successfully prepared using aqueous agar addition, foaming and drop-in-oil processes. The pore-related properties of the prepared spherical silica (SSs) and SSFs were systematically characterized by field emission-scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), small-angle X-ray diffraction (SAXRD), Hg intrusion porosimetry, and N{sub 2} adsorption–desorption isotherm measurements. Improvements in the BET surface area and total pore volume were observed at 504 m{sup 2} g{sup −1} and 5.45 cm{sup 3} g{sup −1}, respectively, after an agar addition and foaming process. Despitemore » the increase in the BET surface area, the mesopore wall thickness and the pore size of the mesopores generated from the block copolymer with agar addition were unchanged based on the SAXRD, TEM, and BJH methods. The SSFs prepared in the present study were confirmed to have improved BET surface area and micropore volume through the agar loading, and to exhibit interconnected 3-dimensional network macropore structure leading to the enhancement of total porosity and BET surface area via the foaming process. - Highlights: • Millimeter-sized spherical silica foams (SSFs) are successfully prepared. • SSFs exhibit high BET surface area and ordered hierarchical pore structure. • Agar addition improves BET surface area and micropore volume of SSFs. • Foaming process generates interconnected 3-D network macropore structure of SSFs.« less
Inferring diameters of spheres and cylinders using interstitial water.
Herrera, Sheryl L; Mercredi, Morgan E; Buist, Richard; Martin, Melanie
2018-06-04
Most early methods to infer axon diameter distributions using magnetic resonance imaging (MRI) used single diffusion encoding sequences such as pulsed gradient spin echo (SE) and are thus sensitive to axons of diameters > 5 μm. We previously simulated oscillating gradient (OG) SE sequences for diffusion spectroscopy to study smaller axons including the majority constituting cortical connections. That study suggested the model of constant extra-axonal diffusion breaks down at OG accessible frequencies. In this study we present data from phantoms to test a time-varying interstitial apparent diffusion coefficient. Diffusion spectra were measured in four samples from water packed around beads of diameters 3, 6 and 10 μm; and 151 μm diameter tubes. Surface-to-volume ratios, and diameters were inferred. The bead pore radii estimates were 0.60±0.08 μm, 0.54±0.06 μm and 1.0±0.1 μm corresponding to bead diameters ranging from 2.9±0.4 μm to 5.3±0.7 μm, 2.6±0.3 μm to 4.8±0.6 μm, and 4.9±0.7 μm to 9±1 μm. The tube surface-to-volume ratio estimate was 0.06±0.02 μm -1 corresponding to a tube diameter of 180±70 μm. Interstitial models with OG inferred 3-10 μm bead diameters from 0.54±0.06 μm to 1.0±0.1 μm pore radii and 151 μm tube diameters from 0.06±0.02 μm -1 surface-to-volume ratios.
Goldberg, Martin W
2016-01-01
Scanning electron microscopy (SEM) is a technique used to image surfaces. Field emission SEMs (feSEMs) can resolve structures that are ~0.5-1.5 nm apart. FeSEM, therefore is a useful technique for imaging molecular structures that exist at surfaces such as membranes. The nuclear envelope consists of four membrane surfaces, all of which may be accessible for imaging. Imaging of the cytoplasmic face of the outer membrane gives information about ribosomes and cytoskeletal attachments, as well as details of the cytoplasmic peripheral components of the nuclear pore complex, and is the most easily accessed surface. The nucleoplasmic face of the inner membrane is easily accessible in some cells, such as amphibian oocytes, giving valuable details about the organization of the nuclear lamina and how it interacts with the nuclear pore complexes. The luminal faces of both membranes are difficult to access, but may be exposed by various fracturing techniques. Protocols are presented here for the preparation, labeling, and feSEM imaging of Xenopus laevis oocyte nuclear envelopes.
Otte, T; Pasch, H; Macko, T; Brüll, R; Stadler, F J; Kaschta, J; Becker, F; Buback, M
2011-07-08
The molar mass distribution (MMD) of synthetic polymers is frequently analyzed by size exclusion chromatography (SEC) coupled to multi angle light scattering (MALS) detection. For ultrahigh molar mass (UHM) or branched polymers this method is not sufficient, because shear degradation and abnormal elution effects falsify the calculated molar mass distribution and information on branching. High temperatures above 130 °C have to be applied for dissolution and separation of semi-crystalline materials like polyolefins which requires special hardware setups. Asymmetrical flow field-flow fractionation (AF4) offers the possibility to overcome some of the main problems of SEC due to the absence of an obstructing porous stationary phase. The SEC-separation mainly depends on the pore size distribution of the used column set. The analyte molecules can enter the pores of the stationary phase in dependence on their hydrodynamic volume. The archived separation is a result of the retention time of the analyte species inside SEC-column which depends on the accessibility of the pores, the residence time inside the pores and the diffusion ability of the analyte molecules. The elution order in SEC is typically from low to high hydrodynamic volume. On the contrary AF4 separates according to the diffusion coefficient of the analyte molecules as long as the chosen conditions support the normal FFF-separation mechanism. The separation takes place in an empty channel and is caused by a cross-flow field perpendicular to the solvent flow. The analyte molecules will arrange in different channel heights depending on the diffusion coefficients. The parabolic-shaped flow profile inside the channel leads to different elution velocities. The species with low hydrodynamic volume will elute first while the species with high hydrodynamic volume elute later. The AF4 can be performed at ambient or high temperature (AT-/HT-AF4). We have analyzed one low molar mass polyethylene sample and a number of narrow distributed polystyrene standards as reference materials with known structure by AT/HT-SEC and AT/HT-AF4. Low density polyethylenes as well as polypropylene and polybutadiene, containing high degrees of branching and high molar masses, have been analyzed with both methods. As in SEC the relationship between the radius of gyration (R(g)) or the molar mass and the elution volume is curved up towards high elution volumes, a correct calculation of the MMD and the molar mass average or branching ratio is not possible using the data from the SEC measurements. In contrast to SEC, AF4 allows the precise determination of the MMD, the molar mass averages as well as the degree of branching because the molar mass vs. elution volume curve and the conformation plot is not falsified in this technique. In addition, higher molar masses can be detected using HT-AF4 due to the absence of significant shear degradation in the channel. As a result the average molar masses obtained from AF4 are higher compared to SEC. The analysis time in AF4 is comparable to that of SEC but the adjustable cross-flow program allows the user to influence the separation efficiency which is not possible in SEC without a costly change of the whole column combination. Copyright © 2011 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Chen, X.; Yao, G.; Cai, J.
2017-12-01
Pore structure characteristics are important factors in influencing the fluid transport behavior of porous media, such as pore-throat ratio, pore connectivity and size distribution, moreover, wettability. To accurately characterize the diversity of pore structure among HFUs, five samples selected from different HFUs (porosities are approximately equal, however permeability varies widely) were chosen to conduct micro-computerized tomography test to acquire direct 3D images of pore geometries and to perform mercury injection experiments to obtain the pore volume-radii distribution. To characterize complex and high nonlinear pore structure of all samples, three classic fractal geometry models were applied. Results showed that each HFU has similar box-counting fractal dimension and generalized fractal dimension in the number-area model, but there are significant differences in multifractal spectrums. In the radius-volume model, there are three obvious linear segments, corresponding to three fractal dimension values, and the middle one is proved as the actual fractal dimension according to the maximum radius. In the number-radius model, the spherical-pore size distribution extracted by maximum ball algorithm exist a decrease in the number of small pores compared with the fractal power rate rather than the traditional linear law. Among the three models, only multifractal analysis can classify the HFUs accurately. Additionally, due to the tightness and low-permeability in reservoir rocks, connate water film existing in the inner surface of pore channels commonly forms bound water. The conventional model which is known as Yu-Cheng's model has been proved to be typically not applicable. Considering the effect of irreducible water saturation, an improved fractal permeability model was also deduced theoretically. The comparison results showed that the improved model can be applied to calculate permeability directly and accurately in such unconventional rocks.
Measurements of unjacketed moduli of porous rock
NASA Astrophysics Data System (ADS)
Tarokh, A.; Makhnenko, R. Y.; Labuz, J.
2017-12-01
Coupling of stress and pore pressure appears in a number of applications dealing with subsurface (sedimentary) rock, including petroleum exploration and waste storage. Poroelastic analyses consider the compressibility of the solid constituents forming the rock, and often times solid bulk modulus Ks is assumed to be the same as the dominant mineral bulk modulus. In fact, there are two different parameters describing solid compressibility of a porous rock: the unjacketed bulk modulus Ks' and the unjacketed pore modulus Ks". Experimental techniques are developed to measure the two poroelastic parameters of fluid-saturated porous rock under the unjacketed condition. In an unjacketed experiment, the rock without a membrane is loaded by the fluid in a pressure vessel. The confining fluid permeates the connected pore space throughout the interior of the rock. Therefore, changes in mean stress P will produce equal changes in pore pressure p, i.e. ΔP = Δp. The test can also be performed with a jacketed rock specimen by applying equal increments of mean stress and pore pressure. The unjacketed bulk modulus, Ks', is obtained by measuring the bulk strain with resistive strain gages. The unjacketed pore modulus, Ks", the pore volume counterpart to Ks', is a measure of the change in pore pressure per unit pore volume strain under the unjacketed condition. Several indirect estimates of Ks" have been reported but limitations of these approaches do not provide an accurate value. We present direct measurements of Ks" with detailed calibration on the system volumetric response. The results indicate that for Dunnville sandstone Ks' and Ks" are equal while for Berea sandstone, a difference between the two moduli exists, which is explained by the presence of non-connected pores. The experiments also strongly suggest that both Ks' and Ks" are independent of effective stress.
Garcia, Jose; Markovski, Jasmina; McKay Gifford, J; Apul, Onur; Hristovski, Kiril D
2017-05-15
The overarching goal of this study was to ascertain the changes in intraparticle mass transport rates for organic contaminants resulting from nano-enabled hybridization of commercially available granular activated carbon (GAC). Three different nano-enabled hybrid media were fabricated by in-situ synthesizing titanium dioxide nanoparticles inside the pores of GAC sorbent, characterized, and evaluated for removal of two model organic contaminants under realistic conditions to obtain the intraparticle mass transport (pore and surface diffusion) coefficients. The results validated the two hypotheses that: (H1) the pore diffusion rates of organic contaminants linearly decrease with decrease in cumulative pore volume caused by increase in metal (hydr)oxide nanoparticle content inside the pores of the hybrid GAC sorbent; and (H2) introduction of metal (hydr)oxide nanoparticles initially increases surface diffusivity, but additional loading causes its decrease as the increase in metal (hydr)oxide nanoparticles content continues to reduce the porosity of the GAC sorbent. Nano-enabled hybridization of commercially available GAC with metal (hydr)oxides has the potential to significantly increase the intraparticle mass transport limitations for organic contaminants. Introduction of metal (hydr)oxide nanoparticles inside the pores of a pristine sorbent causes the pore diffusion rates of organic contaminants to decrease as the cumulative pore volume is reduced. In contrast, the introduction of limited amounts of metal (hydr)oxide nanoparticles appears to facilitate the surface diffusion rates of these contaminants. Copyright © 2017 Elsevier B.V. All rights reserved.
Calibrating the Iowa pore index with mercury intrusion porosimetry and petrography.
DOT National Transportation Integrated Search
2017-10-31
The Iowa Pore Index (IPI) test is a fast, non-destructive, inexpensive, and environmentally friendly test used by several Midwestern state departments of transportation to determine the volume ratio of macropores to micropores in a coarse rock aggreg...
Mars: Crustal pore volume, cryospheric depth, and the global occurrence of groundwater
NASA Technical Reports Server (NTRS)
Clifford, Stephen M.
1987-01-01
It is argued that most of the Martian hydrosphere resides in a porous outer layer of crust that, based on a lunar analogy, appears to extend to a depth of about 10 km. The total pore volume of this layer is sufficient to store the equivalent of a global ocean of water some 500 to 1500 m deep. Thermal modeling suggests that about 300 to 500 m of water could be stored as ice within the crust. Any excess must exist as groundwater.
Xi, Kai; Cao, Shuai; Peng, Xiaoyu; Ducati, Caterina; Kumar, R Vasant; Cheetham, Anthony K
2013-03-18
This paper presents a novel method and rationale for utilizing carbonized MOFs for sulphur loading to fabricate cathode structures for lithium-sulphur batteries. Unique carbon materials with differing hierarchical pore structures were synthesized from four types of zinc-containing metal-organic frameworks (MOFs). It is found that cathode materials made from MOFs-derived carbons with higher mesopore (2-50 nm) volumes exhibit increased initial discharge capacities, whereas carbons with higher micropore (<2 nm) volumes lead to cathode materials with better cycle stability.
Experimental study on pore structure and performance of sintered porous wick
NASA Astrophysics Data System (ADS)
He, Da; Wang, Shufan; Liu, Rutie; Wang, Zhubo; Xiong, Xiang; Zou, Jianpeng
2018-02-01
Porous wicks were prepared via powder metallurgy using NH4HCO3 powders as pore-forming agent. The pore-forming agent particle size was varied to control the pore structure and equivalent pore size distribution feature of porous wick. The effect of pore-forming agent particle size on the porosity, pore structures, equivalent pore size distribution and capillary pumping performance were investigated. Results show that with the particle size of pore-forming agent decrease, the green density and the volume shrinkage of the porous wicks gradually increase and the porosity reduces slightly. There are two types of pores inside the porous wick, large-sized prefabricated pores and small-sized gap pores. With the particle size of pore-forming agent decrease, the size of the prefabricated pores becomes smaller and the distribution tends to be uniform. Gap pores and prefabricated pores inside the wick can make up different types of pore channels. The equivalent pore size of wick is closely related to the structure of pore channels. Furthermore, the equivalent pore size distribution of wick shows an obvious double-peak feature when the pore-forming agent particle size is large. With the particle size of pore-forming agent decrease, the two peaks of equivalent pore size distribution approach gradually to each other, resulting in a single-peak feature. Porous wick with single-peak feature equivalent pore size distribution possesses the better capillary pumping performances.
Popken, Jens; Schmid, Volker J; Strauss, Axel; Guengoer, Tuna; Wolf, Eckhard; Zakhartchenko, Valeri
2016-04-22
Utilizing 3D structured illumination microscopy, we investigated the quality and quantity of nuclear invaginations and the distribution of nuclear pores during rabbit early embryonic development and identified the exact time point of nucleoporin 153 (NUP153) association with chromatin during mitosis. Contrary to bovine early embryonic nuclei, featuring almost exclusively nuclear invaginations containing a small volume of cytoplasm, nuclei in rabbit early embryonic stages show additionally numerous invaginations containing a large volume of cytoplasm. Small-volume invaginations frequently emanated from large-volume nuclear invaginations but not vice versa, indicating a different underlying mechanism. Large- and small-volume nuclear envelope invaginations required the presence of chromatin, as they were restricted to chromatin-positive areas. The chromatin-free contact areas between nucleolar precursor bodies (NPBs) and large-volume invaginations were free of nuclear pores. Small-volume invaginations were not in contact with NPBs. The number of invaginations and isolated intranuclear vesicles per nucleus peaked at the 4-cell stage. At this stage, the nuclear surface showed highly concentrated clusters of nuclear pores surrounded by areas free of nuclear pores. Isolated intranuclear lamina vesicles were usually NUP153 negative. Cytoplasmic, randomly distributed NUP153-positive clusters were highly abundant at the zygote stage and decreased in number until they were almost absent at the 8-cell stage and later. These large NUP153 clusters may represent a maternally provided NUP153 deposit, but they were not visible as clusters during mitosis. Major genome activation at the 8- to 16-cell stage may mark the switch from a necessity for a deposit to on-demand production. NUP153 association with chromatin is initiated during metaphase before the initiation of the regeneration of the lamina. To our knowledge, the present study demonstrates for the first time major remodeling of the nuclear envelope and its underlying lamina during rabbit preimplantation development.
Porous Carbon with Willow-Leaf-Shaped Pores for High-Performance Supercapacitors.
Shi, Yanhong; Zhang, Linlin; Schon, Tyler B; Li, Huanhuan; Fan, Chaoying; Li, Xiaoying; Wang, Haifeng; Wu, Xinglong; Xie, Haiming; Sun, Haizhu; Seferos, Dwight S; Zhang, Jingping
2017-12-13
A novel kind of biomass-derived, high-oxygen-containing carbon material doped with nitrogen that has willow-leaf-shaped pores was synthesized. The obtained carbon material has an exotic hierarchical pore structure composed of bowl-shaped macropores, willow-leaf-shaped pores, and an abundance of micropores. This unique hierarchical porous structure provides an effective combination of high current densities and high capacitance because of a pseudocapacitive component that is afforded by the introduction of nitrogen and oxygen dopants. Our synthetic optimization allows further improvements in the performance of this hierarchical porous carbon (HPC) material by providing a high degree of control over the graphitization degree, specific surface area, and pore volume. As a result, a large specific surface area (1093 m 2 g -1 ) and pore volume (0.8379 cm 3 g -1 ) are obtained for HPC-650, which affords fast ion transport because of its short ion-diffusion pathways. HPC-650 exhibits a high specific capacitance of 312 F g -1 at 1 A g -1 , retaining 76.5% of its capacitance at 20 A g -1 . Moreover, it delivers an energy density of 50.2 W h kg -1 at a power density of 1.19 kW kg -1 , which is sufficient to power a yellow-light-emitting diode and operate a commercial scientific calculator.
Wan, Zhipeng; Jiang, Wentao; Wang, Chong; Wang, Qingyuan; Li, Yalan
2017-10-01
Three dimensional (3D) printing is considered as an advanced manufacturing technology because of its additive nature. Electron beam melting (EBM) is a widely used 3D printing processes for the manufacturing of metal components. However, the products printed via this process generally contain micro porosities which affect mechanical properties, especially the fatigue property. In this paper, two types of EBM printed samples of the Ti-6Al-4V alloy, one with a round cross section and the other with a triangle cross section, were employed to investigate the existence of porosities using computed tomography (CT). Statistical analyses were conducted on the number, volume, shape, and distribution of pores. The results show that small pores (less than 0.000 2 mm 3 ) account for 80% of all pores in each type of samples. Additionally, to some extent, the shape of sample has influence on the number of micro porosities in EBM made Ti-6Al-4V. The sphericity of the pores is relatively low and is inversely proportional to pore volume. It is found that re-melting on the free surface effectively reduce pore density near the surface. This study may help produce a medical implant with better fatigue resistance.
Optimizing heterosurface adsorbent synthesis for liquid chromatography
NASA Astrophysics Data System (ADS)
Bogoslovskii, S. Yu.; Serdan, A. A.
2016-03-01
The structural and geometric parameters of a silica matrix (SM) for the synthesis of heterosurface adsorbents (HAs) are optimized. Modification is performed by shielding the external surfaces of alkyl-modified silica (AS) using human serum albumin and its subsequent crosslinking. The structural and geometric characteristics of the SM, AS, and HA are measured via low-temperature nitrogen adsorption. It is found that the structural characteristics of AS pores with diameters D < 6 nm do not change during HA synthesis, while the volume of pores with diameters of 6 nm < D < 9 nm shrinks slightly due to the adsorption of albumin in the pore orifices. It is established that the volume of pores with diameters D > 9 nm reduces significantly due to adsorption of albumin. It is concluded that silica gel with a maximum pore size distribution close to 5 nm and a minimal proportion of pores with D > 9 nm is optimal for HA synthesis; this allows us to achieve the greatest similarity between the chromatographic retention parameters for HA and AS. The suitability of the synthesized adsorbents for analyzing drugs in biological fluids through direct sample injection is confirmed by chromatography. It was found that the percentage of the protein fraction detected at the outlet of the chromatographic column is 98%.
NASA Astrophysics Data System (ADS)
Arzilli, F.; Cilona, A.; Mancini, L.; Tondi, E.
2016-09-01
In this work we propose a new methodology to calculate pore connectivity in granular rocks. This method is useful to characterize the pore networks of natural and laboratory compaction bands (CBs), and compare them with the host rock pore network. Data were collected using the synchrotron X-ray microtomography technique and quantitative analyses were carried out using the Pore3D software library. The porosity was calculated from segmented tridimensional images of deformed and pristine rocks. A process of skeletonization of the pore space was used to obtain the number of connected pores within the rock volume. By analyzing the skeletons the differences between natural and laboratory CBs were highlighted. The natural CB has a lower porosity than to the laboratory one. In natural CBs, the grain contacts appear welded, whereas laboratory CBs show irregular pore shape. Moreover, we assessed for the first time how pore connectivity evolves as a function of deformation, documenting the mechanism responsible for pore connectivity drop within the CBs.
Estimating pore and cement volumes in thin section
Halley, R.B.
1978-01-01
Point count estimates of pore, grain and cement volumes from thin sections are inaccurate, often by more than 100 percent, even though they may be surprisingly precise (reproducibility + or - 3 percent). Errors are produced by: 1) inclusion of submicroscopic pore space within solid volume and 2) edge effects caused by grain curvature within a 30-micron thick thin section. Submicroscopic porosity may be measured by various physical tests or may be visually estimated from scanning electron micrographs. Edge error takes the form of an envelope around grains and increases with decreasing grain size and sorting, increasing grain irregularity and tighter grain packing. Cements are greatly involved in edge error because of their position at grain peripheries and their generally small grain size. Edge error is minimized by methods which reduce the thickness of the sample viewed during point counting. Methods which effectively reduce thickness include use of ultra-thin thin sections or acetate peels, point counting in reflected light, or carefully focusing and counting on the upper surface of the thin section.
Ceramic impregnated superabrasives
Radtke, Robert P.; Sherman, Andrew
2009-02-10
A superabrasive fracture resistant compact is formed by depositing successive layers of ceramic throughout the network of open pores in a thermally stable self-bonded polycrystalline diamond or cubic boron nitride preform. The void volume in the preform is from approximately 2 to 10 percent of the volume of the preform, and the average pore size is below approximately 3000 nanometers. The preform is evacuated and infiltrated under at least about 1500 pounds per square inch pressure with a liquid pre-ceramic polymerizable precursor. The precursor is infiltrated into the preform at or below the boiling point of the precursor. The precursor is polymerized into a solid phase material. The excess is removed from the outside of the preform, and the polymer is pyrolized to form a ceramic. The process is repeated at least once more so as to achieve upwards of 90 percent filling of the original void volume. When the remaining void volume drops below about 1 percent the physical properties of the compact, such as fracture resistance, improve substantially. Multiple infiltration cycles result in the deposition of sufficient ceramic to reduce the void volume to below 0.5 percent. The fracture resistance of the compacts in which the pores are lined with formed in situ ceramic is generally at least one and one-half times that of the starting preforms.
NASA Astrophysics Data System (ADS)
Georgiadis, A.; Berg, S.; Makurat, A.; Maitland, G.; Ott, H.
2013-09-01
We investigated the cluster-size distribution of the residual nonwetting phase in a sintered glass-bead porous medium at two-phase flow conditions, by means of micro-computed-tomography (μCT) imaging with pore-scale resolution. Cluster-size distribution functions and cluster volumes were obtained by image analysis for a range of injected pore volumes under both imbibition and drainage conditions; the field of view was larger than the porosity-based representative elementary volume (REV). We did not attempt to make a definition for a two-phase REV but used the nonwetting-phase cluster-size distribution as an indicator. Most of the nonwetting-phase total volume was found to be contained in clusters that were one to two orders of magnitude larger than the porosity-based REV. The largest observed clusters in fact ranged in volume from 65% to 99% of the entire nonwetting phase in the field of view. As a consequence, the largest clusters observed were statistically not represented and were found to be smaller than the estimated maximum cluster length. The results indicate that the two-phase REV is larger than the field of view attainable by μCT scanning, at a resolution which allows for the accurate determination of cluster connectivity.
Tomographic image of a seismically active volcano: Mammoth Mountain, California
Dawson, Phillip B.; Chouet, Bernard A.; Pitt, Andrew M.
2016-01-01
High-resolution tomographic P wave, S wave, and VP/VS velocity structure models are derived for Mammoth Mountain, California, using phase data from the Northern California Seismic Network and a temporary deployment of broadband seismometers. An anomalous volume (5.1 × 109 to 5.9 × 1010m3) of low P and low S wave velocities is imaged beneath Mammoth Mountain, extending from near the surface to a depth of ∼2 km below sea level. We infer that the reduction in seismic wave velocities is due to the presence of CO2 distributed in oblate spheroid pores with mean aspect ratio α = 1.6 × 10−3 to 7.9 × 10−3 (crack-like pores) and mean gas volume fraction ϕ = 8.1 × 10−4 to 3.4 × 10−3. The pore density parameter κ = 3ϕ/(4πα) = na3=0.11, where n is the number of pores per cubic meter and a is the mean pore equatorial radius. The total mass of CO2 is estimated to be 4.6 × 109 to 1.9 × 1011 kg. The local geological structure indicates that the CO2 contained in the pores is delivered to the surface through fractures controlled by faults and remnant foliation of the bedrock beneath Mammoth Mountain. The total volume of CO2 contained in the reservoir suggests that given an emission rate of 500 tons day−1, the reservoir could supply the emission of CO2 for ∼25–1040 years before depletion. Continued supply of CO2 from an underlying magmatic system would significantly prolong the existence of the reservoir.
Tomographic image of a seismically active volcano: Mammoth Mountain, California
NASA Astrophysics Data System (ADS)
Dawson, Phillip; Chouet, Bernard; Pitt, Andrew
2016-01-01
High-resolution tomographic P wave, S wave, and VP/VS velocity structure models are derived for Mammoth Mountain, California, using phase data from the Northern California Seismic Network and a temporary deployment of broadband seismometers. An anomalous volume (5.1 × 109 to 5.9 × 1010m3) of low P and low S wave velocities is imaged beneath Mammoth Mountain, extending from near the surface to a depth of ˜2 km below sea level. We infer that the reduction in seismic wave velocities is due to the presence of CO2 distributed in oblate spheroid pores with mean aspect ratio α = 1.6 × 10-3 to 7.9 × 10-3 (crack-like pores) and mean gas volume fraction ϕ = 8.1 × 10-4 to 3.4 × 10-3. The pore density parameter κ = 3ϕ/(4πα) = na3=0.11, where n is the number of pores per cubic meter and a is the mean pore equatorial radius. The total mass of CO2 is estimated to be 4.6 × 109 to 1.9 × 1011 kg. The local geological structure indicates that the CO2 contained in the pores is delivered to the surface through fractures controlled by faults and remnant foliation of the bedrock beneath Mammoth Mountain. The total volume of CO2 contained in the reservoir suggests that given an emission rate of 500 tons day-1, the reservoir could supply the emission of CO2 for ˜25-1040 years before depletion. Continued supply of CO2 from an underlying magmatic system would significantly prolong the existence of the reservoir.
Influence of Rubber Size on Properties of Crumb Rubber Mortars
Yu, Yong; Zhu, Han
2016-01-01
Studies on the properties and applications of rubber cement-based materials are well documented. The sizes of rubbers used in these materials varied. However, information about the effects of rubber size on the properties of rubber cement-based materials, especially pore structure, mechanical strengths, and drying shrinkage properties, remains limited. Three groups of rubber with major particle sizes of 2–4 mm, 1–3 mm, and 0–2 mm were selected in this study. This paper presents experimental studies on the effects of rubber size on the consistency, fresh density, pore structure, mechanical properties, and drying shrinkage properties of crumb rubber mortars (CRMs). Results demonstrated that the consistency and fresh density of CRMs decreased with the rubber size. As to the pore structure, the total pore volume increased with the decrease of the rubber size. By contrast, the influence of the rubber size on the mesopore (<50 nm) volume is not as significant as that of the rubber content. The mechanical properties of CRMs decreased with the rubber size. Low rubber stiffness and large pore volumes, especially those of small sized rubbers, contribute to the reduction of CRMs strength. The drying shrinkage of CRM increases as the rubber size decreases. The influences of rubber size on capillary tension are not significant. Thus, the shrinkage increases with the decrease of rubber size mainly because of its function in the deformation modulus reduction of CRMs. PMID:28773649
NASA Astrophysics Data System (ADS)
Shah, S.; Gray, F.; Yang, J.; Crawshaw, J.; Boek, E.
2016-12-01
Advances in 3D pore-scale imaging and computational methods have allowed an exceptionally detailed quantitative and qualitative analysis of the fluid flow in complex porous media. A fundamental problem in pore-scale imaging and modelling is how to represent and model the range of scales encountered in porous media, starting from the smallest pore spaces. In this study, a novel method is presented for determining the representative elementary volume (REV) of a rock for several parameters simultaneously. We calculate the two main macroscopic petrophysical parameters, porosity and single-phase permeability, using micro CT imaging and Lattice Boltzmann (LB) simulations for 14 different porous media, including sandpacks, sandstones and carbonates. The concept of the `Convex Hull' is then applied to calculate the REV for both parameters simultaneously using a plot of the area of the convex hull as a function of the sub-volume, capturing the different scales of heterogeneity from the pore-scale imaging. The results also show that the area of the convex hull (for well-chosen parameters such as the log of the permeability and the porosity) decays exponentially with sub-sample size suggesting a computationally efficient way to determine the system size needed to calculate the parameters to high accuracy (small convex hull area). Finally we propose using a characteristic length such as the pore size to choose an efficient absolute voxel size for the numerical rock.
Digital Rock Simulation of Flow in Carbonate Samples
NASA Astrophysics Data System (ADS)
Klemin, D.; Andersen, M.
2014-12-01
Reservoir engineering has becomes more complex to deal with current challenges, so core analysts must understand and model pore geometries and fluid behaviors at pores scales more rapidly and realistically. We introduce an industry-unique direct hydrodynamic pore flow simulator that operates on pore geometries from digital rock models obtained using microCT or 3D scanning electron microscope (SEM) images. The PVT and rheological models used in the simulator represent real reservoir fluids. Fluid-solid interactions are introduced using distributed micro-scale wetting properties. The simulator uses density functional approach applied for hydrodynamics of complex systems. This talk covers selected applications of the simulator. We performed microCT scanning of six different carbonate rock samples from homogeneous limestones to vuggy carbonates. From these, we constructed digital rock models representing pore geometries for the simulator. We simulated nonreactive tracer flow in all six digital models using a digital fluid description that included a passive tracer solution. During the simulation, we evaluated the composition of the effluent. Results of tracer flow simulations corresponded well with experimental data of nonreactive tracer floods for the same carbonate rock types. This simulation data of the non-reactive tracer flow can be used to calculate the volume of the rock accessible by the fluid, which can be further used to predict response of a porous medium to a reactive fluid. The described digital core analysis workflow provides a basis for a wide variety of activities, including input to design acidizing jobs and evaluating treatment efficiency and EOR economics. Digital rock multiphase flow simulations of a scanned carbonate rock evaluated the effect of wettability on flow properties. Various wetting properties were tested: slightly oil wet, slightly water wet, and water wet. Steady-state relative permeability simulations yielded curves for all three ranges of wetting properties. The wetting variation affected phase mobility and residual phase saturations for primary oil flood and floods with varying ratios of oil and water.
NASA Astrophysics Data System (ADS)
Akhir, Muhammad Fitri Mohd; Saad, Noor Aida; Zakaria, Nor Azazi
2017-10-01
Commonly, water contaminations occur due to human-induced conditions such as industrial discharge and urban activities. The widely identified contaminants are heavy metal. The toxicity of those heavy metal elements is high and very poisonous to humans' health and environment even at lower dose or concentration of exposure. Chronic poisoning can cause fatal or defect to one's body or environment. Organic contaminants such as oil and microbial are also found due to decomposition of organic matter. The excellent quality adsorption of contaminants is highly related to surface area, pore size, pore volume, and amount plus type of functional group on surface of CSAC. The higher the surface area and pore volume, the higher adsorption that CSAC have towards contaminants. In comparison to meso-pore and macro-pore, micro-pore is better for trapping and adsorbing water contaminants. The purpose of this article is to critically review the potential of CSAC in increasing adsorption to remove contaminants for water quality improvement. A critical review is implemented using search engine like Science Direct. Alkali-modification is shown to have good adsorption in anion elements and organic matter due to improvement of hydrophobic organic compound (HOC) while acid-modification is good in cation elements adsorption. Strong alkali impregnated solution makes CSAC more hydrophobic and positively charge especially after increasing the impregnation dosage. Strong acid of adsorbate affects the quality of adsorption by reducing the surface area, pore volume and it also breaks the Van der Waals forces between adsorbent and adsorbate. However, the formation of oxygen helps the activated carbon surface to become more hydrophilic and negative charge is produced. It helps the effectiveness of metal adsorption. Therefore, by controlling dosage and types of functional groups on surface of CSAC and the pH of adsorbate, it can contribute to high adsorption of organic and inorganic contaminants in the water.
Milovanovic, Petar; Vukovic, Zorica; Antonijevic, Djordje; Djonic, Danijela; Zivkovic, Vladimir; Nikolic, Slobodan; Djuric, Marija
2017-05-01
Bone is a remarkable biological nanocomposite material showing peculiar hierarchical organization from smaller (nano, micro) to larger (macro) length scales. Increased material porosity is considered as the main feature of fragile bone at larger length-scales. However, there is a shortage of quantitative information on bone porosity at smaller length-scales, as well as on the distribution of pore sizes in healthy vs. fragile bone. Therefore, here we investigated how healthy and fragile bones differ in pore volume and pore size distribution patterns, considering a wide range of mostly neglected pore sizes from nano to micron-length scales (7.5 to 15000 nm). Cortical bone specimens from four young healthy women (age: 35 ± 6 years) and five women with bone fracture (age: 82 ± 5 years) were analyzed by mercury porosimetry. Our findings showed that, surprisingly, fragile bone demonstrated lower pore volume at the measured scales. Furtnermore, pore size distribution showed differential patterns between healthy and fragile bones, where healthy bone showed especially high proportion of pores between 200 and 15000 nm. Therefore, although fragile bones are known for increased porosity at macroscopic level and level of tens or hundreds of microns as firmly established in the literature, our study with a unique assessment range of nano-to micron-sized pores reveal that osteoporosis does not imply increased porosity at all length scales. Our thorough assessment of bone porosity reveals a specific distribution of porosities at smaller length-scales and contributes to proper understanding of bone structure which is important for designing new biomimetic bone substitute materials.
Direct Numerical Simulation of Low Capillary Number Pore Scale Flows
NASA Astrophysics Data System (ADS)
Esmaeilzadeh, S.; Soulaine, C.; Tchelepi, H.
2017-12-01
The arrangement of void spaces and the granular structure of a porous medium determines multiple macroscopic properties of the rock such as porosity, capillary pressure, and relative permeability. Therefore, it is important to study the microscopic structure of the reservoir pores and understand the dynamics of fluid displacements through them. One approach for doing this, is direct numerical simulation of pore-scale flow that requires a robust numerical tool for prediction of fluid dynamics and a detailed understanding of the physical processes occurring at the pore-scale. In pore scale flows with a low capillary number, Eulerian multiphase methods are well-known to produce additional vorticity close to the interface. This is mainly due to discretization errors which lead to an imbalance of capillary pressure and surface tension forces that causes unphysical spurious currents. At the pore scale, these spurious currents can become significantly stronger than the average velocity in the phases, and lead to unphysical displacement of the interface. In this work, we first investigate the capability of the algebraic Volume of Fluid (VOF) method in OpenFOAM for low capillary number pore scale flow simulations. Afterward, we compare VOF results with a Coupled Level-Set Volume of Fluid (CLSVOF) method and Iso-Advector method. It has been shown that the former one reduces the VOF's unphysical spurious currents in some cases, and both are known to capture interfaces sharper than VOF. As the conclusion, we will investigate that whether the use of CLSVOF or Iso-Advector will lead to less spurious velocities and more accurate results for capillary driven pore-scale multiphase flows or not. Keywords: Pore-scale multiphase flow, Capillary driven flows, Spurious currents, OpenFOAM
Li, Yanqiang; Roy, Soumyajit; Ben, Teng; Xu, Shixian; Qiu, Shilun
2014-07-07
Micropore engineering of porous carbons on the effect of capacitance was explored using a carbonized porous aromatic framework (PAF-1). The porous carbons obtained through different carbonization methods show different pore structures enabling us to do this. The capacitance was measured both in aqueous electrolyte and different organic electrolytes. The porous carbons prepared by KOH activation show both high microporous volume, which is beneficial for charge storage, and mesoporous volume, which is devoted to fast ion diffusion in the pores; properties which are highly desirable. It shows a capacitance as high as 280 F g(-1) and 203 F g(-1) at a current density of 1 A g(-1) in 6.0 M KOH and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMImTFSI), respectively. We also demonstrate the effect of diffusion and that of geometric packing of the electrolyte ions in the pores, where a commensurate match of the electrolyte ions with the pores of carbonized materials control and influence significantly the capacitance of these materials.
Hierarchically Porous Carbon Materials for CO 2 Capture: The Role of Pore Structure
DOE Office of Scientific and Technical Information (OSTI.GOV)
Estevez, Luis; Barpaga, Dushyant; Zheng, Jian
2018-01-17
With advances in porous carbon synthesis techniques, hierarchically porous carbon (HPC) materials are being utilized as relatively new porous carbon sorbents for CO2 capture applications. These HPC materials were used as a platform to prepare samples with differing textural properties and morphologies to elucidate structure-property relationships. It was found that high microporous content, rather than overall surface area was of primary importance for predicting good CO2 capture performance. Two HPC materials were analyzed, each with near identical high surface area (~2700 m2/g) and colossally high pore volume (~10 cm3/g), but with different microporous content and pore size distributions, which ledmore » to dramatically different CO2 capture performance. Overall, large pore volumes obtained from distinct mesopores were found to significantly impact adsorption performance. From these results, an optimized HPC material was synthesized that achieved a high CO2 capacity of ~3.7 mmol/g at 25°C and 1 bar.« less
NASA Astrophysics Data System (ADS)
Hou, Haihai; Shao, Longyi; Li, Yonghong; Li, Zhen; Zhang, Wenlong; Wen, Huaijun
2018-03-01
The continental shales from the Middle Jurassic Shimengou Formation of the northern Qaidam Basin, northwestern China, have been investigated in recent years because of their shale gas potential. In this study, a total of twenty-two shale samples were collected from the YQ-1 borehole in the Yuqia Coalfield, northern Qaidam Basin. The total organic carbon (TOC) contents, pore structure parameters, and fractal characteristics of the samples were investigated using TOC analysis, low-temperature nitrogen adsorption experiments, and fractal analysis. The results show that the average pore size of the Shimengou shales varied from 8.149 nm to 20.635 nm with a mean value of 10.74 nm, which is considered mesopore-sized. The pores of the shales are mainly inkbottle- and slit-shaped. The sedimentary environment plays an essential role in controlling the TOC contents of the low maturity shales, with the TOC values of shales from deep to semi-deep lake facies (mean: 5.23%) being notably higher than those of the shore-shallow lake facies (mean: 0.65%). The fractal dimensions range from 2.4639 to 2.6857 with a mean of 2.6122, higher than those of marine shales, which indicates that the pore surface was rougher and the pore structure more complex in these continental shales. The fractal dimensions increase with increasing total pore volume and total specific surface area, and with decreasing average pore size. With increasing TOC contents in shales, the fractal dimensions increase first and then decrease, with the highest value occurring at 2% of TOC content, which is in accordance with the trends between the TOC and both total specific surface area and total pore volume. The pore structure complexity and pore surface roughness of these low-maturity shales would be controlled by the combined effects of both sedimentary environments and the TOC contents.
NASA Astrophysics Data System (ADS)
Li, Chong; Zhang, Guilong; Wang, Min; Chen, Jianfeng; Cai, Dongqing; Wu, Zhengyan
2014-08-01
High energy electron beam (HEEB) irradiation and hydrothermal treatment (HT), were applied in order to remove the impurities and enlarge the pore size of diatomite, making diatomite more suitable to be a catalyst support. The results demonstrated that, through thermal, charge, impact and etching effects, HEEB irradiation could make the impurities in the pores of diatomite loose and remove some of them. Then HT could remove rest of them from the pores and contribute significantly to the modification of the pore size distribution of diatomite due to thermal expansion, water swelling and thermolysis effects. Moreover, the pore structure modification improved the properties (BET (Brunauer-Emmett-Teller) specific surface area, bulk density and pore volume) of diatomite and the catalytic efficiency of the catalyst prepared from the treated diatomite.
Template-directed assembly of metal-chalcogenide nanocrystals into ordered mesoporous networks.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Vamvasakis, Ioannis; Subrahmanyam, Kota S.; Kanatzidis, Mercouri G.
Although great progress in the synthesis of porous networks of metal and metal oxide nanoparticles with highly accessible pore surface and ordered mesoscale pores has been achieved, synthesis of assembled 3D mesostructures of metal-chalcogenide nanocrystals is still challenging. In this work we demonstrate that ordered mesoporous networks, which comprise well-defined interconnected metal sulfide nanocrystals, can be prepared through a polymer-templated oxidative polymerization process. The resulting self-assembled mesostructures that were obtained after solvent extraction of the polymer template impart the unique combination of light-emitting metal chalcogenide nanocrystals, three-dimensional open-pore structure, high surface area, and uniform pores. We show that the poremore » surface of these materials is active and accessible to incoming molecules, exhibiting high photocatalytic activity and stability, for instance, in oxidation of 1-phenylethanol into acetophenone. We demonstrate through appropriate selection of the synthetic components that this method is general to prepare ordered mesoporous materials from metal chalcogenide nanocrystals with various sizes and compositions.« less
Gas occurrence property in shales of Tuha basin northwest china
NASA Astrophysics Data System (ADS)
Chen, Jinlong; Huang, Zhilong
2017-04-01
Pore of rock under formation condition must be fulfilled by gas, oil, or water, so the volume of water and gas is equation to porous volume in shale gas. The occurrences states of gas are free gas, solution gas, and absorbed gas. Field analysis is used to obtain total gas content by improved lost gas recover method. Free gas content acquired by pore proportion of gas, which use measured pore volume minus water and oil saturation, convert gas content of standard condition by state equation. Water saturation obtain from core water content, oil saturation obtain from extract carbohydrate. Solution gas need gas solubility in oil and water to calculate solution gas content in standard condition. Absorbed gas, introduce Absorbed Gas Saturation ɛ, which acquire from isothermal adsorption volume vs field analysis gas content in many basins of published paper, need isothermal adsorption and Absorbed Gas Saturation to obtain absorbed gas content. All of the data build connect with logging value by regression equation. The gas content is 0.92-1.53 m3/t from field analysis, evaluate gas content is 1.33 m3/t average, free gas proportion is about 47%, absorbed gas counter for 49%, and solution gas is average 4%.
NASA Astrophysics Data System (ADS)
Lee, Hae-Jeong; Soles, Christopher L.; Liu, Da-Wei; Bauer, Barry J.; Lin, Eric K.; Wu, Wen-Li; Gallagher, Michael
2006-09-01
Methylsilsesquioxane (MSQ) based porous low-k dielectric films are characterized by x-ray porosimetry (XRP) to determine their pore size distribution, average density, wall density, and porosity. By varying the porogen content from 1% to 30% by mass, the porosity changes from 12% to 34% by volume, indicating that the base MSQ matrix material contains approximately 10% by volume inherent microporosity. The wall density of this matrix material is measured to be 1.33-1.35g/cm3, independent of porosity. The average pore radii determined from the XRP adsorption isotherms increase from 6to27Å with increased porogen loadings. Small angle neutron scattering measurements confirm these XRP average pore radii for the films with porogen loading higher than 10% by mass.
Zhao, Jianhua; Jin, Zhijun; Hu, Qinhong; Jin, Zhenkui; Barber, Troy J; Zhang, Yuxiang; Bleuel, Markus
2017-11-13
An integration of small-angle neutron scattering (SANS), low-pressure N 2 physisorption (LPNP), and mercury injection capillary pressure (MICP) methods was employed to study the pore structure of four oil shale samples from leading Niobrara, Wolfcamp, Bakken, and Utica Formations in USA. Porosity values obtained from SANS are higher than those from two fluid-invasion methods, due to the ability of neutrons to probe pore spaces inaccessible to N 2 and mercury. However, SANS and LPNP methods exhibit a similar pore-size distribution, and both methods (in measuring total pore volume) show different results of porosity and pore-size distribution obtained from the MICP method (quantifying pore throats). Multi-scale (five pore-diameter intervals) inaccessible porosity to N 2 was determined using SANS and LPNP data. Overall, a large value of inaccessible porosity occurs at pore diameters <10 nm, which we attribute to low connectivity of organic matter-hosted and clay-associated pores in these shales. While each method probes a unique aspect of complex pore structure of shale, the discrepancy between pore structure results from different methods is explained with respect to their difference in measurable ranges of pore diameter, pore space, pore type, sample size and associated pore connectivity, as well as theoretical base and interpretation.
A multi-scale network method for two-phase flow in porous media
DOE Office of Scientific and Technical Information (OSTI.GOV)
Khayrat, Karim, E-mail: khayratk@ifd.mavt.ethz.ch; Jenny, Patrick
Pore-network models of porous media are useful in the study of pore-scale flow in porous media. In order to extract macroscopic properties from flow simulations in pore-networks, it is crucial the networks are large enough to be considered representative elementary volumes. However, existing two-phase network flow solvers are limited to relatively small domains. For this purpose, a multi-scale pore-network (MSPN) method, which takes into account flow-rate effects and can simulate larger domains compared to existing methods, was developed. In our solution algorithm, a large pore network is partitioned into several smaller sub-networks. The algorithm to advance the fluid interfaces withinmore » each subnetwork consists of three steps. First, a global pressure problem on the network is solved approximately using the multiscale finite volume (MSFV) method. Next, the fluxes across the subnetworks are computed. Lastly, using fluxes as boundary conditions, a dynamic two-phase flow solver is used to advance the solution in time. Simulation results of drainage scenarios at different capillary numbers and unfavourable viscosity ratios are presented and used to validate the MSPN method against solutions obtained by an existing dynamic network flow solver.« less
Degassing, gas retention and release in Fe(0) permeable reactive barriers.
Ruhl, Aki S; Jekel, Martin
2014-04-01
Corrosion of Fe(0) has been successfully utilized for the reductive treatment of multiple contaminants. Under anaerobic conditions, concurrent corrosion leads to the generation of hydrogen and its liberation as a gas. Gas bubbles are mobile or trapped within the irregular pore structure leading to a reduction of the water filled pore volume and thus decreased residence time and permeability (gas clogging). With regard to the contaminant transport to the reactive site, the estimation of surface properties of the reactive material indicated that individual gas bubbles only occupied minor contact areas of the reactive surface. Quantification of gas entrapment by both gravimetrical and tracer investigations revealed that development of preferential flow paths was not significant. A novel continuous gravimetrical method was implemented to record variations in gas entrapment and gas bubble releases from the reactive filling. Variation of grain size fractions revealed that the pore geometry had a significant impact on gas release. Large pores led to the release of comparably large gas amounts while smaller volumes were released from finer pores with a higher frequency. Relevant processes are explained with a simplified pictorial sequence that incorporates relevant mechanisms. Copyright © 2014 Elsevier B.V. All rights reserved.
Exploration of the pore structure of a peptide-gated Na+channel
Poët, Mallorie; Tauc, Michel; Lingueglia, Eric; Cance, Peggy; Poujeol, Philippe; Lazdunski, Michel; Counillon, Laurent
2001-01-01
The FMRF-amide-activated sodium channel (FaNaC), a member of the ENaC/Degenerin family, is a homotetramer, each subunit containing two transmembrane segments. We changed independently every residue of the first transmembrane segment (TM1) into a cysteine and tested each position’s accessibility to the cysteine covalent reagents MTSET and MTSES. Eleven mutants were accessible to the cationic MTSET, showing that TM1 faces the ion translocation pathway. This was confirmed by the accessibility of cysteines present in the acid-sensing ion channels and other mutations introduced in FaNaC TM1. Modification of accessibilities for positions 69, 71 and 72 in the open state shows that the gating mechanism consists of the opening of a constriction close to the intracellular side. The anionic MTSES did not penetrate into the channel, indicating the presence of a charge selectivity filter in the outer vestibule. Furthermore, amiloride inhibition resulted in the channel occlusion in the middle of the pore. Summarizing, the ionic pore of FaNaC includes a large aqueous cavity, with a charge selectivity filter in the outer vestibule and the gate close to the interior. PMID:11598003
Lukacs, Peter; Gawali, Vaibhavkumar S.; Cervenka, Rene; Ke, Song; Koenig, Xaver; Rubi, Lena; Zarrabi, Touran; Hilber, Karlheinz; Stary-Weinzinger, Anna; Todt, Hannes
2014-01-01
Despite the availability of several crystal structures of bacterial voltage-gated Na+ channels, the structure of eukaryotic Na+ channels is still undefined. We used predictions from available homology models and crystal structures to modulate an external access pathway for the membrane-impermeant local anesthetic derivative QX-222 into the internal vestibule of the mammalian rNaV1.4 channel. Potassium channel-based homology models predict amino acid Ile-1575 in domain IV segment 6 to be in close proximity to Lys-1237 of the domain III pore-loop selectivity filter. The mutation K1237E has been shown previously to increase the diameter of the selectivity filter. We found that an access pathway for external QX-222 created by mutations of Ile-1575 was abolished by the additional mutation K1237E, supporting the notion of a close spatial relationship between sites 1237 and 1575. Crystal structures of bacterial voltage-gated Na+ channels predict that the side chain of rNaV1.4 Trp-1531 of the domain IV pore-loop projects into the space between domain IV segment 6 and domain III pore-loop and, therefore, should obstruct the putative external access pathway. Indeed, mutations W1531A and W1531G allowed for exceptionally rapid access of QX-222. In addition, W1531G created a second non-selective ion-conducting pore, bypassing the outer vestibule but probably merging into the internal vestibule, allowing for control by the activation gate. These data suggest a strong structural similarity between bacterial and eukaryotic voltage-gated Na+ channels. PMID:24947510
Savina, Irina N.; Ingavle, Ganesh C.; Cundy, Andrew B.; Mikhalovsky, Sergey V.
2016-01-01
The development of bulk, three-dimensional (3D), macroporous polymers with high permeability, large surface area and large volume is highly desirable for a range of applications in the biomedical, biotechnological and environmental areas. The experimental techniques currently used are limited to the production of small size and volume cryogel material. In this work we propose a novel, versatile, simple and reproducible method for the synthesis of large volume porous polymer hydrogels by cryogelation. By controlling the freezing process of the reagent/polymer solution, large-scale 3D macroporous gels with wide interconnected pores (up to 200 μm in diameter) and large accessible surface area have been synthesized. For the first time, macroporous gels (of up to 400 ml bulk volume) with controlled porous structure were manufactured, with potential for scale up to much larger gel dimensions. This method can be used for production of novel 3D multi-component macroporous composite materials with a uniform distribution of embedded particles. The proposed method provides better control of freezing conditions and thus overcomes existing drawbacks limiting production of large gel-based devices and matrices. The proposed method could serve as a new design concept for functional 3D macroporous gels and composites preparation for biomedical, biotechnological and environmental applications. PMID:26883390
Postseismic rebound in fault step-overs caused by pore fluid flow
Peltzer, G.; Rosen, P.; Rogez, F.; Hudnut, K.
1996-01-01
Near-field strain induced by large crustal earthquakes results in changes in pore fluid pressure that dissipate with time and produce surface deformation. Synthetic aperture radar (SAR) interferometry revealed several centimeters of postseismic uplift in pull-apart structures and subsidence in a compressive jog along the Landers, California, 1992 earthquake surface rupture, with a relaxation time of 270 ?? 45 days. Such a postseismic rebound may be explained by the transition of the Poisson's ratio of the deformed volumes of rock from undrained to drained conditions as pore fluid flow allows pore pressure to return to hydrostatic equilibrium.
Cathode architectures for alkali metal / oxygen batteries
Visco, Steven J; Nimon, Vitaliy; De Jonghe, Lutgard C; Volfkovich, Yury; Bograchev, Daniil
2015-01-13
Electrochemical energy storage devices, such as alkali metal-oxygen battery cells (e.g., non-aqueous lithium-air cells), have a cathode architecture with a porous structure and pore composition that is tailored to improve cell performance, especially as it pertains to one or more of the discharge/charge rate, cycle life, and delivered ampere-hour capacity. A porous cathode architecture having a pore volume that is derived from pores of varying radii wherein the pore size distribution is tailored as a function of the architecture thickness is one way to achieve one or more of the aforementioned cell performance improvements.
NASA Astrophysics Data System (ADS)
Ding, M.; Hartl, M.; Wang, Y.; Hjelm, R.
2013-12-01
In nuclear waste management, clays are canonical materials in the construction of engineered barriers. They are also naturally occurring reactive minerals which play an important role in retention and colloidal facilitated reactive transport in subsurface systems. Knowledge of total and accessible porosity in clays is crucial in determining fluids transport behavior in clays. It will provide fundamental insight on the performance efficiency of specific clays as a barrier material and their role in regulating radionuclide transport in subsurface environments. The aim of the present work is to experimentally investigate the change in pore characteristics of clays as function of moisture content, and to determine their pore character in relation to their water retention capacity. Recent developments in small-angle neutron scattering (SANS) techniques allow quantitative measurement of pore morphology and size distribution of various materials in their pristine state under various sample environments (exposure to solution, high temperature, and so on). Furthermore, due to dramatic different neutron scattering properties of hydrogen and deuterium, one can readily use contrast variation, which is the isotopic labeling with various ratios of H and D (e.g. mixture of H2O/D2O) to highlight or suppress features of the sample. This is particularly useful in the study of complex pore system such as clays. In this study, we have characterized the pore structures for a number of clays including clay minerals and field samples which are relevant to high-level waste systems under various sample environments (e.g., humidity, temperature and pressure) using SANS. Our results suggest that different clays show unique pore features under various sample environments. To distinguish between accessible/non-accessible pores and the nature of pore filling (e.g. the quantity of H2O adsorbed by clays, and the distribution of H2O in relation to pore character) to water, clays were exposed for various periods to a specific humidity (e.g., relative humidity: RH=100%, RH=75%). The humidity is controlled by using saturated aqueous solutions, consisting of specific H2O/D2O mixtures. Our results have shown distinct variations in water adsorption and moisture diffusivity among clays. Our results allow us to obtain on the pore scale porosity changes due to water movement in clays. As emergent transport property, nano- to micro-scale structural characterization is crucial in providing insights into pore-scale transport processes, which are pertinent to upscale continuum model development involving flow and transport at low water content, flow and phase behavior under confinement, and low-permeability media.
Tarlochan, Faris; Mehboob, Hassan; Mehboob, Ali; Chang, Seung-Hwan
2018-06-01
Cementless hip prostheses with porous outer coating are commonly used to repair the proximally damaged femurs. It has been demonstrated that stability of prosthesis is also highly dependent on the bone ingrowth into the porous texture. Bone ingrowth is influenced by the mechanical environment produced in the callus. In this study, bone ingrowth into the porous structure was predicted by using a mechano-regulatory model. Homogenously distributed pores (200 and 800 [Formula: see text]m in diameter) and functionally graded pores along the length of the prosthesis were introduced as a porous coating. Bone ingrowth was simulated using 25 and 12 [Formula: see text]m micromovements. Load control simulations were carried out instead of traditionally used displacement control. Spatial and temporal distributions of tissues were predicted in all cases. Functionally graded pore decreasing models gave the most homogenous bone distribution, the highest bone ingrowth (98%) with highest average Young's modulus of all tissue phenotypes approximately 4.1 GPa. Besides this, the volume of the initial callus increased to 8.33% in functionally graded pores as compared to the 200 [Formula: see text]m pore size models which increased the bone volume. These findings indicate that functionally graded porous surface promote bone ingrowth efficiently which can be considered to design of surface texture of hip prosthesis.
Nguyen, Trang T; Miller, Arthur; Orellana, Maria F
2011-07-01
(1) To quantitatively characterize human enamel porosity and surface area in vitro before and after etching for variable etching times; and (2) to evaluate shear bond strength after variable etching times. Specifically, our goal was to identify the presence of any correlation between enamel porosity and shear bond strength. Pore surface area, pore volume, and pore size of enamel from extracted human teeth were analyzed by Brunauer-Emmett-Teller (BET) gas adsorption before and after etching for 15, 30, and 60 seconds with 37% phosphoric acid. Orthodontic brackets were bonded with Transbond to the samples with variable etch times and were subsequently applied to a single-plane lap shear testing system. Pore volume and surface area increased after etching for 15 and 30 seconds. At 60 seconds, this increase was less pronounced. On the contrary, pore size appears to decrease after etching. No correlation was found between variable etching times and shear strength. Samples etched for 15, 30, and 60 seconds all demonstrated clinically viable shear strength values. The BET adsorption method could be a valuable tool in enhancing our understanding of enamel characteristics. Our findings indicate that distinct quantitative changes in enamel pore architecture are evident after etching. Further testing with a larger sample size would have to be carried out for more definitive conclusions to be made.
Heterogeneous porous structures for the fastest liquid absorption
NASA Astrophysics Data System (ADS)
Shou, Dahua; Ye, Lin; Fan, Jintu
2013-08-01
Engineered porous materials, which have fast absorption of liquids under global constraints (e.g. volume, surface area, or cost of the materials), are useful in many applications including moisture management fabrics, medical wound dressings, paper-based analytical devices, liquid molding composites, etc.. The absorption in capillary tubes and porous media is driven by the surface tension of liquid, which is inversely proportional to the pore size. On the contrary, the ability of conduction (or permeability) of liquid in porous materials is linear with the square of pore size. Both mechanisms superimpose with each other leading to a possibility of the fastest absorption for a porous structure. In this work, we explore the flow behaviors for the fastest absorption using heterogeneous porous architectures, from two-portion tubes to two-layer porous media. The absorption time for filling up the voids in these porous materials is expressed in terms of pore size, height and porosity. It is shown that under the given height and void volume, these two-component porous structures with a negative gradient of pore size/porosity against the imbibition direction, have a faster absorption rate than controlled samples with uniform pore size/porosity. Particularly, optimal structural parameters including pore size, height and porosity are found for the minimum absorption time. The obtained results will be used as a priori for the design of porous structures with excellent water absorption and moisture management property in various fields.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Babarao, Ravichandar; Dai, Sheng; Jiang, Deen
2011-01-01
When all cages are assumed to be accessible, popular force fields such as universal force field (UFF) and DREIDING dramatically overpredicted gas adsorption capacity in two widely studied zeolitic-imidazolate frameworks (ZIFs), ZIF-68 and -69. Instead of adjusting the force-field parameters to match the experiments, herein we show that when the pore topology and accessibility are correctly taken into account, simulations with the standard force fields agree very well with the experiments. Careful inspection shows that ZIF-68 and -69 have two one-dimensional channels, which are not interaccessible to gases. The small channel consists of alternating small (HPR) and medium (GME) cages,more » while the large channel comprises the large (KNO) cages. Our analysis indicates that the small channel is not accessible to gases such as CO{sub 2}. So when the cages in the small channel are intentionally blocked in our simulation, the predicted adsorption capacities of CO{sub 2}, CH{sub 4} and N{sub 2} at room temperature from standard force-field parameters for the framework show excellent agreement with the experimental results. In the case of H{sub 2}, all cages are accessible, so simulation results without cage-blocking show excellent agreement with experiment. Due to the promising potential of ZIFs in gas storage and separation, our work here shows that pore topology and accessibility should be carefully examined to understand how gases adsorb in ZIFs.« less
Pore size engineering applied to the design of separators for nickel-hydrogen cells and batteries
NASA Technical Reports Server (NTRS)
Abbey, K. M.; Britton, D. L.
1983-01-01
Pore size engineering in starved alkaline multiplate cells involves adopting techniques to widen the volume tolerance of individual cells. Separators with appropriate pore size distributions and wettability characteristics (capillary pressure considerations) to have wider volume tolerances and an ability to resist dimensional changes in the electrodes were designed. The separators studied for potential use in nickel-hydrogen cells consist of polymeric membranes as well as inorganic microporous mats. In addition to standard measurements, the resistance and distribution of electrolyte as a function of total cell electrolyte content were determined. New composite separators consisting of fibers, particles and/or binders deposited on Zircar cloth were developed in order to engineer the proper capillary pressure characteristics in the separator. These asymmetric separators were prepared from a variety of fibers, particles and binders.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Tammas-Williams, S., E-mail: Samuel.tammas-wiliams@manchester.ac.uk; Department of Materials Science and Engineering, University of Sheffield, Sheffield S1 3JD; Zhao, H.
Selective Electron Beam Melting (SEBM) is a promising powder bed Additive Manufacturing technique for near-net-shape manufacture of high-value titanium components. However without post-manufacture HIPing the fatigue life of SEBM parts is currently dominated by the presence of porosity. In this study, the size, volume fraction, and spatial distribution of the pores in model samples have been characterised in 3D, using X-ray Computed Tomography, and correlated to the process variables. The average volume fraction of the pores (< 0.2%) was measured to be lower than that usually observed in competing processes, such as selective laser melting, but a strong relationship wasmore » found with the different beam strategies used to contour, and infill by hatching, a part section. The majority of pores were found to be small spherical gas pores, concentrated in the infill hatched region; this was attributed to the lower energy density and less focused beam used in the infill strategy allowing less opportunity for gas bubbles to escape the melt pool. Overall, increasing the energy density or focus of the beam was found to correlate strongly to a reduction in the level of gas porosity. Rarer irregular shaped pores were mostly located in the contour region and have been attributed to a lack of fusion between powder particles. - Graphical abstract: Display Omitted - Highlights: • Vast majority of defects detected were small spherical gas pores. • Gas bubbles trapped in the powder granules expand and coalesce in the melt pool. • Pores have been shown not to be randomly distributed. • Larger and deeper melt pools give more opportunity for gas to escape. • Minor changes to melt strategy result in significant reductions in pore population.« less
NASA Astrophysics Data System (ADS)
Zhou, BeiBei; Wang, QuanJiu
2017-09-01
Studies on solute transport under different pore water velocity and solute input methods in undisturbed soil could play instructive roles for crop production. Based on the experiments in the laboratory, the effect of solute input methods with small pulse input and large pulse input, as well as four pore water velocities, on chloride transport in the undisturbed soil columns obtained from the Loess Plateau under controlled condition was studied. Chloride breakthrough curves (BTCs) were generated using the miscible displacement method under water-saturated, steady flow conditions. Using the 0.15 mol L-1 CaCl2 solution as a tracer, a small pulse (0.1 pore volumes) was first induced, and then, after all the solution was wash off, a large pulse (0.5 pore volumes) was conducted. The convection-dispersion equation (CDE) and the two-region model (T-R) were used to describe the BTCs, and their prediction accuracies and fitted parameters were compared as well. All the BTCs obtained for the different input methods and the four pore water velocities were all smooth. However, the shapes of the BTCs varied greatly; small pulse inputs resulted in more rapid attainment of peak values that appeared earlier with increases in pore water velocity, whereas large pulse inputs resulted in an opposite trend. Both models could fit the experimental data well, but the prediction accuracy of the T-R was better. The values of the dispersivity, λ, calculated from the dispersion coefficient obtained from the CDE were about one order of magnitude larger than those calculated from the dispersion coefficient given by the T-R, but the calculated Peclet number, Pe, was lower. The mobile-immobile partition coefficient, β, decreased, while the mass exchange coefficient increased with increases in pore water velocity.
Predicting Impact of Biochar Addition on Soil Hydraulic Properties
NASA Astrophysics Data System (ADS)
Nakhli, S. A. A.; Yudi, Y.; Imhoff, P. T.
2017-12-01
Biochar has been proposed as a soil amendment to improve soil hydraulic properties, including water retention and saturated and unsaturated hydraulic conductivity, for agricultural and environmental applications. However, its effect on hydraulic properties is difficult to predict and often with mixed results: in some cases biochar enhances soil hydraulic properties, while in other cases it degrades them. Despite several published observational studies, there are no models that can reliably predict biochar's impact on soil hydraulic properties. In this project we developed models to describe the effect of addition of a commercial wood biochar pyrolyzed at 550° on soil hydraulic properties in laboratory-scale experiments. The effects of biochar addition at 2% and 6% (w/w) on water retention and saturated and unsaturated hydraulic conductivity were evaluated for silt loam, sandy loam, and loamy sand. The addition of 6% (w/w) biochar increased the available water content of silt loam, sandy loam and loamy sand by 25, 20 and 70%, respectively. The impact of biochar addition on water retention was predicted reasonably well using information on the intra particle pore volume of biochar (mercury porosimetry, N2 and CO2 sorption) and the particle size distribution of the soil/biochar mixture. When amended with 6% biochar, saturated hydraulic conductivity increased 17% for loamy sand, but decreased 30% and 54% for silt loam and sandy loam, respectively. The Kozeny-Carman equation modified to account for changes in inter pore volume predicted saturated hydraulic conductivities of the biochar-amended soils reasonably well, with RMSE ranging from 0.06 to 5.06 cm h-1 for silt loam and loamy sand, respectively. While intra particle pore volume of biochar contributed significantly to higher water retention, changes in hydraulic conductivity were correlated instead with changes in inter pore volume - the large pores between biochar and soil particles.
Tomographic analysis of reactive flow induced pore structure changes in column experiments
NASA Astrophysics Data System (ADS)
Cai, Rong; Lindquist, W. Brent; Um, Wooyong; Jones, Keith W.
2009-09-01
We utilize synchrotron X-ray computed micro-tomography to capture and quantify snapshots in time of dissolution and secondary precipitation in the microstructure of Hanford sediments exposed to simulated caustic waste in flow-column experiments. The experiment is complicated somewhat as logistics dictated that the column spent significant amounts of time in a sealed state (acting as a batch reactor). Changes accompanying a net reduction in porosity of 4% were quantified including: (1) a 25% net decrease in pores resulting from a 38% loss in the number of pores <10-4mm in volume and a 13% increase in the number of pores of larger size; and (2) a 38% decrease in the number of throats. The loss of throats resulted in decreased coordination number for pores of all sizes and significant reduction in the number of pore pathways.
Characterization of natural organic matter adsorption in granular activated carbon adsorbers.
Velten, Silvana; Knappe, Detlef R U; Traber, Jacqueline; Kaiser, Hans-Peter; von Gunten, Urs; Boller, Markus; Meylan, Sébastien
2011-07-01
The removal of natural organic matter (NOM) from lake water was studied in two pilot-scale adsorbers containing granular activated carbon (GAC) with different physical properties. To study the adsorption behavior of individual NOM fractions as a function of time and adsorber depth, NOM was fractionated by size exclusion chromatography (SEC) into biopolymers, humics, building blocks, and low molecular weight (LMW) organics, and NOM fractions were quantified by both ultraviolet and organic carbon detectors. High molecular weight biopolymers were not retained in the two adsorbers. In contrast, humic substances, building blocks and LMW organics were initially well and irreversibly removed, and their effluent concentrations increased gradually in the outlet of the adsorbers until a pseudo-steady state concentration was reached. Poor removal of biopolymers was likely a result of their comparatively large size that prevented access to the internal pore structure of the GACs. In both GAC adsorbers, adsorbability of the remaining NOM fractions, compared on the basis of partition coefficients, increased with decreasing molecular size, suggesting that increasingly larger portions of the internal GAC surface area could be accessed as the size of NOM decreased. Overall DOC uptake at pseudo-steady state differed between the two tested GACs (18.9 and 28.6 g-C/kg GAC), and the percent difference in DOC uptake closely matched the percent difference in the volume of pores with widths in the 1-50 nm range that was measured for the two fresh GACs. Despite the differences in NOM uptake capacity, individual NOM fractions were removed in similar proportions by the two GACs. Copyright © 2011 Elsevier Ltd. All rights reserved.
Multiple Approaches to Characterizing Nano-Pore Structure of Barnett Shale
NASA Astrophysics Data System (ADS)
Hu, Q.; Gao, Z.; Ewing, R. P.; Dultz, S.; Kaufmann, J.; Hamamoto, S.; Webber, B.; Ding, M.
2013-12-01
Microscopic characteristics of porous media - pore shape, pore-size distribution, and pore connectivity - control fluid flow and mass transport. This presentation discusses various approaches to investigating nano-pore structure of Barnett shale, with its implications in gas production behavior. The innovative approaches include imbibition, tracer diffusion, edge-accessible porosity, porosimetry (mercury intrusion porosimetry, nitrogen and water vapor sorption isotherms, and nuclear magnetic resonance cyroporometry), and imaging (Wood's metal impregnation followed with laser ablation-inductively coupled plasma-mass spectrometry, focused ion beam/scanning electron microscopy, and small angle neutron scattering). Results show that the shale pores are predominantly in the nm size range, with measured median pore-throat diameters about 5 nm. But small pore size is not the major contributor to low gas recovery; rather, the low mass diffusivity appears to be caused by low pore connectivity of Barnett shale. Chemical diffusion in sparsely-connected pore spaces is not well described by classical Fickian behavior; anomalous behavior is suggested by percolation theory, and confirmed by results of imbibition and diffusion tests. Our evolving complementary approaches, with their several advantages and disadvantages, provide a rich toolbox for tackling the nano-pore structure characteristics of shales and other natural rocks.
Li, Yin; Fu, Jie; Deng, Shuguang; Lu, Xiuyang
2014-06-15
Sixteen mesoporous carbon adsorbents were synthesized by varying the ratio of soft to hard templates in order to optimize the pore textural properties of these adsorbents. The mesoporous carbon adsorbents have a high BET specific surface area (1590.3-2193.5 m(2)/g), large pore volume (1.72-2.56 cm(3)/g), and uniform pore size distribution with a median pore diameter ranging from 3.51 nm to 4.52 nm. It was observed that pore textural properties of the carbon adsorbents critically depend on the molar ratio of carbon sources to templates, and the hard template plays a more important role than the soft template in manipulating the pore textures. Adsorption isotherms of berberine hydrochloride at 303 K were measured to evaluate the adsorption efficacy of these adsorbents. The adsorption of berberine hydrochloride from aqueous solutions on the sixteen mesoporous carbon adsorbents synthesized in this work is very efficient, and the adsorption equilibrium capacities on all samples are more than double the adsorption capacities of berberine hydrochloride of the benchmark adsorbents (polymer resins and spherical activated carbons) at similar conditions. It was observed from the adsorption experiments that the equilibrium adsorption amounts of berberine hydrochloride are strongly correlated with the BET specific surface area and pore volume of the adsorbents. The adsorbent with the highest BET of 2193.5 m(2)/g displayed the largest adsorption capacity of 574 mg/g at an equilibrium concentration of 0.10mg/mL of berberine hydrochloride in an aqueous solution. Copyright © 2014 Elsevier Inc. All rights reserved.
Multiscale pore structure and constitutive models of fine-grained rocks
NASA Astrophysics Data System (ADS)
Heath, J. E.; Dewers, T. A.; Shields, E. A.; Yoon, H.; Milliken, K. L.
2017-12-01
A foundational concept of continuum poromechanics is the representative elementary volume or REV: an amount of material large enough that pore- or grain-scale fluctuations in relevant properties are dissipated to a definable mean, but smaller than length scales of heterogeneity. We determine 2D-equivalent representative elementary areas (REAs) of pore areal fraction of three major types of mudrocks by applying multi-beam scanning electron microscopy (mSEM) to obtain terapixel image mosaics. Image analysis obtains pore areal fraction and pore size and shape as a function of progressively larger measurement areas. Using backscattering imaging and mSEM data, pores are identified by the components within which they occur, such as in organics or the clastic matrix. We correlate pore areal fraction with nano-indentation, micropillar compression, and axysimmetic testing at multiple length scales on a terrigenous-argillaceous mudrock sample. The combined data set is used to: investigate representative elementary volumes (and areas for the 2D images); determine if scale separation occurs; and determine if transport and mechanical properties at a given length scale can be statistically defined. Clear scale separation occurs between REAs and observable heterogeneity in two of the samples. A highly-laminated sample exhibits fine-scale heterogeneity and an overlapping in scales, in which case typical continuum assumptions on statistical variability may break down. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology and Engineering Solutions of Sandia LLC, a wholly owned subsidiary of Honeywell International Inc. for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-NA0003525.
Jiang, Tao; Abdel-Fattah, Wafa I; Laurencin, Cato T
2006-10-01
A three-dimensional (3-D) scaffold is one of the major components in many tissue engineering approaches. We developed novel 3-D chitosan/poly(lactic acid-glycolic acid) (PLAGA) composite porous scaffolds by sintering together composite chitosan/PLAGA microspheres for bone tissue engineering applications. Pore sizes, pore volume, and mechanical properties of the scaffolds can be manipulated by controlling fabrication parameters, including sintering temperature and sintering time. The sintered microsphere scaffolds had a total pore volume between 28% and 37% with median pore size in the range 170-200microm. The compressive modulus and compressive strength of the scaffolds are in the range of trabecular bone making them suitable as scaffolds for load-bearing bone tissue engineering. In addition, MC3T3-E1 osteoblast-like cells proliferated well on the composite scaffolds as compared to PLAGA scaffolds. It was also shown that the presence of chitosan on microsphere surfaces increased the alkaline phosphatase activity of the cells cultured on the composite scaffolds and up-regulated gene expression of alkaline phosphatase, osteopontin, and bone sialoprotein.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhang, Wei-Min, E-mail: chm_zhangwm@ujn.edu.cn; Jiang, Yao-Quan; Cao, Xiao-Yan
2013-10-15
Graphical abstract: - Highlights: • Self-templated synthesis of tubular CdS. • Cadmium complexes of aliphatic acids sustain the network of mesoporous structures. • Aliphatic acids affect the phase composition and particle size. • Pore size and volume vary with aliphatic acids having different hydrocarbonyl. - Abstract: In this study, mesoporous CdS polycrystallites have been synthesized using aliphatic acids of hexanoic acid, octanoic acid, and oleic acid as coordinating and capping agents, respectively. The fibrous Cd–fatty acid salts act as a template to form the tubular CdS. The organic species are found to be necessary for maintaining the network of mesoporousmore » CdS. The characterization results indicate that the shorter carbon chain length in aliphatic acids favors the wurtzite phase and particle size growth the specific surface area, pore diameter and pore volume show a monotonic raise with increasing carbon chain. The photocatalytic activities of mesoporous CdS tubes exhibit much higher efficiency than those of nanosized CdS powders in decolorizing methylene blue under simulated visible light.« less
Seuba, Jordi; Deville, Sylvain; Guizard, Christian; Stevenson, Adam J
2016-01-01
Macroporous ceramics exhibit an intrinsic strength variability caused by the random distribution of defects in their structure. However, the precise role of microstructural features, other than pore volume, on reliability is still unknown. Here, we analyze the applicability of the Weibull analysis to unidirectional macroporous yttria-stabilized-zirconia (YSZ) prepared by ice-templating. First, we performed crush tests on samples with controlled microstructural features with the loading direction parallel to the porosity. The compressive strength data were fitted using two different fitting techniques, ordinary least squares and Bayesian Markov Chain Monte Carlo, to evaluate whether Weibull statistics are an adequate descriptor of the strength distribution. The statistical descriptors indicated that the strength data are well described by the Weibull statistical approach, for both fitting methods used. Furthermore, we assess the effect of different microstructural features (volume, size, densification of the walls, and morphology) on Weibull modulus and strength. We found that the key microstructural parameter controlling reliability is wall thickness. In contrast, pore volume is the main parameter controlling the strength. The highest Weibull modulus ([Formula: see text]) and mean strength (198.2 MPa) were obtained for the samples with the smallest and narrowest wall thickness distribution (3.1 [Formula: see text]m) and lower pore volume (54.5%).
NASA Astrophysics Data System (ADS)
Seuba, Jordi; Deville, Sylvain; Guizard, Christian; Stevenson, Adam J.
2016-01-01
Macroporous ceramics exhibit an intrinsic strength variability caused by the random distribution of defects in their structure. However, the precise role of microstructural features, other than pore volume, on reliability is still unknown. Here, we analyze the applicability of the Weibull analysis to unidirectional macroporous yttria-stabilized-zirconia (YSZ) prepared by ice-templating. First, we performed crush tests on samples with controlled microstructural features with the loading direction parallel to the porosity. The compressive strength data were fitted using two different fitting techniques, ordinary least squares and Bayesian Markov Chain Monte Carlo, to evaluate whether Weibull statistics are an adequate descriptor of the strength distribution. The statistical descriptors indicated that the strength data are well described by the Weibull statistical approach, for both fitting methods used. Furthermore, we assess the effect of different microstructural features (volume, size, densification of the walls, and morphology) on Weibull modulus and strength. We found that the key microstructural parameter controlling reliability is wall thickness. In contrast, pore volume is the main parameter controlling the strength. The highest Weibull modulus (?) and mean strength (198.2 MPa) were obtained for the samples with the smallest and narrowest wall thickness distribution (3.1 ?m) and lower pore volume (54.5%).
NASA Astrophysics Data System (ADS)
Wigger, Cornelia; Van Loon, Luc R.
2018-06-01
The effect of the pore water composition on the diffusive anion transport was studied for two different argillaceous, low permeability sedimentary rocks, Opalinus Clay (OPA) and Helvetic Marl (HM). The samples were saturated with different solutions with varying molar concentration and different main cations in the solution: NaCl based pore solutions and CaCl2 based pore solutions. The total porosity was measured by through-diffusion experiments with the neutral tracer HTO. Experiments performed in NaCl solutions resulted in a porosity of 0.12 for OPA and 0.03 for HM, and are consistent with results of the experiments in CaCl2 solutions. The total porosity was independent of the molar concentration, in contrast to the measured anion porosity, which increased with increasing molar concentration. It could further be observed that the pore solution based on the bivalent cation calcium shielded the negative surface charge stronger than the monovalent cation sodium, resulting in a larger measureable anion-accessible porosity in the case of CaCl2 solutions. The data was modelled based on an adapted Donnan approach of Birgersson and Karnland (2009). The model had to be adjusted with a permanent free, uncharged porosity, as well as with structural information on the permanent anion exclusion because of so-called bottleneck pores. Both parameters can only be evaluated from experiments. Nevertheless, taking these two adaptions into account, the effect of varying pore water compositions on the anion-accessible porosity of the investigated argillaceous rocks could be satisfactorily described.
Wigger, Cornelia; Van Loon, Luc R
2018-06-01
The effect of the pore water composition on the diffusive anion transport was studied for two different argillaceous, low permeability sedimentary rocks, Opalinus Clay (OPA) and Helvetic Marl (HM). The samples were saturated with different solutions with varying molar concentration and different main cations in the solution: NaCl based pore solutions and CaCl 2 based pore solutions. The total porosity was measured by through-diffusion experiments with the neutral tracer HTO. Experiments performed in NaCl solutions resulted in a porosity of 0.12 for OPA and 0.03 for HM, and are consistent with results of the experiments in CaCl 2 solutions. The total porosity was independent of the molar concentration, in contrast to the measured anion porosity, which increased with increasing molar concentration. It could further be observed that the pore solution based on the bivalent cation calcium shielded the negative surface charge stronger than the monovalent cation sodium, resulting in a larger measureable anion-accessible porosity in the case of CaCl 2 solutions. The data was modelled based on an adapted Donnan approach of Birgersson and Karnland (2009). The model had to be adjusted with a permanent free, uncharged porosity, as well as with structural information on the permanent anion exclusion because of so-called bottleneck pores. Both parameters can only be evaluated from experiments. Nevertheless, taking these two adaptions into account, the effect of varying pore water compositions on the anion-accessible porosity of the investigated argillaceous rocks could be satisfactorily described. Copyright © 2018 Elsevier B.V. All rights reserved.
Pore and grain boundary migration under a temperature gradient: A phase-field model study
Biner, S. B.
2016-03-16
In this study, the collective migration behavior of pores and grain boundaries under a temperature gradient is studied for simple single crystal, bi-crystal and polycrystal configurations with a phase-field model formulism. For simulation of the microstructure of solids, composed of pores and grain boundaries, the results indicate that not only the volume fraction of pores, but also its spatial partitioning between the grain boundary junctions and the grain boundary segments appears to be important. In addition to various physical properties, the evolution kinetics, under given temperature gradients, will be strongly influenced with the initial morphology of a poly-crystalline microstructure.
NASA Astrophysics Data System (ADS)
Xu, Hailing; Li, Xingwei; Wang, Gengchao
2015-10-01
Polyaniline (PANI) with a high specific surface area and an improved pore structure (HSSA-PANI) has been prepared by using a facile method, treating PANI nanofibers with chloroform (CHCl3), and its structure, morphology and pore structure are investigated. The specific surface area and pore volume of HSSA-PANI are 817.3 m2 g-1 and 0.6 cm3 g-1, and those of PANI are 33.6 m2 g-1 and 0.2 cm3 g-1. As electrode materials, a large specific surface area and pore volume can provide high electroactive regions, accelerate the diffusion of ions, and mitigate the electrochemical degradation of active materials. Compared with PANI, the capacity retention rate of HSSA-PANI is 90% with a growth of current density from 5.0 to 30 A g-1, and that of PANI is 29%. At a current density of 30 A g-1, the specific capacitance of HSSA-PANI still reaches 278.3 F g-1, and that of PANI is 86.7 F g-1. At a current density of 5.0 A g-1, the capacitance retention of HSSA-PANI is 53.1% after 2000 cycles, and that of PANI electrode is only 28.1%.
Mesoporous carbon spheres with controlled porosity for high-performance lithium-sulfur batteries
NASA Astrophysics Data System (ADS)
Wang, Dexian; Fu, Aiping; Li, Hongliang; Wang, Yiqian; Guo, Peizhi; Liu, Jingquan; Zhao, Xiu Song
2015-07-01
Mesoporous carbon (MC) spheres with hierarchical pores, controlled pore volume and high specific surface areas have been prepared by a mass-producible spray drying assisted template method using sodium alginate as carbon precursor and commercial colloidal silica particles as hard template. The resulting MC spheres, possessing hierarchical pores in the range of 3-30 nm, are employed as conductive matrices for the preparation of cathode materials for lithium-sulfur batteries. A high pressure induced one-step impregnation of elemental sulfur into the pore of the MC spheres has been exploited. The electrochemical performances of sulfur-impregnated MC spheres (S-MC) derived from MC spheres with different pore volume and specific surface area but with the same sulfur loading ratio of 60 wt% (S-MC-X-60) have been investigated in details. The S-MC-4-60 composite cathode material displayed a high initial discharge capacity of 1388 mAhg-1 and a good cycling stability of 857 mAhg-1 after 100 cycles at 0.2C, and shows also excellent rate capability of 864 mAhg-1 at 2C. More importantly, the sulfur loading content in MC-4 spheres can reach as high as 80%, and it still can deliver a capacity of 569 mAhg-1 after 100 cycles at 0.2C.
NASA Astrophysics Data System (ADS)
Nermoen, Anders; Korsnes, Reidar I.; Hiorth, Aksel; Madland, Merete V.
2015-05-01
We report the complete chemical alteration of a Liège outcrop chalk core resulting from a 1072 flow-through experiment performed during mechanical compaction at 130°C. Chemical rock-fluid interactions alter the volumetric strain, porosity, and permeability in a nontrivial way. The porosity reduced only from 41.32% to 40.14%, even though the plug compacted more than 25%. We present a novel analysis of the experimental data, which demonstrates that the geochemical alteration does not conserve the volume of the solids, and therefore, the strain is partitioned additively into a pore volume and solid volume component. At stresses beyond yield, the observed deformation can be explained by grain reorganization reducing the pore space between grains and solid volume changes from the rock-fluid interactions. The mechanical and chemical effects are discussed in relation to the observed permeability development.
Volume change measurements of rice by environmental scanning electron microscopy and stereoscopy.
Tang, Xiaohu; De Rooij, Mario; De Jong, Liesbeth
2007-01-01
The measurement of volume change, which is induced by changing the relative humidity, is performed on rice by using environmental scanning electron microscope (ESEM) and stereoscopy techniques. The typical DeltaV% approximately RH curve of rice in both sorption and desorption can be categorized into three regions: low, intermediate, and high dependence on relative humidity from low- to high-relative humidity. The volume changes faster for rice samples with lower crystallinity, which is because the amorphous component is easier to absorb moisture than the crystalline component. The volume change behavior in various relative humidity environments is comparable with rice isotherm curve in sorption process though discrepancies exist in desorption, which are thought to be the presence of small pores and microstructure changes at high relative humidity. The volume in the desorption branch is less than that in the sorption branch at the same relative humidity, which can be attributed to the collapse of interior structures, existence of small pores, surface topography loss, and amylose leach.
NASA Astrophysics Data System (ADS)
Yuan, Chao; Chareyre, Bruno; Darve, Félix
2016-09-01
A pore-scale model is introduced for two-phase flow in dense packings of polydisperse spheres. The model is developed as a component of a more general hydromechanical coupling framework based on the discrete element method, which will be elaborated in future papers and will apply to various processes of interest in soil science, in geomechanics and in oil and gas production. Here the emphasis is on the generation of a network of pores mapping the void space between spherical grains, and the definition of local criteria governing the primary drainage process. The pore space is decomposed by Regular Triangulation, from which a set of pores connected by throats are identified. A local entry capillary pressure is evaluated for each throat, based on the balance of capillary pressure and surface tension at equilibrium. The model reflects the possible entrapment of disconnected patches of the receding wetting phase. It is validated by a comparison with drainage experiments. In the last part of the paper, a series of simulations are reported to illustrate size and boundary effects, key questions when studying small samples made of spherical particles be it in simulations or experiments. Repeated tests on samples of different sizes give evolution of water content which are not only scattered but also strongly biased for small sample sizes. More than 20,000 spheres are needed to reduce the bias on saturation below 0.02. Additional statistics are generated by subsampling a large sample of 64,000 spheres. They suggest that the minimal sampling volume for evaluating saturation is one hundred times greater that the sampling volume needed for measuring porosity with the same accuracy. This requirement in terms of sample size induces a need for efficient computer codes. The method described herein has a low algorithmic complexity in order to satisfy this requirement. It will be well suited to further developments toward coupled flow-deformation problems in which evolution of the microstructure require frequent updates of the pore network.
Thermally-driven Coupled THM Processes in Shales
NASA Astrophysics Data System (ADS)
Rutqvist, J.
2017-12-01
Temperature changes can trigger strongly coupled thermal-hydrological-mechanical (THM) processes in shales that are important to a number of subsurface energy applications, including geologic nuclear waste disposal and hydrocarbon extraction. These coupled processes include (1) direct pore-volume couplings, by thermal expansion of trapped pore-fluid that triggers instantaneous two-way couplings between pore fluid pressure and mechanical deformation, and (2) indirect couplings in terms of property changes, such as changes in mechanical stiffness, strength, and permeability. Direct pore-volume couplings have been studied in situ during borehole heating experiments in shale (or clay stone) formations at Mont Terri and Bure underground research laboratories in Switzerland and France. Typically, the temperature changes are accompanied with a rapid increase in pore pressure followed by a slower decrease towards initial (pre-heating) pore pressure. Coupled THM modeling of these heater tests shows that the pore pressure increases because the thermal expansion coefficient of the fluid is much higher than that of the porous clay stone. Such thermal pressurization induces fluid flow away from the pressurized area towards areas of lower pressure. The rate of pressure increase and magnitude of peak pressure depends on the rate of heating, pore-compressibility, and permeability of the shale. Modeling as well as laboratory experiments have shown that if the pore pressure increase is sufficiently large it could lead to fracturing of the shale or shear slip along pre-existing bedding planes. Another set of data and observations have been collected associated with studies related to concentrated heating and cooling of oil-shales and shale-gas formations. Heating may be used to enhance production from tight oil-shale, whereas thermal stimulation has been attempted for enhanced shale-gas extraction. Laboratory experiments on shale have shown that strength and elastic deformation modulus decreases with temperature while the rate creep deformations increase with temperature. Such temperature dependency also affects the well stability and zonal sealing across shale layers.
Zieliński, Tomasz G
2015-04-01
This paper proposes and discusses an approach for the design and quality inspection of the morphology dedicated for sound absorbing foams, using a relatively simple technique for a random generation of periodic microstructures representative for open-cell foams with spherical pores. The design is controlled by a few parameters, namely, the total open porosity and the average pore size, as well as the standard deviation of pore size. These design parameters are set up exactly and independently, however, the setting of the standard deviation of pore sizes requires some number of pores in the representative volume element (RVE); this number is a procedure parameter. Another pore structure parameter which may be indirectly affected is the average size of windows linking the pores, however, it is in fact weakly controlled by the maximal pore-penetration factor, and moreover, it depends on the porosity and pore size. The proposed methodology for testing microstructure-designs of sound absorbing porous media applies the multi-scale modeling where some important transport parameters-responsible for sound propagation in a porous medium-are calculated from microstructure using the generated RVE, in order to estimate the sound velocity and absorption of such a designed material.
Pore size engineering applied to the design of separators for nickel-hydrogen cells and batteries
NASA Technical Reports Server (NTRS)
Abbey, K. M.; Britton, D. L.
1983-01-01
Pore size engineering in starved alkaline multiplate cells involves adopting techniques to widen the volume tolerance of individual cells. Separators with appropriate pore size distributions and wettability characteristics (capillary pressure considerations) to have wider volume tolerances and an ability to resist dimensional changes in the electrodes were designed. The separators studied for potential use in nickel-hydrogen cells consist of polymeric membranes as well as inorganic microporous mats. In addition to standard measurements, the resistance and distribution of electrolyte as a function of total cell electrolyte content were determined. New composite separators consisting of fibers, particles and/or binders deposited on Zircar cloth were developed in order to engineer the proper capillary pressure characteristics in the separator. These asymmetric separators were prepared from a variety of fibers, particles and binders. Previously announced in STAR as N83-24571
Catalyst comprising Ir or Ir and Ru for hydrazine decomposition
NASA Technical Reports Server (NTRS)
Armstrong, Warren E. (Inventor); Voge, Hervey H. (Inventor); Ryland, Lloyd B. (Inventor)
1978-01-01
A catalyst for hydrazine decomposition consisting essentially of a carrier having a pore volume of at least 0.1 cubic centimeters per gram and a specific surface area, measured in square meters per gram, equal to 195 (C.sub.p + 0.013 + 0.736 V.sub.p) where C.sub.p is the specific heat capacity of the carrier at about 25.degree. C in calories per gram per degree and V.sub.p is the pore volume of the carrier in cubic centimeters per gram and metal of the group consisting of iridium, and mixtures consisting of iridium and ruthenium deposited on said carrier in an amount between 20% and about 40% by weight of the catalyst and distributed through the pores thereof in discrete particles sufficiently separated from each other so that they do not sinter or fuse together when the catalyst is at hydrazine decomposition temperature.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Rao, Suraj; Cunningham, Ross; Ozturk, Tugce
Aluminum alloys are candidate materials for weight critical applications because of their excellent strength and stiffness to weight ratio. However, defects such as voids decrease the strength and fatigue life of these alloys, which can limit the application of Selective Laser Melting. In this study, the average volume fraction, average size, and size distribution of pores in Al10-Si-1Mg samples built using Selective Laser Melting have been characterized. Synchrotron high energy X-rays were used to perform computed tomography on volumes of order one cubic millimeter with a resolution of approximately 1.5 μm. Substantial variations in the pore size distributions were foundmore » as a function of process conditions. Even under conditions that ensured that all locations were melted at least once, a significant number density was found of pores above 5 μm in diameter.« less
NASA Astrophysics Data System (ADS)
Hu, R.; Wan, J.
2015-12-01
Wettability of reservoir minerals along pore surfaces plays a controlling role in capillary trapping of supercritical (sc) CO2 in geologic carbon sequestration. The mechanisms controlling scCO2 residual trapping are still not fully understood. We studied the effect of pore surface wettability on CO2 residual saturation at the pore-scale using engineered high pressure and high temperature micromodel (transparent pore networks) experiments and numerical modeling. Through chemical treatment of the micromodel pore surfaces, water-wet, intermediate-wet, and CO2-wet micromodels can be obtained. Both drainage and imbibition experiments were conducted at 8.5 MPa and 45 °C with controlled flow rate. Dynamic images of fluid-fluid displacement processes were recorded using a microscope with a CCD camera. Residual saturations were determined by analysis of late stage imbibition images of flow path structures. We performed direct numerical simulations of the full Navier-Stokes equations using a volume-of-fluid based finite-volume framework for the primary drainage and the followed imbibition for the micromodel experiments with different contact angles. The numerical simulations agreed well with our experimental observations. We found that more scCO2 can be trapped within the CO2-wet micromodel whereas lower residual scCO2 saturation occurred within the water-wet micromodels in both our experiments and the numerical simulations. These results provide direct and consistent evidence of the effect of wettability, and have important implications for scCO2 trapping in geologic carbon sequestration.
Yang, Xi; Yi, Honghong; Tang, Xiaolong; Zhao, Shunzheng; Yang, Zhongyu; Ma, Yueqiang; Feng, Tiecheng; Cui, Xiaoxu
2018-05-01
This work was undertaken to investigate the behaviors and kinetics of toluene adsorption and desorption on activated carbons with varying pore structure. Five kinds of activated carbon from different raw materials were selected. Adsorption isotherms and breakthrough curves for toluene were measured. Langmuir and Freundlich equations were fitted to the equilibrium data, and the Freundlich equation was more suitable for simulating toluene adsorption. The process consisted of monolayer, multilayer and partial active site adsorption types. The effect of the pore structure of the activated carbons on toluene adsorption capacity was investigated. The quasi-first-order model was more suitable for describing the process than the quasi-second-order model. The adsorption data was also modeled by the internal particle diffusion model and it was found that the adsorption process could be divided into three stages. In the external surface adsorption process, the rate depended on the specific surface area. During the particle diffusion stage, pore structure and volume were the main factors affecting adsorption rate. In the final equilibrium stage, the rate was determined by the ratio of meso- and macro-pores to total pore volume. The rate over the whole adsorption process was dominated by the toluene concentration. The desorption behavior of toluene on activated carbons was investigated, and the process was divided into heat and mass transfer parts corresponding to emission and diffusion mechanisms, respectively. Physical adsorption played the main role during the adsorption process. Copyright © 2017. Published by Elsevier B.V.
Liu, Xiaofeng S; Patterson, Leslie D; Miller, Marvin J; Theil, Elizabeth C
2007-11-02
Pores regulate access between ferric-oxy biomineral inside and reductants/chelators outside the ferritin protein nanocage to control iron demineralization rates. The pore helix/loop/helix motifs that are contributed by three subunits unfold independently of the protein cage, as observed by crystallography, Fe removal rates, and CD spectroscopy. Pore unfolding is induced in wild type ferritin by increased temperature or urea (1-10 mM), a physiological urea range, 0.1 mM guanidine, or mutation of conserved pore amino acids. A peptide selected for ferritin pore binding from a combinatorial, heptapeptide library increased the rate of Fe demineralization 3-fold (p<0.001), similarly to a mutation that unfolded the pores. Conjugating the peptide to Desferal (desferrioxamine B mesylate), a chelator in therapeutic use, increased the rates to 8-fold (p<0.001). A second pore binding peptide had the opposite effect and decreased the rate of Fe demineralization 60% (p<0.001). The peptides could have pharmacological uses and may model regulators of ferritin demineralization rates in vivo or peptide regulators of gated pores in membranes. The results emphasize that small peptides can exploit the structural plasticity of protein pores to modulate function.
NASA Astrophysics Data System (ADS)
Fu, An; Palakurthi, Nikhil; Konangi, Santosh; Comer, Ken; Jog, Milind
2017-11-01
The physics of capillary flow is used widely in multiple fields. Lucas-Washburn equation is developed by using a single pore-sized capillary tube with continuous pore connection. Although this equation has been extended to describe the penetration kinetics into porous medium, multiple studies have indicated L-W does not accurately predict flow patterns in real porous media. In this study, the penetration kinetics including the effect of pore size and pore connectivity will be closely examined since they are expected to be the key factors effecting the penetration process. The Liquid wicking process is studied from a converging and diverging capillary tube to the complex virtual 3-D porous structures with Direct Numerical Simulation (DNS) using the Volume-Of-Fluid (VOF) method within the OpenFOAM CFD Solver. Additionally Porous Medium properties such as Permeability (k) , Tortuosity (τ) will be also analyzed.
Measurements of pore-scale flow through apertures
DOE Office of Scientific and Technical Information (OSTI.GOV)
Chojnicki, Kirsten
Pore-scale aperture effects on flow in pore networks was studied in the laboratory to provide a parameterization for use in transport models. Four cases were considered: regular and irregular pillar/pore alignment with and without an aperture. The velocity field of each case was measured and simulated, providing quantitatively comparable results. Two aperture effect parameterizations were considered: permeability and transmission. Permeability values varied by an order of magnitude between the cases with and without apertures. However, transmission did not correlate with permeability. Despite having much greater permeability the regular aperture case permitted less transmission than the regular case. Moreover, both irregularmore » cases had greater transmission than the regular cases, a difference not supported by the permeabilities. Overall, these findings suggest that pore-scale aperture effects on flow though a pore-network may not be adequately captured by properties such as permeability for applications that are interested in determining particle transport volume and timing.« less
Metal-organic frameworks for Xe/Kr separation
Ryan, Patrick J.; Farha, Omar K.; Broadbelt, Linda J.; Snurr, Randall Q.; Bae, Youn-Sang
2014-07-22
Metal-organic framework (MOF) materials are provided and are selectively adsorbent to xenon (Xe) over another noble gas such as krypton (Kr) and/or argon (Ar) as a result of having framework voids (pores) sized to this end. MOF materials having pores that are capable of accommodating a Xe atom but have a small enough pore size to receive no more than one Xe atom are desired to preferentially adsorb Xe over Kr in a multi-component (Xe--Kr mixture) adsorption method. The MOF material has 20% or more, preferably 40% or more, of the total pore volume in a pore size range of 0.45-0.75 nm which can selectively adsorb Xe over Kr in a multi-component Xe--Kr mixture over a pressure range of 0.01 to 1.0 MPa.
Metal-organic frameworks for Xe/Kr separation
Ryan, Patrick J.; Farha, Omar K.; Broadbelt, Linda J.; Snurr, Randall Q.; Bae, Youn-Sang
2013-08-27
Metal-organic framework (MOF) materials are provided and are selectively adsorbent to xenon (Xe) over another noble gas such as krypton (Kr) and/or argon (Ar) as a result of having framework voids (pores) sized to this end. MOF materials having pores that are capable of accommodating a Xe atom but have a small enough pore size to receive no more than one Xe atom are desired to preferentially adsorb Xe over Kr in a multi-component (Xe--Kr mixture) adsorption method. The MOF material has 20% or more, preferably 40% or more, of the total pore volume in a pore size range of 0.45-0.75 nm which can selectively adsorb Xe over Kr in a multi-component Xe--Kr mixture over a pressure range of 0.01 to 1.0 MPa.
Mesoporous Akaganeite of Adjustable Pore Size Synthesized using Mixed Templates
NASA Astrophysics Data System (ADS)
Zhang, Y.; Ge, D. L.; Ren, H. P.; Fan, Y. J.; Wu, L. M.; Sun, Z. X.
2017-12-01
Mesoporous akaganeite with large and adjustable pore size was synthesized through a co-template method, which was achieved by the combined interaction between PEG2000 and alkyl amines with different lengths of the straight carbon chain. The characterized results indicate that the synthesized samples show comparatively narrow BJH pore size distributions and centered at 14.3 nm when PEG and HEPA was used, and it could be enlarged to 16.8 and 19.4 nm respectively through changing the alkyl amines to DDA and HDA. Meanwhile, all the synthesized akaganeite possess relativity high specific surface area ranging from 183 to 281 m2/g and high total pore volume of 0.98 to 1.5 cm3/g. A possible mechanism leading to the pore size changing was also proposed.
NASA Technical Reports Server (NTRS)
Chao, Luen-Yuan; Shetty, Dinesh K.
1992-01-01
Statistical analysis and correlation between pore-size distribution and fracture strength distribution using the theory of extreme-value statistics is presented for a sintered silicon nitride. The pore-size distribution on a polished surface of this material was characterized, using an automatic optical image analyzer. The distribution measured on the two-dimensional plane surface was transformed to a population (volume) distribution, using the Schwartz-Saltykov diameter method. The population pore-size distribution and the distribution of the pore size at the fracture origin were correllated by extreme-value statistics. Fracture strength distribution was then predicted from the extreme-value pore-size distribution, usin a linear elastic fracture mechanics model of annular crack around pore and the fracture toughness of the ceramic. The predicted strength distribution was in good agreement with strength measurements in bending. In particular, the extreme-value statistics analysis explained the nonlinear trend in the linearized Weibull plot of measured strengths without postulating a lower-bound strength.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Dieter Leckel
2008-01-15
The effect of the pore structure on the hydroprocessing of heavy distillate oils derived from low-temperature coal gasification residues was studied using four NiW catalysts with different pore size distributions. The hydroprocessing was conducted at a pressure of 17.5 MPa, a temperature range of 370-410{sup o}C, and a 0.50 h{sup -1} space velocity. The degree of hydrodeoxygenation (HDO) in terms of phenolics removal was influenced by the catalyst pore structure, with the most preferable peak pore diameter for HDO ranging between 6.8 and 16 nm. The catalyst with the highest volume of pores in the 3.5-6 nm range showed themore » lowest HDO activity. The apparent activation energies for the HDO reaction varied between 59 and 87 kJ/mol, whereby the lowest values are obtained for the catalysts with a peak pore diameter of 11 and 16 nm. 30 refs., 5 figs., 6 tabs.« less
A vacuum-operated pore-water extractor for estuarine and freshwater sediments
Winger, Parley V.; Lasier, Peter J.
1991-01-01
A vacuum-operated pore-water extractor for estuarine and freshwater sediments was developed and constructed from a fused-glass air stone attached with aquarium airline tubing to a 30 or 60 cc polypropylene syringe. Pore water is extracted by inserting the air stone into the sediment and creating a vacuum by retracting and bracing the syringe plunger. A hand-operated vacuum pump attached to a filtration flask was also evaluated as an alternative vacuum source. The volume and time to extract pore water varies with the number of devices and the sediment particle size. Extraction time is longer for fine sediments than for sandy sediments. Four liters of sediment generally yield between 500 and 1,500 mL of pore water. The sediment that surrounds and accumulates on the air stone acts as a filter, and, except for the first few milliliters, the collected pore water is clear. Because there is no exposure to air or avenue for escape, volatile compounds andin situ characteristics are retained in the extracted pore water.
NASA Astrophysics Data System (ADS)
Fotopoulou, Kalliopi N.; Karapanagioti, Hrissi K.; Manariotis, Ioannis D.
2015-04-01
Various organic-rich wastes including wood chips, animal manure, and crop residues have been used for biochar production. Biochar is used as an additive to soils to sequester carbon and improve soil fertility but its use as a sorbent for environmental remediation processes is gaining increased attention. Surface properties such as point of zero charge, surface area and pore volume, surface topography, surface functional groups and acid-base behavior are important factors, which affect sorption efficiency. Understanding the surface alteration of biochars increases our understanding of the pollutant-sorbent interaction. The scope of the present work was to evaluate the effect of key characteristics of biochars on their sorptive properties. Raw materials for biochar production were evaluated including byproducts from brewering, coffee, wine, and olive oil industry. The charring process was performed at different temperatures under limited-oxygen conditions using specialized containers. The surface area, the pore volume, and the average pore size of the biochars were determined. Open surface area and micropore volume were determined using t-plot method and Harkins & Jura equation. Raw food-processing waste demonstrates low surface area that increases by 1 order of magnitude by thermal treatment up to 750oC. At temperatures from 750 up to 900oC, pyrolysis results to biochars with surface areas 210-700 m2/g. For the same temperature range, a high percentage (46 to73%) of the pore volume of the biochars is due to micropores. Positive results were obtained when high surface area biochars were tested for their ability to remove organic (i.e. phenanthrene) and inorganic (i.e. mercury) compounds from aqueous solutions. All these properties point to new materials that can effectively be used for environmental remediation.
NASA Astrophysics Data System (ADS)
Cao, Zhe; Liu, Guangdi; Zhan, Hongbin; Li, Chaozheng; You, Yuan; Yang, Chengyu; Jiang, Hang
2016-11-01
Understanding the pore networks of unconventional tight reservoirs such as tight sandstones and shales is crucial for extracting oil/gas from such reservoirs. Mercury injection capillary pressure (MICP) and N2 gas adsorption (N2GA) are performed to evaluate pore structure of Chang-7 tight sandstone. Thin section observation, scanning electron microscope, grain size analysis, mineral composition analysis, and porosity measurement are applied to investigate geological control factors of pore structure. Grain size is positively correlated with detrital mineral content and grain size standard deviation while negatively related to clay content. Detrital mineral content and grain size are positively correlated with porosity, pore throat radius and withdrawal efficiency and negatively related to capillary pressure and pore-to-throat size ratio; while interstitial material is negatively correlated with above mentioned factors. Well sorted sediments with high debris usually possess strong compaction resistance to preserve original pores. Although many inter-crystalline pores are produced in clay minerals, this type of pores is not the most important contributor to porosity. Besides this, pore shape determined by N2GA hysteresis loop is consistent with SEM observation on clay inter-crystalline pores while BJH pore volume is positively related with clay content, suggesting N2GA is suitable for describing clay inter-crystalline pores in tight sandstones.
Cao, Zhe; Liu, Guangdi; Zhan, Hongbin; Li, Chaozheng; You, Yuan; Yang, Chengyu; Jiang, Hang
2016-01-01
Understanding the pore networks of unconventional tight reservoirs such as tight sandstones and shales is crucial for extracting oil/gas from such reservoirs. Mercury injection capillary pressure (MICP) and N2 gas adsorption (N2GA) are performed to evaluate pore structure of Chang-7 tight sandstone. Thin section observation, scanning electron microscope, grain size analysis, mineral composition analysis, and porosity measurement are applied to investigate geological control factors of pore structure. Grain size is positively correlated with detrital mineral content and grain size standard deviation while negatively related to clay content. Detrital mineral content and grain size are positively correlated with porosity, pore throat radius and withdrawal efficiency and negatively related to capillary pressure and pore-to-throat size ratio; while interstitial material is negatively correlated with above mentioned factors. Well sorted sediments with high debris usually possess strong compaction resistance to preserve original pores. Although many inter-crystalline pores are produced in clay minerals, this type of pores is not the most important contributor to porosity. Besides this, pore shape determined by N2GA hysteresis loop is consistent with SEM observation on clay inter-crystalline pores while BJH pore volume is positively related with clay content, suggesting N2GA is suitable for describing clay inter-crystalline pores in tight sandstones. PMID:27830731
NASA Technical Reports Server (NTRS)
Ishaug-Riley, S. L.; Crane, G. M.; Gurlek, A.; Miller, M. J.; Yasko, A. W.; Yaszemski, M. J.; Mikos, A. G.; McIntire, L. V. (Principal Investigator)
1997-01-01
Porous biodegradable poly(DL-lactic-co-glycolic acid) foams were seeded with rat marrow stromal cells and implanted into the rat mesentery to investigate in vivo bone formation at an ectopic site. Cells were seeded at a density of 6.83 x 10(5) cells/cm2 onto polymer foams having pore sizes ranging from either 150 to 300 to 710 microns and cultured for 7 days in vitro prior to implantation. The polymer/cell constructs were harvested after 1, 7, 28, or 49 days in vivo and processed for histology and gel permeation chromatography. Visual observation of hematoxylin and eosin-stained sections and von Kossa-stained sections revealed the formation of mineralized bonelike tissue in the constructs within 7 days postimplantation. Ingrowth of vascular tissue was also found adjacent to the islands of bone, supplying the necessary metabolic requirements to the newly formed tissue. Mineralization and bone tissue formation were investigated by histomorphometry. The average penetration depth of mineralized tissue in the construct ranged from 190 +/- 50 microns for foams with 500-710-microns pores to 370 +/- 160 microns for foams with 150-300-microns pores after 49 days in vivo. The mineralized bone volume per surface area and total bone volume per surface area had maximal values of 0.28 +/- 0.21 mm (500-710-microns pore size, day 28) and 0.038 +/- 0.024 mm (150-300-microns, day 28), respectively. As much as 11% of the foam volume penetrated by bone tissue was filled with mineralized tissue. No significant trends over time were observed for any of the measured values (penetration depth, bone volume/surface area, or percent mineralized bone volume). These results suggest the feasibility of bone formation by osteoblast transplantation in an orthotopic site where not only bone formation from transplanted cells but also ingrowth from adjacent bone may occur.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Smith, A. Peyton; Bond-Lamberty, Ben; Benscoter, Brian W.
Droughts and other extreme precipitation events are predicted to increase in intensity, duration and extent, with uncertain implications for terrestrial carbon (C) sequestration. Soil wetting from above (precipitation) results in a characteristically different pattern of pore-filling than wetting from below (groundwater), with larger, well-connected pores filling before finer pore spaces, unlike groundwater rise in which capillary forces saturate the finest pores first. Here we demonstrate that pore-scale wetting patterns interact with antecedent soil moisture conditions to alter pore-, core- and field-scale C dynamics. Drought legacy and wetting direction are perhaps more important determinants of short-term C mineralization than current soilmore » moisture content in these soils. Our results highlight that microbial access to C is not solely limited by physical protection, but also by drought or wetting-induced shifts in hydrologic connectivity. We argue that models should treat soil moisture within a three-dimensional framework emphasizing hydrologic conduits for C and resource diffusion.« less
Soils are sensitive reactors - do we need a paradigm change towards a more sustainable soil use?
NASA Astrophysics Data System (ADS)
Horn, Rainer; Holthusen, Dörthe
2015-04-01
The aim of the lecture is to clarify the effect of soil management and the consequences of physical degradation on processes like soil aggregation and changes in the accessibility and functionality of structured soils. If due to soil management strategies the internal soil strength will be exceeded by external stresses applied not only the available pore space is reduced while the solid mass is increased but especially the pore continuity and the accessibility of exchange places for nutrients or heavy metals are altered. In addition, the root distribution in soils becomes not only reduced but also unevenly distributed which again hinders the possibility to evenly uptake plant available water and nutrient out of the pores. The applied stresses also create an anisotropic arrangement of the pores and their functions and also result in a more pronounced lateral mass transport by surface runoff including soil erosion by water and wind. Thus, also the water balance on all scales (from the pedon to the catchment) shows an increased water loss by evaporation and surface water while the groundwater recharge and the transpiration rates are reduced. If we analyze the scale dependency of nutrient adsorption and desorption phenomena it has to be stated, that the accessibility of exchange places within soil aggregates are the better the more structured and the more rigid these aggregates are, while with increasing mechanical stress applied aggregates are deformed and as a consequences they become less porous with a severe differentiation between the outer and the inner part of the aggregate volume. On the bulk soil scale, we can analyze the platy structure as a visible hint for anthropogenic soil degradation which affects amongst others also the ion exchange processes. Furthermore an uneven aeration within such degraded soils results in a very pronounced anoxia on all scales (from the aggregate to the hectare scale) which can be quantified not only by corresponding measurements of the spatial distribution of redox potential values. In recent studies under "normal" wheeling conditions in arable fields and also in harvested forest sites it was proofed that Eh values close to 0 mV or even a methane emission have to be expected (with consequences for the global warming). Finally anoxic conditions also affect the redox induced mobilization of Fe and Mn which even results in a more rapid soil development with consequences also for yield and further soil functions. Consequently a shift to a more sustainable landuse or soil management strategy is urgently requested in order to prevent a further soil degradation. The scenario of peak soil must and can be prevented by a more site specific soil management. In the lecture, these effects will be discussed as well as a soil protection guide line (based on the German soil protection law) will be presented in order to prevent further irreversible soil degradation phenomena. Keywords: mechanical strength, mechanical stress and strain effects soil degradation, pore functions, ad-/desorption processes, redox potential, anoxia;, global change
Orsolini, Paola; Michen, Benjamin; Huch, Anja; Tingaut, Philippe; Caseri, Walter R; Zimmermann, Tanja
2015-11-25
Nanofibrillated cellulose (NFC) is a natural fibrous material that can be readily processed into membranes. NFC membranes for fluid separation work in aqueous medium, thus in their swollen state. The present study is devoted to a critical investigation of porosity, pore volume, specific surface area, and pore size distribution of dry and wet NFC nanopapers, also known as membranes, with various established techniques, such as electron microscopy, helium pycnometry, mercury intrusion, gas adsorption (N2 and Kr), and thermoporometry. Although these techniques can be successfully applied to inorganic materials (e.g., mesoporous silica), it is necessary to appraise them for organic and hydrophilic products such as NFC membranes. This is due to different phenomena occurring at the materials interfaces with the probing fluids. Mercury intrusion and gas adsorption are often used for the characterization of porosity-related properties; nevertheless, both techniques characterize materials in the dry state. In parallel, thermoporometry was employed to monitor the structure changes upon swelling, and a water permeance test was run to show the accessibility of the membranes to fluids. For the first time, the methods were systematically screened, and we highlighted the need of uniform sample treatments prior to the measurements (i.e., sample cutting and outgassing protocols) in order to harmonize results from the literature. The need for revising the applicability range of mercury intrusion and the inappropriateness of nitrogen adsorption were pointed out. We finally present a table for selecting the most appropriate method to determine a desired property and propose guidelines for results interpretation from which future users could profit.
Spatially resolved D-T(2) correlation NMR of porous media.
Zhang, Yan; Blümich, Bernhard
2014-05-01
Within the past decade, 2D Laplace nuclear magnetic resonance (NMR) has been developed to analyze pore geometry and diffusion of fluids in porous media on the micrometer scale. Many objects like rocks and concrete are heterogeneous on the macroscopic scale, and an integral analysis of microscopic properties provides volume-averaged information. Magnetic resonance imaging (MRI) resolves this spatial average on the contrast scale set by the particular MRI technique. Desirable contrast parameters for studies of fluid transport in porous media derive from the pore-size distribution and the pore connectivity. These microscopic parameters are accessed by 1D and 2D Laplace NMR techniques. It is therefore desirable to combine MRI and 2D Laplace NMR to image functional information on fluid transport in porous media. Because 2D Laplace resolved MRI demands excessive measuring time, this study investigates the possibility to restrict the 2D Laplace analysis to the sum signals from low-resolution pixels, which correspond to pixels of similar amplitude in high-resolution images. In this exploratory study spatially resolved D-T2 correlation maps from glass beads and mortar are analyzed. Regions of similar contrast are first identified in high-resolution images to locate corresponding pixels in low-resolution images generated with D-T2 resolved MRI for subsequent pixel summation to improve the signal-to-noise ratio of contrast-specific D-T2 maps. This method is expected to contribute valuable information on correlated sample heterogeneity from the macroscopic and the microscopic scales in various types of porous materials including building materials and rock. Copyright © 2014 Elsevier Inc. All rights reserved.
NASA Astrophysics Data System (ADS)
Pekor, Christopher Michael
Porous ceramics can be divided into three separate classes based on their pore size: microporous ceramics with pores less than 2 nm, mesoporous ceramics with pores in the range of 2--50 nm and macroporous ceramics with pores that are greater than 50 nm. In particular, macroporous ceramics are used in a variety of applications such as refractories, molten metal filtration, diesel particulate filters, heterogeneous catalyst supports and biomedical scaffolds. Freeze casting is a novel method used to create macroporous ceramics. In this method growing ice crystals act as a template for the pores and are solidified, often directionally, through a ceramic dispersion and removed from the green body through a freeze drying procedure. This method has attracted some attention over the past few years due to its relative simplicity, flexibility and environmental friendliness. On top of this freeze casting is capable of producing materials with high pore volume fractions, which is an advantage over processing by packing and necking of particles, where the pore volume fraction is typically less than 50%. Many of the basic processing variables that affect the freeze cast microstructure, such as the temperature gradient, interfacial velocity and solid loading of the dispersion have been well established in the literature. On the other hand, areas such as the effect of additives on the microstructure and mechanical properties have not been covered in great detail. In this study the concept of constitutional supercooling from basic solidification theory is used to explain the effects of two water-soluble polymers, polyethylene glycol and polyvinyl alcohol, on the microstructure of freeze cast alumina ceramics. In addition, changes in the observed microstructure will be related to experimentally determined values of permeability and compressive strength.
Growth of nanostructures with controlled diameter
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pfefferle, Lisa; Haller, Gary; Ciuparu, Dragos
2009-02-03
Transition metal-substituted MCM-41 framework structures with a high degree of structural order and a narrow pore diameter distribution were reproducibly synthesized by a hydrothermal method using a surfactant and an anti-foaming agent. The pore size and the mesoporous volume depend linearly on the surfactant chain length. The transition metals, such as cobalt, are incorporated substitutionally and highly dispersed in the silica framework. Single wall carbon nanotubes with a narrow diameter distribution that correlates with the pore diameter of the catalytic framework structure were prepared by a Boudouard reaction. Nanostructures with a specified diameter or cross-sectional area can therefore be predictablymore » prepared by selecting a suitable pore size of the framework structure.« less
Wang, Y X; Ngo, H H; Guo, W S
2015-11-15
The studied bamboo based activated carbon (BbAC) with high specific surface area (SSA) and high micro pore volume was prepared from bamboo scraps by the combined activation of H3PO4 and K2CO3. The BbAC was characterized based on the N2 adsorption isotherm at 77K. The results showed that the SSA and pore volume of BbAC increased with increasing impregnation ratio and reached maxima at the impregnation ratio of 3:1 at 750°C. Under these optimal conditions, the BbAC obtained could have a maximum SSA of 2237 m(2)/g and a maximum total pore volume of 1.23 cm(3)/g with the micro pore ratio of more than 90%. The adsorption performance of ciprofloxacin (CIP) on the BbAC was determined at 298 K. The Langmuir and Freundlich models were employed to describe the adsorption equilibrium and the kinetic data were fitted by pseudo first-order and pseudo second-order kinetic models. The results showed that the Langmuir model and the pseudo second-order kinetic model presented better fittings for the adsorption equilibrium and kinetics data, respectively. The maximum adsorption amount of CIP (613 mg/g) on the BbAC was much higher than the report in the literature. Conclusively, the BbAC could be a promising adsorption material for CIP removal from water. Copyright © 2015 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Daigle, Hugh; Hayman, Nicholas; Jiang, Han; Tian, Xiao; Jiang, Chunbi
2017-04-01
Multiple lines of evidence indicate that, during a hydraulic fracture stimulation, the permeability of the unfractured matrix far from the main, induced tensile fracture increases by one to two orders of magnitude. This permeability enhancement is associated with pervasive shear failure in a large region surrounding the main induced fracture. We have performed low-pressure gas sorption, mercury intrusion, and nuclear magnetic resonance measurements along with high-resolution scanning electron microscope imaging on several preserved and unpreserved shale samples from North American basins before and after inducing failure in confined compressive strength tests. We have observed that the pore structure in intact samples exhibits multiscale behavior, with sub-micron-scale pores in organic matter connected in isolated, micron-scale clusters which themselves are connected to each other through a network of microcracks. The organic-hosted pore networks are poorly connected due to a significant number of dead-end pores within the organic matter. Following shear failure, we often observe an increase in pore volume in the sub-micron range, which appears to be related to the formation of microcracks that propagate along grain boundaries and other planes of mechanical strength contrast. This is consistent with other experimental and field evidence. In some cases these microcracks cross or terminate in organic matter, intersecting the organic-hosted pores. The induced microcrack networks typically have low connectivity and do not appreciably increase the connectivity of the overall pore network. However, in other cases the shear deformation results in an overall pore volume decrease; samples which exhibit this behavior tend to have more clay minerals. Our interpretation of these phenomena is as follows. As organic matter is converted to hydrocarbons, organic-hosted pores develop, and the hydrocarbons contained in these pores are overpressured. The disconnected nature of these clusters of organic-hosted pores prevents the overpressure from dissipating, resulting in localized overpressure at the micron scale. When the rock is subjected to a hydraulic fracture stimulation, the rock surrounding the main induced fracture experiences shear deformation. Those parts of the rock that contain overpressured fluids in the organic-hosted pores will be more likely to experience dilatancy in the form of brittle deformation; the portions of the rock lacking in organic-hosted pores will tend to experience compactive shear failure since the effective normal stresses are larger. The microcrack networks that propagate into the regions of organic-hosted porosity allow the hydrocarbons resident in those pores to migrate to the main induced tensile fractures. The disconnected nature of the microcrack networks causes only a slight increase in permeability, which is consistent with other observations. Our work illustrates how multiscale pore networks in shale interact with in situ stresses to affect the bulk shale rheology.
Pore network extraction from pore space images of various porous media systems
NASA Astrophysics Data System (ADS)
Yi, Zhixing; Lin, Mian; Jiang, Wenbin; Zhang, Zhaobin; Li, Haishan; Gao, Jian
2017-04-01
Pore network extraction, which is defined as the transformation from irregular pore space to a simplified network in the form of pores connected by throats, is significant to microstructure analysis and network modeling. A physically realistic pore network is not only a representation of the pore space in the sense of topology and morphology, but also a good tool for predicting transport properties accurately. We present a method to extract pore network by employing the centrally located medial axis to guide the construction of maximal-balls-like skeleton where the pores and throats are defined and parameterized. To validate our method, various rock samples including sand pack, sandstones, and carbonates were used to extract pore networks. The pore structures were compared quantitatively with the structures extracted by medial axis method or maximal ball method. The predicted absolute permeability and formation factor were verified against the theoretical solutions obtained by lattice Boltzmann method and finite volume method, respectively. The two-phase flow was simulated through the networks extracted from homogeneous sandstones, and the generated relative permeability curves were compared with the data obtained from experimental method and other numerical models. The results show that the accuracy of our network is higher than that of other networks for predicting transport properties, so the presented method is more reliable for extracting physically realistic pore network.
Understanding fluid transport through the multiscale pore network of a natural shale
NASA Astrophysics Data System (ADS)
Davy, Catherine; Adler, Pierre; Song, Yang; Nguyen, Thang Kim; Troadec, David; Dhénin, Jean-Francois
2017-04-01
Natural shales have a complex pore structure, which is only partly understood today. In the present contribution, a combination of different techniques is used to get information on three different scales. On each scale, the relevant flow equation is solved and provides input for the flow equation of the next higher scale. More precisely, micro-CT, FIB/SEM (Focused Ion Beam/Scanning Electron Microscopy) and TEM (Transmission Electron Microscopy) provide a full representative 3D pore space on the macroscopic scale, the mesoscale and the nanoscale. The corresponding typical voxel sizes are 0.7 μm, 10 nm and 1 nm, respectively. The porosity on the micro-CT images is 0.5 %, and it is not connected. One can distinguish between the pores, the porous clay matrix and non porous minerals; the volume percentages of these last two phases are 0.6 and 0.395, respectively. Samples of the porous clay matrix were analyzed by FIB/SEM which yields 3D information. They have a porosity ranging from 2 to 6 %. In some of them, the pore space is connected. Finally, TEM provides 2D images with a porosity of about 10 to 25 %. These information were used in the following way to estimate the macroscopic permeability which has been measured independently and found equal to 6 x10-20 m2. At the nanoscopic scale analyzed by 2D TEM, in the absence of 3D images, the pore structure is reconstructed by using a technique based on truncated Gaussian fields. Then, the Stokes equations are solved by using a 3D Lattice Boltzmann method. The resulting velocity field is averaged and this provides the permeability K_n. The permeability of the nanoscale structure varies between 0.7x 10-20 and 1.8x10-19 m2. As expected, the material is anisotropic. At the mesoscale, percolation of the FIB/SEM pore volume occurs only along a single direction. The Stokes equations are again solved by the same method and the mesoscopic permeability Km varies between 3.3 10-20 and 1.20 10-18 m2, depending on the nature of the percolating volume. The influence of the nanoscale porosity on the mesoscopic permeability is also studied. Two examples show that despite the scale ratio between the mesoscopic and nanoscopic pores, the nanoscopic pore structure cannot be neglected to estimate the permeability of the pore clay matrix. Finally, the sample provided by micro-CT is considered as a porous medium composed of three phases with permeabilities 0 (for the non porous minerals), 1 (for the porous clay matrix) and infinity (for the macroscopic pores). The overall permeability Kmacro is obtained by solving the Darcy's equation with a variable local permeability with spatially periodic boundary conditions. Kmacro is found of the order of 0.4 and the medium is relatively isotropic on this scale. This estimation of Kmacro is in agreement with the measured value.
NASA Astrophysics Data System (ADS)
Heimböckel, Ruben; Kraas, Sebastian; Hoffmann, Frank; Fröba, Michael
2018-01-01
A series of porous carbon samples were prepared by combining a semi-carbonization process of acidic polymerized phenol-formaldehyde resins and a following chemical activation with KOH used in different ratios to increase specific surface area, micropore content and pore sizes of the carbons which is favourable for supercapacitor applications. Samples were characterized by nitrogen physisorption, powder X-ray diffraction, Raman spectroscopy and scanning electron microscopy. The results show that the amount of KOH, combined with the semi-carbonization step had a remarkable effect on the specific surface area (up to SBET: 3595 m2 g-1 and SDFT: 2551 m2 g-1), pore volume (0.60-2.62 cm3 g-1) and pore sizes (up to 3.5 nm). The carbons were tested as electrode materials for electrochemical double layer capacitors (EDLC) in a two electrode setup with tetraethylammonium tetrafluoroborate in acetonitrile as electrolyte. The prepared carbon material with the largest surface area, pore volume and pore sizes exhibits a high specific capacitance of 145.1 F g-1 at a current density of 1 A g-1. With a high specific energy of 31 W h kg-1 at a power density of 33028 W kg-1 and a short time relaxation constant of 0.29 s, the carbon showed high power capability as an EDLC electrode material.
Analytical electron tomography mapping of the SiCporeoxidation at the nanoscale
NASA Astrophysics Data System (ADS)
Florea, Ileana; Ersen, Ovidiu; Hirlimann, Charles; Roiban, Lucian; Deneuve, Adrien; Houllé, Matthieu; Janowska, Izabela; Nguyen, Patrick; Pham, Charlotte; Pham-Huu, Cuong
2010-12-01
Silicon carbide is a ceramic material that has been widely studied because of its potential applications, ranging from electronics to heterogeneous catalysis. Recently, a new type of SiC materials with a medium specific surface area and thermal conductivity, called β-SiC, has attracted overgrowing interest as a new class of catalyst support in several catalytic reactions. A primary electron tomography study, performed in usual mode, has revealed a dual surface structure defined by two types of porosities made of networks of connected channels with sizes larger than 50 nm and ink-bottled pores with sizes spanning from 4 to 50 nm. Depending on the solvent nature, metal nanoparticles could be selectively deposited inside one of the two porosities, a fact that illustrates a selective wetting titration of the two types of surfaces by different liquids. The explaining hypothesis that has been put forward was that this selectivity against solvents is related to the pore surface oxidation degree of the two types of pores. A new technique of analytical electron tomography, where the series of projections used to reconstruct the volume of an object is recorded in energy filtered mode (EFTEM), has been implemented to map the poreoxidation state and to correlate it with the morphology and the accessibility of the porous network. Applied, for the first time, at a nanoscale resolution, this technique allowed us to obtain 3D elemental maps of different elements present in the analysed porous grains, in particular oxygen; we found thus that the interconnected channelpores are more rapidly oxidized than the ink-bottled ones. Alternatively, our study highlights the great interest of this method that opens the way for obtaining precise information on the chemical composition of a 3D surface at a nanometer scale.Silicon carbide is a ceramic material that has been widely studied because of its potential applications, ranging from electronics to heterogeneous catalysis. Recently, a new type of SiC materials with a medium specific surface area and thermal conductivity, called β-SiC, has attracted overgrowing interest as a new class of catalyst support in several catalytic reactions. A primary electron tomography study, performed in usual mode, has revealed a dual surface structure defined by two types of porosities made of networks of connected channels with sizes larger than 50 nm and ink-bottled pores with sizes spanning from 4 to 50 nm. Depending on the solvent nature, metal nanoparticles could be selectively deposited inside one of the two porosities, a fact that illustrates a selective wetting titration of the two types of surfaces by different liquids. The explaining hypothesis that has been put forward was that this selectivity against solvents is related to the pore surface oxidation degree of the two types of pores. A new technique of analytical electron tomography, where the series of projections used to reconstruct the volume of an object is recorded in energy filtered mode (EFTEM), has been implemented to map the poreoxidation state and to correlate it with the morphology and the accessibility of the porous network. Applied, for the first time, at a nanoscale resolution, this technique allowed us to obtain 3D elemental maps of different elements present in the analysed porous grains, in particular oxygen; we found thus that the interconnected channelpores are more rapidly oxidized than the ink-bottled ones. Alternatively, our study highlights the great interest of this method that opens the way for obtaining precise information on the chemical composition of a 3D surface at a nanometer scale. Electronic supplementary information (ESI) available: SI-1-SI-4. See DOI: 10.1039/c0nr00449a
NASA Astrophysics Data System (ADS)
Hicks, Randall Wayne
Aluminas are utilized in many industrial applications, including as adsorbents, abrasives, ceramics, catalysts, and catalyst supports. Many different phases of aluminas exist, but due to its favorable combination of surface and textural properties, the most important phase is gamma-alumina. Surface areas and pore volumes of conventional aluminas are typically less than 250 m 2/g and 0.5 cc/g, respectively. Performance in catalytic applications is limited in part by these properties. As has been shown in silica chemistry, the use of surfactants to aid in the assembly of a mesostructure leads to improvement in textural properties. Similar advances are anticipated in alumina chemistry, but to date, little progress has been made in this area. Since the disclosure of mesostructured aluminas in 1996, all but a couple of subsequent reports have described compositions of mesostructured aluminas with amorphous walls. This limits their thermal and hydrothermal stability, and thus their potential use in catalytic applications. The present work describes the synthesis of the first members of a new family of crystalline mesostructured aluminas prepared from the hydrolysis of aluminum sec-butoxide in the presence of either polyethylene oxide (PEO) or amine surfactants as porogens. Members of this family exhibiting the gamma-Al 2O3 phase, denoted MSU-gamma aluminas, have surface areas, pore sizes, and pore volumes in excess of 400 m2/g, 15 nm, and 1.5 cc/g, respectively. In addition, forms of these aluminas have expressed thermal and hydrothermal stability. Mesostructured boehmites, MSU-B aluminas, have also been obtained using similar synthetic methods. In the synthesis of either alumina, the key step is the formation of an MSU-S/B surfactant-boehmite precursor, which is converted to the desired final product through calcination. To demonstrate their usefulness, MSU-gamma aluminas have been utilized as catalyst supports in dibenzothiophene hydrodesulfurization reactions. Conversions and selectivities superior to that of a commercial catalyst have been achieved. Their success in this capacity can be traced to the stability of the gamma-Al 2O3 phase, the ability to effectively disperse the active catalytic component, and increased accessibility to the active sites.
Wi, Seunghwan; Chang, Seong Jin; Jeong, Su-Gwang; Lee, Jongki; Kim, Taeyeon; Park, Kyung-Won; Lee, Dong Ryeol; Kim, Sumin
2017-07-26
Porous carbon materials are advantageous in adsorbing pollutants due to their wide range of specific surface areas, pore diameter, and pore volume. Among the porous carbon materials in the current study, expanded graphite, xGnP, xGnP C-300, xGnP C-500, and xGnP C-750 were prepared as adsorbent materials. Brunauer-Emmett-Teller (BET) analysis was conducted to select the adsorbent material through the analysis of the specific surface area, pore size, and pore volume of the prepared porous carbon materials. Morphological analysis using SEM was also performed. The xGnP C-500 as adsorbent material was applied to a mortar adhesive that is widely used in the installation of interior building materials. The toluene adsorption performances of the specimens were evaluated using 20 L small chamber. Furthermore, the performance of the mortar adhesive, as indicated by the shear bond strength, length change rate, and water retention rate, was analyzed according to the required test method specified in the Korean standards. It was confirmed that for the mortar adhesives prepared using the xGnP C-500 as adsorbent material, the toluene adsorption performance was excellent and satisfied the required physical properties.
Pietrucha, Krystyna
2015-09-01
Collagen-based composite scaffolds have considerable potential due to their well-known ability to regenerate skin, bone and cartilage. However, the precise composition and structure of scaffolds that optimize their interaction with neural cells remains incompletely understood and yet to be explored. In the present study, a new family of bi-component 3D scaffolds consisting of collagen (Col) and chondroitin sulphate (CS) were synthesized using a two-stage process: multiple freeze-drying followed by carbodiimide modification. Col-CS matrices had an average pore diameter of 31 μm and a relatively high surface area to pore volume ratio. Importantly, the FTIR data indicated that the ratio between the intensity of amide III and 1452 cm(-1) for Col-CS scaffold was 0.87, which indicates that the Col triple helix was preserved during the formation of the bond between Col and CS. All experiments also clearly showed that the Col-CS matrices have a lower enzyme sensitivity and higher thermal resistance than Col alone. These differences are likely due to the relatively large amount of CS in the collagen sponges, which hinders access for attack at specific active sites of the Col triple helix. Improved binary composite scaffolds were designed for neural tissue engineering applications. Copyright © 2015 Elsevier B.V. All rights reserved.
Characterization of porosity in sulfide ore minerals: A USANS/SANS study
DOE Office of Scientific and Technical Information (OSTI.GOV)
Xia, F.; Zhao, J.; Etschmann, B. E.
Porosity plays a key role in the formation and alteration of sulfide ore minerals, yet our knowledge of the nature and formation of the residual pores is very limited. Herein, we report the application of ultra-small-angle neutron scattering and small-angle neutron scattering (USANS/SANS) to assess the porosity in five natural sulfide minerals (violarite, marcasite, pyrite, chalcopyrite, and bornite) possibly formed by hydrothermal mineral replacement reactions and two synthetic sulfide minerals (violarite and marcasite) prepared experimentally by mimicking natural hydrothermal conditions. USANS/SANS data showed very different pore size distributions for these minerals. Natural violarite and marcasite tend to possess less poresmore » in the small size range (<100 nm) compared with their synthetic counterparts. This phenomenon is consistent with a higher degree of pore healing or diagenetic compaction experienced by the natural violarite and marcasite. Surprisingly, nanometer-sized (<20 nm) pores were revealed for a natural pyrite cube from La Rioga, Spain, and the sample has a pore volume fraction of ~7.7%. Both chalcopyrite and bornite from the massive sulfide assemblage of the Olympic Dam deposit in Roxby Downs, South Australia, were found to be porous with a similar pore volume fraction (~15%), but chalcopyrite tends to have a higher proportion of nanometer-size pores centered at ~4 nm while bornite tends to have a broader pore size distribution. The specific surface area is generally low for these minerals ranging from 0.94 to 6.28 m2/g, and the surfaces are generally rough as surface fractal behavior was observed for all these minerals. This investigation has demonstrated that USANS/SANS is a very useful tool for analyzing porosity in ore minerals. We believe that with this quantified porosity information a deeper understanding of the complex fluid flow behavior within the porous minerals can be expected.« less
Hussein, Esam M A; Agbogun, H M D; Al, Tom A
2015-03-01
A method is presented for interpreting the values of x-ray attenuation coefficients reconstructed in computed tomography of porous media, while overcoming the ambiguity caused by the multichromatic nature of x-rays, dilution by void, and material heterogeneity. The method enables determination of porosity without relying on calibration or image segmentation or thresholding to discriminate pores from solid material. It distinguishes between solution-accessible and inaccessible pores, and provides the spatial and frequency distributions of solid-matrix material in a heterogeneous medium. This is accomplished by matching an image of a sample saturated with a contrast solution with that saturated with a transparent solution. Voxels occupied with solid-material and inaccessible pores are identified by the fact that they maintain the same location and image attributes in both images, with voxels containing inaccessible pores appearing empty in both images. Fully porous and accessible voxels exhibit the maximum contrast, while the rest are porous voxels containing mixtures of pore solutions and solid. This matching process is performed with an image registration computer code, and image processing software that requires only simple subtraction and multiplication (scaling) processes. The process is demonstrated in dolomite (non-uniform void distribution, homogeneous solid matrix) and sandstone (nearly uniform void distribution, heterogeneous solid matrix) samples, and its overall performance is shown to compare favorably with a method based on calibration and thresholding. Copyright © 2014 Elsevier Ltd. All rights reserved.
Fineberg, Jeffrey D.; Szanto, Tibor G.; Panyi, Gyorgy; Covarrubias, Manuel
2016-01-01
Voltage-gated K+ (Kv) channel activation depends on interactions between voltage sensors and an intracellular activation gate that controls access to a central pore cavity. Here, we hypothesize that this gate is additionally responsible for closed-state inactivation (CSI) in Kv4.x channels. These Kv channels undergo CSI by a mechanism that is still poorly understood. To test the hypothesis, we deduced the state of the Kv4.1 channel intracellular gate by exploiting the trap-door paradigm of pore blockade by internally applied quaternary ammonium (QA) ions exhibiting slow blocking kinetics and high-affinity for a blocking site. We found that inactivation gating seemingly traps benzyl-tributylammonium (bTBuA) when it enters the central pore cavity in the open state. However, bTBuA fails to block inactivated Kv4.1 channels, suggesting gated access involving an internal gate. In contrast, bTBuA blockade of a Shaker Kv channel that undergoes open-state P/C-type inactivation exhibits fast onset and recovery inconsistent with bTBuA trapping. Furthermore, the inactivated Shaker Kv channel is readily blocked by bTBuA. We conclude that Kv4.1 closed-state inactivation modulates pore blockade by QA ions in a manner that depends on the state of the internal activation gate. PMID:27502553
NMR-based diffusion lattice imaging
NASA Astrophysics Data System (ADS)
Laun, Frederik Bernd; Müller, Lars; Kuder, Tristan Anselm
2016-03-01
Nuclear magnetic resonance (NMR) diffusion experiments are widely employed as they yield information about structures hindering the diffusion process, e.g., about cell membranes. While it has been shown in recent articles that these experiments can be used to determine the shape of closed pores averaged over a volume of interest, it is still an open question how much information can be gained in open well-connected systems. In this theoretical work, it is shown that the full structure information of connected periodic systems is accessible. To this end, the so-called "SEquential Rephasing by Pulsed field-gradient Encoding N Time intervals" (SERPENT) sequence is used, which employs several diffusion encoding gradient pulses with different amplitudes. Two two-dimensional solid matrices that are surrounded by an NMR-visible medium are considered: a hexagonal lattice of cylinders and a rectangular lattice of isosceles triangles.
NASA Astrophysics Data System (ADS)
Wallace, Kotska; Bavdaz, Marcos; Collon, Maximilien; Beijersbergen, Marco; Kraft, Stefan; Fairbend, Ray; Séguy, Julien; Blanquer, Pascal; Graue, Roland; Kampf, Dirk
2017-11-01
In support of future x-ray telescopes ESA is developing new optics for the x-ray regime. To date, mass and volume have made x-ray imaging technology prohibitive to planetary remote sensing imaging missions. And although highly successful, the mirror technology used on ESA's XMM-Newton is not sufficient for future, large, x-ray observatories, since physical limits on the mirror packing density mean that aperture size becomes prohibitive. To reduce telescope mass and volume the packing density of mirror shells must be reduced, whilst maintaining alignment and rigidity. Structures can also benefit from a modular optic arrangement. Pore optics are shown to meet these requirements. This paper will discuss two pore optic technologies under development, with examples of results from measurement campaigns on samples. One activity has centred on the use of coated, silicon wafers, patterned with ribs, that are integrated onto a mandrel whose form has been polished to the required shape. The wafers follow the shape precisely, forming pore sizes in the sub-mm region. Individual stacks of mirrors can be manufactured without risk to, or dependency on, each other and aligned in a structure from which they can also be removed without hazard. A breadboard is currently being built to demonstrate this technology. A second activity centres on glass pore optics. However an adaptation of micro channel plate technology to form square pores has resulted in a monolithic material that can be slumped into an optic form. Alignment and coating of two such plates produces an x-ray focusing optic. A breadboard 20cm aperture optic is currently being built.
Mastalerz, Maria; Drobniak, A.; Strapoc, D.; Solano-Acosta, W.; Rupp, J.
2008-01-01
The Seelyville Coal Member of the Linton Formation (Pennsylvanian) in Indiana was studied to: 1) understand variations in pore characteristics within a coal seam at a single location and compare these variations with changes occurring between the same coal at different locations, 2) elaborate on the influence of mineral-matter and maceral composition on mesopore and micropore characteristics, and 3) discuss implications of these variations for coal bed gas content. The coal is high volatile bituminous rank with R0 ranging from 0.57% to 0.60%. BET specific surface areas (determined by nitrogen adsorption) of the coals samples studied range from 1.8 to 22.9??m2/g, BJH adsorption mesopore volumes from 0.0041 to 0.0339??cm3/g, and micropore volumes (determined by carbon dioxide adsorption) from 0.0315 to 0.0540??cm3/g. The coals that had the largest specific surface areas and largest mesopore volumes occur at the shallowest depths, whereas the smallest values for these two parameters occur in the deepest coals. Micropore volumes, in contrast, are not depth-dependent. In the coal samples examined for this study, mineral-matter content influenced both specific surface area as well as mesopore and micropore volumes. It is especially clear in the case of micropores, where an increase in mineral-matter content parallels the decrease of micropore volume of the coal. No obvious relationships were observed between the total vitrinite content and pore characteristics but, after splitting vitrinite into individual macerals, we see that collotelinite influences both meso- and micropore volume positively, whereas collodetrinite contributes to the reduction of mesopore and micropore volumes. There are large variations in gas content within a single coal at a single location. Because of this variability, the entire thickness of the coal must be desorbed in order to determine gas content reliably and to accurately calculate the level of gas saturation. ?? 2008 Elsevier B.V. All rights reserved.
Impact of the titania nanostructure on charge transport and its application in hybrid solar cells
NASA Astrophysics Data System (ADS)
Koffman-Frischknecht, Alejandro; Gonzalez, Fernando; Plá, Juan; Violi, Ianina; Soler-Illia, Galo J. A. A.; Perez, M. Dolores
2018-02-01
Porous titania films are widely studied in a number of optoelectronic applications due to its favorable optical and electronic characteristics. Mesoporous titania thin films (MTTFs) with tunable pore size, pore order, accessibility and crystallinity are of interest in electronic devices due to the potential for optimization of the desired characteristics for charge separation and carrier transport. In this work, several MTTFs were prepared by sol-gel chemistry with different structural properties tuned by post-synthesis thermal treatment. The effect of the structural properties (pore diameter, order and accessibility) on the electrical properties of the material was studied by films fabrication onto a transparent conducting electrode, ITO, such that it enables optoelectronic applications. The performance as photoanode was explored by the fabrication of hybrid polymer (P3HT): titania solar cells. Not only does structural properties affect polymer impregnation inside the titania pores as expected and hence impacts charge separation at the interface, but also the thermal treatment affects crystallinity and the films electronic properties. A more complete picture about the electronic properties of the different MTTFs prepared in this work was studied by mobility measurement by space charge limited current and impedance spectroscopy.
Adsorption and wetting characterization of hydrophobic SBA-15 silicas.
Bernardoni, Frank; Fadeev, Alexander Y
2011-04-15
This work describes adsorption and wetting characterization of hydrophobic ordered mesoporous silicas (OMSs) with the SBA-15 motif. Three synthetic approaches to prepare hydrophobic SBA-15 silicas were explored: grafting with (1) covalently-attached monolayers (CAMs) of C(n)H(2)(n+1)Si(CH(3))(2)N(CH(3))(2), (2) self-assembled monolayers (SAMs) of C(n)H(2)(n+1)Si(OEt)(3), and (3) direct ("one-pot") co-condensation of TEOS with C(n)H(2)(n+1)Si(OEt)(3) in presence of P123 (n=1-18). The materials prepared were characterized by nitrogen adsorption, TEM, and chemical analysis. The surface properties of the materials were assessed by water contact angles (CAs) and by BET C constants. The results showed that, while loadings of the alkyl groups (%C) were comparable, the surface properties and pore ordering of the materials prepared through different methods were quite different. The best quality hydrophobic surfaces were prepared for SBA-15 grafted with CAMs of alkylsilanes. For these materials, the water CAs were above ∼120°/100° (adv/rec) and BET C constants were in the range of ∼15-25, indicating uniform low-energy surfaces of closely packed alkyl groups on external and internal surfaces of the pores respectively. Moreover, surfaces grafted with the long-chained (C(12)-C(18)) silanes showed super-hydrophobic behavior (CAs∼150-180°) and extremely low adhesion for water. The pore uniformity of parental SBA-15 was largely preserved and the pore volume and pore diameter were consistent with the formation of a single layer of alkylsilyl groups inside the pores. Post-synthesis grafting of SBA-15 with SAMs worked not as well as CAMs: the surfaces prepared demonstrated lower water CAs and higher BET C constants, thereby indicating a small amount of accessible polar groups (Si-OH) related to packing constrains for SAMs supported on highly curved surfaces of mesopores. The co-condensation method produced substantially more disordered materials and less hydrophobic surfaces than any of the grafting methods. The surfaces of these materials showed low water CAs and high BET C constants (∼100-200) thereby demonstrating a non-uniform surface coverage and presence of unmodified silica. It is concluded that CAMs chemistry is the most efficient approach in preparation of the functionalized OMS materials with uniform surfaces and pores. Copyright © 2011 Elsevier Inc. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
McCray, John; Navarre-Sitchler, Alexis; Mouzakis, Katherine
Injection of CO2 into underground rock formations can reduce atmospheric CO2 emissions. Caprocks present above potential storage formations are the main structural trap inhibiting CO2 from leaking into overlying aquifers or back to the Earth's surface. Dissolution and precipitation of caprock minerals resulting from reaction with CO2 may alter the pore network where many pores are of the micrometer to nanometer scale, thus altering the structural trapping potential of the caprock. However, the distribution, geometry and volume of pores at these scales are poorly characterized. In order to evaluate the overall risk of leakage of CO2 from storage formations, amore » first critical step is understanding the distribution and shape of pores in a variety of different caprocks. As the caprock is often comprised of mudstones, we analyzed samples from several mudstone formations with small angle neutron scattering (SANS) and high-resolution transmission electron microscopy (TEM) imaging to compare the pore networks. Mudstones were chosen from current or potential sites for carbon sequestration projects including the Marine Tuscaloosa Group, the Lower Tuscaloosa Group, the upper and lower shale members of the Kirtland Formation, and the Pennsylvanian Gothic shale. Expandable clay contents ranged from 10% to approximately 40% in the Gothic shale and Kirtland Formation, respectively. During SANS, neutrons effectively scatter from interfaces between materials with differing scattering length density (i.e., minerals and pores). The intensity of scattered neutrons, I(Q), where Q is the scattering vector, gives information about the volume and arrangement of pores in the sample. The slope of the scattering data when plotted as log I(Q) vs. log Q provides information about the fractality or geometry of the pore network. On such plots slopes from -2 to -3 represent mass fractals while slopes from -3 to -4 represent surface fractals. Scattering data showed surface fractal dimensions for the Kirtland formation and one sample from the Tuscaloosa formation close to 3, indicating very rough surfaces. In contrast, scattering data for the Gothic shale formation exhibited mass fractal behavior. In one sample of the Tuscaloosa formation the data are described by a surface fractal at low Q (larger pores) and a mass fractal at high Q (smaller pores), indicating two pore populations contributing to the scattering behavior. These small angle neutron scattering results, combined with high-resolution TEM imaging, provided a means for both qualitative and quantitative analysis of the differences in pore networks between these various mudstones.« less
Single water channels of aquaporin-1 do not obey the Kedem-Katchalsky equations.
Curry, M R; Shachar-Hill, B; Hill, A E
2001-05-15
The Kedem-Katchalsky (KK) equations are often used to obtain information about the osmotic properties and conductance of channels to water. Using human red cell membranes, in which the osmotic flow is dominated by Aquaporin-1, we show here that compared to NaCl the reflexion coefficient of the channel for methylurea, when corrected for solute volume exchange and for the water permeability of the lipid membrane, is 0.54. The channels are impermeable to these two solutes which would seem to rule out flow interaction and require a reflexion coefficient close to 1.0 for both. Thus, two solutes can give very different osmotic flow rates through a semi-permeable pore, a result at variance with both classical theory and the KK formulation. The use of KK equations to analyze osmotic volume changes, which results in a single hybrid reflexion coefficient for each solute, may explain the discrepancy in the literature between such results and those where the equations have not been employed. Osmotic reflexion coefficients substantially different from 1.0 cannot be ascribed to the participation of other 'hidden' parallel aqueous channels consistently with known properties of the membrane. Furthermore, we show that this difference cannot be due to second-order effects, such as a solute-specific interaction with water in only part of the channel, because the osmosis is linear with driving force down to zero solute concentration, a finding which also rules out the involvement of unstirred-layer effects. Reflexion coefficients smaller than 1.0 do not necessitate water-solute flow interaction in permeable aqueous channels; rather, the osmotic behaviour of impermeable molecular-sized pores can be explained by differences in the fundamental nature of water flow in regions either accessible or inaccessible to solute, created by a varying cross-section of the channel.
Qiu, Yuping; Xiao, Xiaoyu; Cheng, Haiyan; Zhou, Zunlong; Sheng, G Daniel
2009-07-01
Loading two organic acids of known molecular structures onto a black carbon was conducted to study the influence of pH and dissolved organic matter on the adsorption of pesticides. Tannic acid at the loading rates of 100 and 300 micromol/g reduced the surface area of black carbon by 18 and 63%, respectively. This was due principally to the blockage of micropores, as verified by measured pore volumes and pore-size distributions. With a comparatively much smaller molecular structure, gallic acid did not apparently influence these properties. The intrinsic acidities of the two acids increased the surface acidity from 1.88 mmol/g of black carbon to 1.93-2.02 mmol/g after DOM loading, resulting in a reduction in isoelectric point pH from 1.93 to 1.66-1.82. The adsorption of propanil, 2,4-D and prometon by black carbon free and loaded of DOM was dependent on pH because major adsorptive forces were the interactions between neutral pesticide molecules and uncharged carbon surfaces. The adsorption was diminished considerably by the deprotonation of 2,4-D and protonation of prometon, as well as the surface charge change of black carbon. Tannic acid of 100 and 300 micromol/g on black carbon reduced the pesticide adsorption at the equilibrium concentration of 10 mg/L by an average of 46 and 81%, respectively, consistent with the reductions of 42 and 81% in micropore volume. At the equilibrium concentration of 30 mg/L, the mesopore surface became the additional adsorptive domain for propanil. Loading tannic acid made the mesopore surface less accessible, due presumably to the enhanced obstruction by tannic acid.
Nano- to Formation-Scale Estimates of Mineral-Specific Reactive Surface Area
NASA Astrophysics Data System (ADS)
Cole, D. R.; Swift, A.; Sheets, J.; Anovitz, L. M.
2017-12-01
Predictions of changes in fluid composition, coupled with the evolution of the solid matrix, include the generation and testing of reactive transport models. However, translating a heterogeneous natural system into physical and chemical model parameters, including the critical but poorly-constrained metric of fluid-accessible surface area, continues to challenge Earth scientists. Studies of carbon storage capacity, permeability, rock strain due to mineral dissolution and precipitation, or the prediction of rock evolution through diagenesis and weathering each consider macroscale outcomes of processes that often are critically impacted by rock surface geometry at the nanoscale. The approach taken here is to consider the whole vertical extent of a saline reservoir and then to address two questions. First, what is the accessible surface area for each major mineral, and for all adjacent pore sizes from <2 nm on up, within each major lithofacies in that formation? Second, with the formation thus divided into units of analysis, parameterized, and placed into geologic context, what constraints can be placed on reactive surface area as a function of mineral composition? A complex sandstone covering a substantial fraction of the quartz-K-feldspar-illite ternary is selected and mineral-specific surface area quantified using neutron scattering, nitrogen and mercury porosimetry, multi-signal high-resolution mineral mapping, and other techniques. For neutron scattering, scale-specific pore geometries enable more accurate translation of volume into surface area. By applying this workflow to all end-member lithologies of this reservoir formation, equations and maps of surface area as a function of position on a quartz-feldspar-clay ternary plot are developed for each major mineral. Results from this work therefore advance our ability to parameterize models not just for the particular formation studied, but for similar geologic units as well.
NASA Astrophysics Data System (ADS)
Chen, Yu; Wang, Qihua; Wang, Tingmei
2015-10-01
The core-shell structured mesoporous silica nanomaterials (MSNs) are experiencing rapid development in many applications such as heterogeneous catalysis, bio-imaging and drug delivery wherein a large pore volume is desirable. We develop a one-pot method for large-scale synthesis of brain-like mesoporous silica nanocomposites based on the reasonable change of the intrinsic nature of the -Si-O-Si- framework of silica nanoparticles together with a selective etching strategy. The as-synthesized products show good monodispersion and a large pore volume of 1.0 cm3 g-1. The novelty of this approach lies in the use of an inorganic-organic hybrid layer to assist the creation of large-pore morphology on the outermost shell thereby promoting efficient mass transfer or storage. Importantly, the method is reliable and grams of products can be easily prepared. The morphology on the outermost silica shell can be controlled by simply adjusting the VTES-to-TEOS molar ratio (VTES: triethoxyvinylsilane, TEOS: tetraethyl orthosilicate) as well as the etching time. The as-synthesized products exhibit fluorescence performance by incorporating rhodamine B isothiocyanate (RITC) covalently into the inner silica walls, which provide potential application in bioimaging. We also demonstrate the applications of as-synthesized large-pore structured nanocomposites in drug delivery systems and stimuli-responsive nanoreactors for heterogeneous catalysis.The core-shell structured mesoporous silica nanomaterials (MSNs) are experiencing rapid development in many applications such as heterogeneous catalysis, bio-imaging and drug delivery wherein a large pore volume is desirable. We develop a one-pot method for large-scale synthesis of brain-like mesoporous silica nanocomposites based on the reasonable change of the intrinsic nature of the -Si-O-Si- framework of silica nanoparticles together with a selective etching strategy. The as-synthesized products show good monodispersion and a large pore volume of 1.0 cm3 g-1. The novelty of this approach lies in the use of an inorganic-organic hybrid layer to assist the creation of large-pore morphology on the outermost shell thereby promoting efficient mass transfer or storage. Importantly, the method is reliable and grams of products can be easily prepared. The morphology on the outermost silica shell can be controlled by simply adjusting the VTES-to-TEOS molar ratio (VTES: triethoxyvinylsilane, TEOS: tetraethyl orthosilicate) as well as the etching time. The as-synthesized products exhibit fluorescence performance by incorporating rhodamine B isothiocyanate (RITC) covalently into the inner silica walls, which provide potential application in bioimaging. We also demonstrate the applications of as-synthesized large-pore structured nanocomposites in drug delivery systems and stimuli-responsive nanoreactors for heterogeneous catalysis. Electronic supplementary information (ESI) available: The average particle size distribution of LPASN-1, LPASN-2 and LPASN-3; the wide-angle XRD pattern of LPASN-2/LPASN-3/LPASN-4; the catalytic properties of LPASN-PNIPAM at different temperatures (15 °C and 33 °C). See DOI: 10.1039/c5nr04123f
Ultrasonic sensing of powder densification
NASA Technical Reports Server (NTRS)
Lu, Yichi; Wadley, Haydn N. G.; Parthasarathi, Sanjai
1992-01-01
An independent scattering theory has been applied to the interpretation of ultrasonic velocity measurements made on porous metal samples produced either by a cold or a high-temperature compaction process. The results suggest that the pores in both processes are not spherical, an aspect ration of 1:3 fitting best with the data for low (less than 4 percent) pore volume fractions. For the hot compacted powders, the pores are smooth due to active diffusional processes during processing. For these types of voids, the results can be extended to a pore fraction of 10 percent, at which point voids form an interconnected network that violates the model assumptions. The cold pressed samples are not as well predicted by the theory because of poor particle bonding.
The influence of pore textures on the permeability of volcanic rocks
NASA Astrophysics Data System (ADS)
Mueller, S.; Spieler, O.; Scheu, B.; Dingwell, D.
2006-12-01
The permeability of a porous medium is strongly dependent on its porosity, as a higher proportion of pore volume is generally expected to lead to a greater probability of pore interconnectedness and the formation of a fluid-flow providing pathway. However, the relationship between permeability and porosity is not a unique one, as many other textural parameters may play an important role and substantially affect gas flow properties. Among these parameters are (a) the connection geometry (i.e. intergranular pore spaces in clastic sediments vs. bubble interconnections), (b) the pore sizes, (c) pore shape and (d) pore size distribution. The gas permeability of volcanic rocks may influence various eruptive processes. The transition from a quiescent degassing dome to rock failure (fragmentation) may, for example, be controlled by the rock's permeability, in as much as it affects the speed by which a gas overpressure in vesicles is reduced in response to decompression. It is therefore essential to understand and quantify influences of different pore textures on the degassing properties of volcanic rocks, as well as investigate the effects of permeability on eruptive processes. Using a modified shock-tube-based fragmentation apparatus, we have measured unsteady-state permeability at a high initial pressure differential. Following sudden decompression above the rock cylinder, pressurized gas flows through the sample in a steel autoclave. A transient 1D filtration code has been developed to calculate permeability using the experimental pressure decay curve within a defined volume below the sample. An external furnace around the autoclave and the use of compressed salt as sealant allows also measurements at high temperatures up to 800 °C. Over 130 permeability measurements have been performed on samples of different volcanic settings, covering a wide range of porosity. The results show a general positive relationship between porosity and permeability with a high data scatter. Analysis of the samples eruptive origin as well as the pore sizes, shapes and size distribution allow an estimation of the contribution of various textural effects to the overall permeability.
Wagner, Brian M.; Schuster, Stephanie A.; Boyes, Barry E.; Shields, Taylor J.; Miles, William L.; Haynes, Mark J.; Moran, Robert E.; Kirkland, Joseph J.; Schure, Mark R.
2017-01-01
To facilitate mass transport and column efficiency, solutes must have free access to particle pores to facilitate interactions with the stationary phase. To ensure this feature, particles should be used for HPLC separations which have pores sufficiently large to accommodate the solute without restricted diffusion. This paper describes the design and properties of superficially porous (also called Fused-Core®, core shell or porous shell) particles with very large (1000 Å) pores specifically developed for separating very large biomolecules and polymers. Separations of DNA fragments, monoclonal antibodies, large proteins and large polystyrene standards are used to illustrate the utility of these particles for efficient, high-resolution applications. PMID:28213987
Wagner, Brian M; Schuster, Stephanie A; Boyes, Barry E; Shields, Taylor J; Miles, William L; Haynes, Mark J; Moran, Robert E; Kirkland, Joseph J; Schure, Mark R
2017-03-17
To facilitate mass transport and column efficiency, solutes must have free access to particle pores to facilitate interactions with the stationary phase. To ensure this feature, particles should be used for HPLC separations which have pores sufficiently large to accommodate the solute without restricted diffusion. This paper describes the design and properties of superficially porous (also called Fused-Core ® , core shell or porous shell) particles with very large (1000Å) pores specifically developed for separating very large biomolecules and polymers. Separations of DNA fragments, monoclonal antibodies, large proteins and large polystyrene standards are used to illustrate the utility of these particles for efficient, high-resolution applications. Copyright © 2017 Elsevier B.V. All rights reserved.
Goldschen-Ohm, Marcel P.; Capes, Deborah L.; Oelstrom, Kevin M.; Chanda, Baron
2013-01-01
Voltage-dependent Na+ channels are crucial for electrical signalling in excitable cells. Membrane depolarization initiates asynchronous movements in four non-identical voltage-sensing domains of the Na+ channel. It remains unclear to what extent this structural asymmetry influences pore gating as compared with outwardly rectifying K+ channels, where channel opening results from a final concerted transition of symmetric pore gates. Here we combine single channel recordings, cysteine accessibility and voltage clamp fluorimetry to probe the relationships between voltage sensors and pore conformations in an inactivation deficient Nav1.4 channel. We observe three distinct conductance levels such that DI-III voltage sensor activation is kinetically correlated with formation of a fully open pore, whereas DIV voltage sensor movement underlies formation of a distinct subconducting pore conformation preceding inactivation in wild-type channels. Our experiments reveal that pore gating in sodium channels involves multiple transitions driven by asynchronous movements of voltage sensors. These findings shed new light on the mechanism of coupling between activation and fast inactivation in voltage-gated sodium channels. PMID:23322038
Dynamics of water in the amphiphilic pore of amyloid β fibrils
NASA Astrophysics Data System (ADS)
GhattyVenkataKrishna, Pavan K.; Mostofian, Barmak
2013-09-01
Alzheimers disease related amyloid peptide, Aβ, forms a fibrillar structure through aggregation. The aggregate is stabilized by a salt bridge that is responsible for the formation of an amphiphilic pore that can accommodate water molecules. None of the reported structures of Aβ, however, contain water. We present results from molecular dynamics simulations on dimeric Aβ fibrils solvated in water. Water penetrates and fills the amphiphilic pore increasing its volume. We observe a thick wire of water that is translationally and rotationally stiff in comparison to bulk water and may be essential for the stabilization of the amyloid Aβ protein.
Reactive Melt Infiltration Of Silicon Into Porous Carbon
NASA Technical Reports Server (NTRS)
Behrendt, Donald R.; Singh, Mrityunjay
1994-01-01
Report describes study of synthesis of silicon carbide and related ceramics by reactive melt infiltration of silicon and silicon/molybdenum alloys into porous carbon preforms. Reactive melt infiltration has potential for making components in nearly net shape, performed in less time and at lower temperature. Object of study to determine effect of initial pore volume fraction, pore size, and infiltration material on quality of resultant product.
DOE Office of Scientific and Technical Information (OSTI.GOV)
McCray, John; Navarre-Sitchler, Alexis; Mouzakis, Katherine
Geological carbon sequestration relies on the principle that CO{sub 2} injected deep into the subsurface is unable to leak to the atmosphere. Structural trapping by a relatively impermeable caprock (often mudstone such as a shale) is the main trapping mechanism that is currently relied on for the first hundreds of years. Many of the pores of the caprock are of micrometer to nanometer scale. However, the distribution, geometry and volume of porosity at these scales are poorly characterized. Differences in pore shape and size can cause variation in capillary properties and fluid transport resulting in fluid pathways with different capillarymore » entry pressures in the same sample. Prediction of pore network properties for distinct geologic environments would result in significant advancement in our ability to model subsurface fluid flow. Specifically, prediction of fluid flow through caprocks of geologic CO{sub 2} sequestration reservoirs is a critical step in evaluating the risk of leakage to overlying aquifers. The micro- and nanoporosity was analyzed in four mudstones using small angle neutron scattering (SANS). These mudstones are caprocks of formations that are currently under study or being used for carbon sequestration projects and include the Marine Tuscaloosa Group, the Lower Tuscaloosa Group, the upper and lower shale members of the Kirtland Formation, and the Pennsylvanian Gothic shale. Total organic carbon varies from <0.3% to 4% by weight. Expandable clay contents range from 10% to {approx}40% in the Gothic shale and Kirtland Formation, respectively. Neutrons effectively scatter from interfaces between materials with differing scattering length density (i.e. minerals and pores). The intensity of scattered neutrons, I(Q), where Q is the scattering vector, gives information about the volume of pores and their arrangement in the sample. The slope of the scattering data when plotted as log I(Q) vs. log Q provides information about the fractality or geometry of the pore network. Results from this study, combined with high-resolution TEM imaging, provide insight into the differences in volume and geometry of porosity between these various mudstones.« less
Wu, Chengtie; Miron, Richard; Sculean, Anton; Kaskel, Stefan; Doert, Thomas; Schulze, Renate; Zhang, Yufeng
2011-10-01
Boron is one of the trace elements in the human body which plays an important role in bone growth. Porous mesopore bioactive glass (MBG) scaffolds are proposed as potential bone regeneration materials due to their excellent bioactivity and drug-delivery ability. The aims of the present study were to develop boron-containing MBG (B-MBG) scaffolds by sol-gel method and to evaluate the effect of boron on the physiochemistry of B-MBG scaffolds and the response of osteoblasts to these scaffolds. Furthermore, the effect of dexamethasone (DEX) delivery in B-MBG scaffold system was investigated on the proliferation, differentiation and bone-related gene expression of osteoblasts. The composition, microstructure and mesopore properties (specific surface area, nano-pore volume and nano-pore distribution) of B-MBG scaffolds have been characterized. The effect of boron contents and large-pore porosity on the loading and release of DEX in B-MBG scaffolds were also investigated. The results have shown that the incorporation of boron into MBG scaffolds slightly decreases the specific surface area and pore volume, but maintains well-ordered mesopore structure and high surface area and nano-pore volume compared to non-mesopore bioactive glass. Boron contents in MBG scaffolds did not influence the nano-pore size distribution or the loading and release of DEX. B-MBG scaffolds have the ability to maintain a sustained release of DEX in a long-term span. Incorporating boron into MBG glass scaffolds led to a controllable release of boron ions and significantly improved the proliferation and bone-related gene expression (Col I and Runx2) of osteoblasts. Furthermore, the sustained release of DEX from B-MBG scaffolds significantly enhanced alkaline phosphatase (ALP) activity and gene expressions (Col I, Runx2, ALP and BSP) of osteoblasts. These results suggest that boron plays an important role in enhancing osteoblast proliferation in B-MBG scaffold system and DEX-loaded B-MBG scaffolds show great potential as a release system to enhance osteogenic property for bone tissue engineering application. Crown Copyright © 2011. Published by Elsevier Ltd. All rights reserved.
Construction of hierarchically porous metal–organic frameworks through linker labilization
Yuan, Shuai; Zou, Lanfang; Qin, Jun-Sheng; ...
2017-05-25
One major goal of metal–organic framework (MOF) research is the expansion of pore size and volume. Although many approaches have been attempted to increase the pore size of MOF materials, it is still a challenge to construct MOFs with precisely customized pore apertures for specific applications. W present a new method, namely linker labilization, to increase the MOF porosity and pore size, giving rise to hierarchical-pore architectures. Microporous MOFs with robust metal nodes and pro-labile linkers were initially synthesized. The mesopores were subsequently created as crystal defects through the splitting of a pro-labile-linker and the removal of the linker fragmentsmore » by acid treatment. We also demonstrate that linker labilization method can create controllable hierarchical porous structures in stable MOFs, which facilitates the diffusion and adsorption process of guest molecules to improve the performances of MOFs in adsorption and catalysis.« less
Construction of hierarchically porous metal-organic frameworks through linker labilization
NASA Astrophysics Data System (ADS)
Yuan, Shuai; Zou, Lanfang; Qin, Jun-Sheng; Li, Jialuo; Huang, Lan; Feng, Liang; Wang, Xuan; Bosch, Mathieu; Alsalme, Ali; Cagin, Tahir; Zhou, Hong-Cai
2017-05-01
A major goal of metal-organic framework (MOF) research is the expansion of pore size and volume. Although many approaches have been attempted to increase the pore size of MOF materials, it is still a challenge to construct MOFs with precisely customized pore apertures for specific applications. Herein, we present a new method, namely linker labilization, to increase the MOF porosity and pore size, giving rise to hierarchical-pore architectures. Microporous MOFs with robust metal nodes and pro-labile linkers were initially synthesized. The mesopores were subsequently created as crystal defects through the splitting of a pro-labile-linker and the removal of the linker fragments by acid treatment. We demonstrate that linker labilization method can create controllable hierarchical porous structures in stable MOFs, which facilitates the diffusion and adsorption process of guest molecules to improve the performances of MOFs in adsorption and catalysis.
Monitoring CO2 invasion processes at the pore scale using geological labs on chip.
Morais, S; Liu, N; Diouf, A; Bernard, D; Lecoutre, C; Garrabos, Y; Marre, S
2016-09-21
In order to investigate at the pore scale the mechanisms involved during CO2 injection in a water saturated pore network, a series of displacement experiments is reported using high pressure micromodels (geological labs on chip - GLoCs) working under real geological conditions (25 < T (°C) < 75 and 4.5 < p (MPa) < 8). The experiments were focused on the influence of three experimental parameters: (i) the p, T conditions, (ii) the injection flow rates and (iii) the pore network characteristics. By using on-chip optical characterization and imaging approaches, the CO2 saturation curves as a function of either time or the number of pore volume injected were determined. Three main mechanisms were observed during CO2 injection, namely, invasion, percolation and drying, which are discussed in this paper. Interestingly, besides conventional mechanisms, two counterintuitive situations were observed during the invasion and drying processes.
Construction of hierarchically porous metal–organic frameworks through linker labilization
DOE Office of Scientific and Technical Information (OSTI.GOV)
Yuan, Shuai; Zou, Lanfang; Qin, Jun-Sheng
One major goal of metal–organic framework (MOF) research is the expansion of pore size and volume. Although many approaches have been attempted to increase the pore size of MOF materials, it is still a challenge to construct MOFs with precisely customized pore apertures for specific applications. W present a new method, namely linker labilization, to increase the MOF porosity and pore size, giving rise to hierarchical-pore architectures. Microporous MOFs with robust metal nodes and pro-labile linkers were initially synthesized. The mesopores were subsequently created as crystal defects through the splitting of a pro-labile-linker and the removal of the linker fragmentsmore » by acid treatment. We also demonstrate that linker labilization method can create controllable hierarchical porous structures in stable MOFs, which facilitates the diffusion and adsorption process of guest molecules to improve the performances of MOFs in adsorption and catalysis.« less
Code of Federal Regulations, 2011 CFR
2011-01-01
... which there is recurrent movement, which is usually indicated by small, periodic displacements or... of fluids, expressed as the ratio of the volume of interconnected pores and openings to the volume of... displacement of the side relative to one another parallel to the fracture or zone of fractures. Faulting means...
Code of Federal Regulations, 2012 CFR
2012-01-01
... which there is recurrent movement, which is usually indicated by small, periodic displacements or... of fluids, expressed as the ratio of the volume of interconnected pores and openings to the volume of... displacement of the side relative to one another parallel to the fracture or zone of fractures. Faulting means...
Code of Federal Regulations, 2013 CFR
2013-01-01
... which there is recurrent movement, which is usually indicated by small, periodic displacements or... of fluids, expressed as the ratio of the volume of interconnected pores and openings to the volume of... displacement of the side relative to one another parallel to the fracture or zone of fractures. Faulting means...
Code of Federal Regulations, 2014 CFR
2014-01-01
... which there is recurrent movement, which is usually indicated by small, periodic displacements or... of fluids, expressed as the ratio of the volume of interconnected pores and openings to the volume of... displacement of the side relative to one another parallel to the fracture or zone of fractures. Faulting means...
NASA Astrophysics Data System (ADS)
Demberg, Kerstin; Laun, Frederik Bernd; Windschuh, Johannes; Umathum, Reiner; Bachert, Peter; Kuder, Tristan Anselm
2017-02-01
Diffusion pore imaging is an extension of diffusion-weighted nuclear magnetic resonance imaging enabling the direct measurement of the shape of arbitrarily formed, closed pores by probing diffusion restrictions using the motion of spin-bearing particles. Examples of such pores comprise cells in biological tissue or oil containing cavities in porous rocks. All pores contained in the measurement volume contribute to one reconstructed image, which reduces the problem of vanishing signal at increasing resolution present in conventional magnetic resonance imaging. It has been previously experimentally demonstrated that pore imaging using a combination of a long and a narrow magnetic field gradient pulse is feasible. In this work, an experimental verification is presented showing that pores can be imaged using short gradient pulses only. Experiments were carried out using hyperpolarized xenon gas in well-defined pores. The phase required for pore image reconstruction was retrieved from double diffusion encoded (DDE) measurements, while the magnitude could either be obtained from DDE signals or classical diffusion measurements with single encoding. The occurring image artifacts caused by restrictions of the gradient system, insufficient diffusion time, and by the phase reconstruction approach were investigated. Employing short gradient pulses only is advantageous compared to the initial long-narrow approach due to a more flexible sequence design when omitting the long gradient and due to faster convergence to the diffusion long-time limit, which may enable application to larger pores.
Regional Disparities in Online Map User Access Volume and Determining Factors
NASA Astrophysics Data System (ADS)
Li, R.; Yang, N.; Li, R.; Huang, W.; Wu, H.
2017-09-01
The regional disparities of online map user access volume (use `user access volume' in this paper to indicate briefly) is a topic of growing interest with the increment of popularity in public users, which helps to target the construction of geographic information services for different areas. At first place we statistically analysed the online map user access logs and quantified these regional access disparities on different scales. The results show that the volume of user access is decreasing from east to the west in China as a whole, while East China produces the most access volume; these cities are also the crucial economic and transport centres. Then Principal Component Regression (PCR) is applied to explore the regional disparities of user access volume. A determining model for Online Map access volume is proposed afterwards, which indicates that area scale is the primary determining factor for regional disparities, followed by public transport development level and public service development level. Other factors like user quality index and financial index have very limited influence on the user access volume. According to the study of regional disparities in user access volume, map providers can reasonably dispatch and allocate the data resources and service resources in each area and improve the operational efficiency of the Online Map server cluster.
Soft-Template-Synthesized Mesoporous Carbon for Oral Drug Delivery
DOE Office of Scientific and Technical Information (OSTI.GOV)
Saha, Dipendu; Warren, Kaitlyn E; Naskar, Amit K
Template-synthesized mesoporous carbons were successfully used in in vitro investigations of controlled delivery of three model drugs, captopril, furosemide, and ranitidine hydrochloride. Captopril and furosemide exhibited desorption kinetics over 30 40 h, and ranitidine HCl had a complete release time of 5 10 h. As evident from the slow release kinetics, we contend that our mesoporous carbon is an improved drug-delivery medium compared to state-of-the-art porous silica-based substrates. The mesoporous carbons, synthesized from phloroglucinol and lignin, a synthetic and a sustainable precursor, respectively, exhibit BET surface area of 200 400 m2 g-1 and pore volume of 0.2 0.6 cm3 g-1.more » The phloroglucinol-based carbon has narrower pore widths and higher pore volume than the lignin-derived counterpart and maintains a longer release time. Numerical modeling of the release kinetics data reveals that the diffusivities of all the drugs from lignin-based carbon media are of equivalent magnitude (10-22 to 10-24 m2 s-1). However, a tailored reduction of pore width in the sorbent reduces the diffusivity of smaller drug molecules (captopril) by an order of magnitude. Thus, engineered pore morphology in our synthesized carbon sorbent, along with its potential to tailor the chemistry of its interaction with sorbet, can be exploited for optimal delivery system of a preferred drug within its therapeutic level and below the level of toxicity.« less
Lee, Myung W.; Collett, Timothy S.
2005-01-01
Physical properties of gas-hydrate-bearing sediments depend on the pore-scale interaction between gas hydrate and porous media as well as the amount of gas hydrate present. Well log measurements such as proton nuclear magnetic resonance (NMR) relaxation and electromagnetic propagation tool (EPT) techniques depend primarily on the bulk volume of gas hydrate in the pore space irrespective of the pore-scale interaction. However, elastic velocities or permeability depend on how gas hydrate is distributed in the pore space as well as the amount of gas hydrate. Gas-hydrate saturations estimated from NMR and EPT measurements are free of adjustable parameters; thus, the estimations are unbiased estimates of gas hydrate if the measurement is accurate. However, the amount of gas hydrate estimated from elastic velocities or electrical resistivities depends on many adjustable parameters and models related to the interaction of gas hydrate and porous media, so these estimates are model dependent and biased. NMR, EPT, elastic-wave velocity, electrical resistivity, and permeability measurements acquired in the Mallik 5L-38 well in the Mackenzie Delta, Canada, show that all of the well log evaluation techniques considered provide comparable gas-hydrate saturations in clean (low shale content) sandstone intervals with high gas-hydrate saturations. However, in shaly intervals, estimates from log measurement depending on the pore-scale interaction between gas hydrate and host sediments are higher than those estimates from measurements depending on the bulk volume of gas hydrate.
Carter, D.S.
1996-01-01
This report describes a method for the determination of atrazine, desethylatrazine, deisopropylatrazine, didealkylatrazine, and hydroxyatrazine from soil pore waters by use of solid-phase extractionfollowed by chemical derivatization and gas chromatography/mass spectrometry. The analytes are isolated from the pore-water matrix byextraction onto a graphitized carbon-black cartridge. The cartridge is dried under vacuum, and adsorbed analytes are removed by elution with ethyl acetate followed by dichloromethane/methanol (7:3, volume/volume). Water is removed from the ethyl acetate fraction on an anhydrous sodium sulfate column. The combined fractions are solvent exchanged into acetonitrile, evaporated by use of a nitrogen stream, and derivatized by use of N- methyl-N-(tert-butyldimethylsilyl)- trifluoroacetamide. The derivatized extracts are analyzed by capillary-column gaschromatography/electron-impact mass spectrometry in the scan mode. Estimated method detection limits range from 0.03 to 0.07 micrograms per liter. The mean recoveries of all analytes and surrogates determined at 0.74 to 0.82 micrograms per liter in reagent water in soil pore water were 94 percent and 98 percent, respectively. The mean recoveries of all analytes and surrogates determined at 7.4 to 8.2 micrograms per liter in reagent water and in soil pore water were 96 percent and 97 percent,respectively. Recoveries were 90 percent or higher, regardless of analyte concentration or matrix composition, for all compounds excepthydroxyatrazine, whose recoveries were slightly lower (77 percent) at the low concentration.
Hadi, Pejman; Yeung, Kit Ying; Guo, Jiaxin; Wang, Huaimin; McKay, Gordon
2016-04-01
This paper aims at the sustainable development of activated carbons for value-added applications from the waste tyre pyrolysis product, tyre char, in order to make pyrolysis economically favorable. Two activation process parameters, activation temperature (900, 925, 950 and 975 °C) and residence time (2, 4 and 6 h) with steam as the activating agent have been investigated. The textural properties of the produced tyre char activated carbons have been characterized by nitrogen adsorption-desorption experiments at -196 °C. The activation process has resulted in the production of mesoporous activated carbons confirmed by the existence of hysteresis loops in the N2 adsorption-desorption curves and the pore size distribution curves obtained from BJH method. The BET surface area, total pore volume and mesopore volume of the activated carbons from tyre char have been improved to 732 m(2)/g, 0.91 cm(3)/g and 0.89 cm(3)/g, respectively. It has been observed that the BET surface area, mesopore volume and total pore volume increased linearly with burnoff during activation in the range of experimental parameters studied. Thus, yield-normalized surface area, defined as the surface area of the activated carbon per gram of the precursor, has been introduced to optimize the activation conditions. Accordingly, the optimized activation conditions have been demonstrated as an activation temperature of 975 °C and an activation time of 4 h. Copyright © 2016 Elsevier Ltd. All rights reserved.
Lim, Won-Gwang; Mun, Yeongdong; Cho, Ara; Jo, Changshin; Lee, Seonggyu; Han, Jeong Woo; Lee, Jinwoo
2018-05-14
Lithium-sulfur (Li-S) batteries are regarded as potential high-energy storage devices due to their outstanding energy density. However, the low electrical conductivity of sulfur, dissolution of the active material, and sluggish reaction kinetics cause poor cycle stability and rate performance. A variety of approaches have been attempted to resolve the above issues and achieve enhanced electrochemical performance. However, inexpensive multifunctional host materials which can accommodate large quantities of sulfur and exhibit high electrode density are not widely available, which hinders the commercialization of Li-S batteries. Herein, mesoporous carbon microspheres with ultrahigh pore volume are synthesized, followed by the incorporation of Fe-N-C molecular catalysts into the mesopores, which can act as sulfur hosts. The ultrahigh pore volume of the prepared host material can accommodate up to ∼87 wt % sulfur, while the uniformly controlled spherical morphology and particle size of the carbon microspheres enable high areal/volumetric capacity with high electrode density. Furthermore, the uniform distribution of Fe-N-C (only 0.33 wt %) enhances the redox kinetics of the conversion reaction of sulfur and efficiently captures the soluble intermediates. The resulting electrode with 5.2 mg sulfur per cm 2 shows excellent cycle stability and 84% retention of the initial capacity even after 500 cycles at a 3 C rate.
Zhang, Shujuan; Shao, Ting; Kose, H Selcen; Karanfil, Tanju
2010-08-15
Adsorption of three aromatic organic compounds (AOCs) by four types of carbonaceous adsorbents [a granular activated carbon (HD4000), an activated carbon fiber (ACF10), two single-walled carbon nanotubes (SWNT, SWNT-HT), and a multiwalled carbon nanotube (MWNT)] with different structural characteristics but similar surface polarities was examined in aqueous solutions. Isotherm results demonstrated the importance of molecular sieving and micropore effects in the adsorption of AOCs by carbonaceous porous adsorbents. In the absence of the molecular sieving effect, a linear relationship was found between the adsorption capacities of AOCs and the surface areas of adsorbents, independent of the type of adsorbent. On the other hand, the pore volume occupancies of the adsorbents followed the order of ACF10 > HD4000 > SWNT > MWNT, indicating that the availability of adsorption site was related to the pore size distributions of the adsorbents. ACF10 and HD4000 with higher microporous volumes exhibited higher adsorption affinities to low molecular weight AOCs than SWNT and MWNT with higher mesopore and macropore volumes. Due to their larger pore sizes, SWNTs and MWNTs are expected to be more efficient in adsorption of large size molecules. Removal of surface oxygen-containing functional groups from the SWNT enhanced adsorption of AOCs.
Fluctuation of Ultrafiltration Coefficient of Hemodialysis Membrane During Reuse
NASA Astrophysics Data System (ADS)
Arif, Idam; Christin
2010-12-01
Hemodialysis treatment for patient with kidney failure is to regulate body fluid and to excrete waste products of metabolism. The patient blood and the dialyzing solution (dialysate) are flowed counter currently in a dialyzer to allow volume flux of fluid and diffusion of solutes from the blood to the dialysate through a semipermiable membrane. The volume flux of fluid depends on the hydrostatic and the osmotic pressure difference between the blood and the dialysate. It also depends on the membrane parameter that represents how the membrane allows the fluid and the solutes to move across as a result of the pressure difference, known as the ultrafiltration coefficient Kuf. The coefficient depends on the number and the radius of membrane pores for the movement of the fluids and the solutes across the membrane. The measured membrane ultrafiltration coefficient of reused dialyzer shows fluctuation between one uses to another without any significant trend of change. This indicates that the cleaning process carried out before reuse does not cause perfect removal of clots that happen in the previous use. Therefore the unblocked pores are forced to work hardly to obtain targeted volume flux in a certain time of treatment. This may increase the unblocked pore radius. Reuse is stopped when there is indication of blood leakage during the hemodialysis treatment.
NASA Astrophysics Data System (ADS)
Wójcicki, Adam; Jarosiński, Marek
2017-04-01
For the stage of shale gas production, like in the USA, prediction of the CO2 storage potential in shale reservoir can be performed by dynamic modeling. We have made an attempt to estimate this potential at an early stage of shale gas exploration in the Lower Paleozoic Baltic Basin, based on data from 3,800 m deep vertical well (without hydraulic fracking stimulation), supplemented with additional information from neighboring boreholes. Such an attempt makes a sense as a first guess forecast for company that explores a new basin. In our approach, the storage capacity is build by: (1) sorption potential of organic matter, (2) open pore space and (3) potential fracture space. the sequence. our estimation is done for 120 m long shale sequence including three shale intervals enriched with organic mater. Such an interval is possible to be fracked from a single horizontal borehole as known from hydraulic fracture treatment in the other boreholes in this region. The potential for adsorbed CO2 is determined from Langmuir isotherm parameters taken from laboratory measurements in case of both CH4 and CO2 adsorption, as well as shale density and volume. CO2 has approximately three times higher sorption capacity than methane to the organic matter contained in the Baltic Basin shales. Finally, due to low permeability of shale we adopt the common assumption for the USA shale basins that the CO2 will be able to reach effectively only 10% of theoretical total sorption volume. The pore space capacity was estimated by utilizing results of laboratory measurements of dynamic capacity for pores bigger than 10 nm. It is assumed for smaller pores adsorption prevails over free gas. Similarly to solution for sorption, we have assumed that only 10 % of the tight pore space will be reached by CO2. For fracture space we have considered separately natural (tectonic-origin) and technological (potentially produced by hydraulic fracturing treatment) fractures. From fracture density profile and typical permeability of fractures under lithostatic stress we inferred negligible open space of natural fractures. Technological fracture space was calculated as an potential for hydraulic stimulation of vertical fractures until, due to elastic expansion of reservoir, the horizontal minimum stress equals the vertical one. In such a case, horizontal fractures start to open and the stimulation process gets to fail. Based on elastic anisotropy and tectonic stress differentiation, the maximum hydraulic horizontal extension was calculated for separated shale complexes. For further storage capacity we assumed that technological fracture space create primary pathway for CO2 transport is entirely accessible for the CO2. In general, the CO2 sorption capacity makes the predominant contribution and fracture space capacity is comparable or smaller than pore space contribution. When compare this with the best recognized Marcellus shale basin we can see that our calculations for the 35 m depth interval comprising formations with the higher TOC content show a slightly lower value than in the case of Marcellus.
Evolutionarily conserved intracellular gate of voltage-dependent sodium channels
NASA Astrophysics Data System (ADS)
Oelstrom, Kevin; Goldschen-Ohm, Marcel P.; Holmgren, Miguel; Chanda, Baron
2014-03-01
Members of the voltage-gated ion channel superfamily (VGIC) regulate ion flux and generate electrical signals in excitable cells by opening and closing pore gates. The location of the gate in voltage-gated sodium channels, a founding member of this superfamily, remains unresolved. Here we explore the chemical modification rates of introduced cysteines along the S6 helix of domain IV in an inactivation-removed background. We find that state-dependent accessibility is demarcated by an S6 hydrophobic residue; substituted cysteines above this site are not modified by charged thiol reagents when the channel is closed. These accessibilities are consistent with those inferred from open- and closed-state structures of prokaryotic sodium channels. Our findings suggest that an intracellular gate composed of a ring of hydrophobic residues is not only responsible for regulating access to the pore of sodium channels, but is also a conserved feature within canonical members of the VGIC superfamily.
An analysis of electrical conductivity model in saturated porous media
NASA Astrophysics Data System (ADS)
Cai, J.; Wei, W.; Qin, X.; Hu, X.
2017-12-01
Electrical conductivity of saturated porous media has numerous applications in many fields. In recent years, the number of theoretical methods to model electrical conductivity of complex porous media has dramatically increased. Nevertheless, the process of modeling the spatial conductivity distributed function continues to present challenges when these models used in reservoirs, particularly in porous media with strongly heterogeneous pore-space distributions. Many experiments show a more complex distribution of electrical conductivity data than the predictions derived from the experiential model. Studies have observed anomalously-high electrical conductivity of some low-porosity (tight) formations compared to more- porous reservoir rocks, which indicates current flow in porous media is complex and difficult to predict. Moreover, the change of electrical conductivity depends not only on the pore volume fraction but also on several geometric properties of the more extensive pore network, including pore interconnection and tortuosity. In our understanding of electrical conductivity models in porous media, we study the applicability of several well-known methods/theories to electrical characteristics of porous rocks as a function of pore volume, tortuosity and interconnection, to estimate electrical conductivity based on the micro-geometrical properties of rocks. We analyze the state of the art of scientific knowledge and practice for modeling porous structural systems, with the purpose of identifying current limitations and defining a blueprint for future modeling advances. We compare conceptual descriptions of electrical current flow processes in pore space considering several distinct modeling approaches. Approaches to obtaining more reasonable electrical conductivity models are discussed. Experiments suggest more complex relationships between electrical conductivity and porosity than experiential models, particularly in low-porosity formations. However, the available theoretical models combined with simulations do provide insight to how microscale physics affects macroscale electrical conductivity in porous media.
NASA Astrophysics Data System (ADS)
Imhoff, P. T.; Nakhli, S. A. A.; Mills, G.; Yudi, Y.; Abera, K.; Williams, R.; Manahiloh, K. N.; Willson, C. S.
2017-12-01
Biochar has been proposed as an amendment to stormwater infiltration media to enhance pollutant capture (metals, organics) or transformation (e.g., nitrate). Because stormwater media must maintain sufficient infiltration capacity, it is critical that biochar amendment not reduce saturated hydraulic conductivity. We present experimental measurements of saturated hydraulic conductivity for mixtures of wood biochar, sieved to various size fractions, and uniform sands or bioretention media (mixtures of sand, clay, and sawdust). While the influence of biochar on the inter particle pore volume of the mixtures explained most changes in hydraulic conductivity, for mixtures containing large biochar particles results were unexpected. For example, while large biochar particles (2 - 4.75 mm) increased inter particle porosity from 0.35 to 0.48 for a sand/biochar mixture, hydraulic conductivity decreased from 820 ± 90 cm/h to 323 ± 2 cm/h. To understand this and other unusual data, biochar was doped with 3% CsCl, mixed with uniform sand using different packing techniques, and analyzed with X-ray computed tomography to assess biochar distribution and pore structure. Depending on packing technique, biochar particles were either segregated or uniformly mixed, which influenced pore structure. Biochar content and inter particle pore volume determined from X-ray images were in excellent agreement with experimental data (< 5% difference). Grain-based algorithms were then used to generate physically-representative pore networks, and single-phase permeability models were employed to estimate saturated hydraulic conductivity of sand and biochar-amended sand packings for specimens prepared with different packing techniques. Results from these analyses will be presented and compared with experimental measurements to elucidate the mechanisms by which large biochar particles alter the saturated hydraulic conductivity of engineered media.
NASA Astrophysics Data System (ADS)
Biggin, C.; Ota, K.; Siittari-Kauppi, M.; Moeri, A.
2004-12-01
In the context of a repository for radioactive waste, 'matrix diffusion' is used to describe the process by which solute, flowing in distinct flow paths, penetrates the surrounding rock matrix. Diffusion into the matrix occurs in a connected system of pores or microfractures. Matrix diffusion provides a mechanism for greatly enlarging the area of rock surface in contact with advecting radionuclides, from that of the flow path surfaces (and infills), to a much larger portion of the bulk rock and increases the global pore volume which can retard radionuclides. In terms of a repository safety assessment, demonstration of a significant depth of diffusion-accessible pore space may result in a significant delay in the calculated release of any escaping radionuclides to the environment and a dramatic reduction in the resulting concentration released into the biosphere. For the last decade, Nagra has investigated in situ matrix diffusion at the Grimsel Test Site (GTS) in the Swiss Alps. The in situ investigations offer two distinct advantages to those performed in the lab, namely: 1. Lab-based determination of porosity and diffusivity can lead to an overestimation of matrix diffusion due to stress relief when the rock is sampled (which would overestimate the retardation in the geosphere) 2. Lab-based analysis usually examines small (cm scale) samples and cannot therefore account for any matrix heterogeneity over the hundreds or thousands of metres a typical flow path The in situ investigations described began with the Connected Porosity project, wherein a specially developed acrylic resin was injected into the rock matrix to fill the pore space and determine the depth of connected porosity. The resin was polymerised in situ and the entire rock mass removed by overcoring. The results indicated that lab-based porosity measurements may be two to three times higher than those obtained in situ. While the depth of accessible matrix from a water-conducting feature assumed in repository performance assessments is generally 1 to 10 cm, the results from the GTS in situ experiment suggested depths of several metres could be more appropriate. More recently, the Pore Space Geometry (PSG) experiment at the GTS has used a C-14 doped acrylic resin, combined with state-of-the-art digital beta autoradiography and fluorescence detection to examine a larger area of rock for determination of porosity and the degree of connected pore space. Analysis is currently ongoing and the key findings will be reported in this paper. Starting at the GTS in 2005, the Long-term Diffusion (LTD) project will investigate such processes over spatial and temporal scales more relevant to a repository than traditional lab-based experiments. In the framework of this experiment, long-term (10 to 50 years) in situ diffusion experiments and resin injection experiments are planned to verify current models for matrix diffusion as a radionuclide retardation process. This paper will discuss the findings of the first two experiments and their significance to repository safety assessments before discussing the strategy for the future in relation to the LTD project.
Porous Materials from Thermally Activated Kaolinite: Preparation, Characterization and Application
Luo, Jun; Jiang, Tao; Li, Guanghui; Peng, Zhiwei; Rao, Mingjun; Zhang, Yuanbo
2017-01-01
In the present study, porous alumina/silica materials were prepared by selective leaching of silicon/aluminum constituents from thermal-activated kaolinite in inorganic acid or alkali liquor. The correlations between the characteristics of the prepared porous materials and the dissolution properties of activated kaolinite were also investigated. The results show that the specific surface area (SSA) of porous alumina/silica increases with silica/alumina dissolution, but without marked change of the BJH pore size. Furthermore, change in pore volume is more dependent on activation temperature. The porous alumina and silica obtained from alkali leaching of kaolinite activated at 1150 °C for 15 min and acid leaching of kaolinite activated at 850 °C for 15 min are mesoporous, with SSAs, BJH pore sizes and pore volumes of 55.8 m2/g and 280.3 m2/g, 6.06 nm and 3.06 nm, 0.1455 mL/g and 0.1945 mL/g, respectively. According to the adsorption tests, porous alumina has superior adsorption capacities for Cu2+, Pb2+ and Cd2+ compared with porous silica and activated carbon. The maximum capacities of porous alumina for Cu2+, Pb2+ and Cd2+ are 134 mg/g, 183 mg/g and 195 mg/g, respectively, at 30 °C. PMID:28773002
Prediction of Hot Tearing Using a Dimensionless Niyama Criterion
NASA Astrophysics Data System (ADS)
Monroe, Charles; Beckermann, Christoph
2014-08-01
The dimensionless form of the well-known Niyama criterion is extended to include the effect of applied strain. Under applied tensile strain, the pressure drop in the mushy zone is enhanced and pores grow beyond typical shrinkage porosity without deformation. This porosity growth can be expected to align perpendicular to the applied strain and to contribute to hot tearing. A model to capture this coupled effect of solidification shrinkage and applied strain on the mushy zone is derived. The dimensionless Niyama criterion can be used to determine the critical liquid fraction value below which porosity forms. This critical value is a function of alloy properties, solidification conditions, and strain rate. Once a dimensionless Niyama criterion value is obtained from thermal and mechanical simulation results, the corresponding shrinkage and deformation pore volume fractions can be calculated. The novelty of the proposed method lies in using the critical liquid fraction at the critical pressure drop within the mushy zone to determine the onset of hot tearing. The magnitude of pore growth due to shrinkage and deformation is plotted as a function of the dimensionless Niyama criterion for an Al-Cu alloy as an example. Furthermore, a typical hot tear "lambda"-shaped curve showing deformation pore volume as a function of alloy content is produced for two Niyama criterion values.
Adsorption of sulfur dioxide on ammonia-treated activated carbon fibers
Mangun, C.L.; DeBarr, J.A.; Economy, J.
2001-01-01
A series of activated carbon fibers (ACFs) and ammonia-treated ACFs prepared from phenolic fiber precursors have been studied to elucidate the role of pore size, pore volume, and pore surface chemistry on adsorption of sulfur dioxide and its catalytic conversion to sulfuric acid. As expected, the incorporation of basic functional groups into the ACFs was shown as an effective method for increasing adsorption of sulfur dioxide. The adsorption capacity for dry SO2 did not follow specific trends; however the adsorption energies calculated from the DR equation were found to increase linearly with nitrogen content for each series of ACFs. Much higher adsorption capacities were achieved for SO2 in the presence of oxygen and water due to its catalytic conversion to H2SO4. The dominant factor for increasing adsorption of SO2 from simulated flue gas for each series of fibers studied was the weight percent of basic nitrogen groups present. In addition, the adsorption energies calculated for dry SO2 were shown to be linearly related to the adsorption capacity of H2SO4 from this flue gas for all fibers. It was shown that optimization of this parameter along with the pore volume results in higher adsorption capacities for removal of SO2 from flue gases. ?? 2001 Elsevier Science Ltd. All rights reserved.
Chang, Seong Jin; Jeong, Su-Gwang; Lee, Jongki; Kim, Taeyeon; Park, Kyung-Won; Lee, Dong Ryeol; Kim, Sumin
2017-01-01
Porous carbon materials are advantageous in adsorbing pollutants due to their wide range of specific surface areas, pore diameter, and pore volume. Among the porous carbon materials in the current study, expanded graphite, xGnP, xGnP C-300, xGnP C-500, and xGnP C-750 were prepared as adsorbent materials. Brunauer–Emmett–Teller (BET) analysis was conducted to select the adsorbent material through the analysis of the specific surface area, pore size, and pore volume of the prepared porous carbon materials. Morphological analysis using SEM was also performed. The xGnP C-500 as adsorbent material was applied to a mortar adhesive that is widely used in the installation of interior building materials. The toluene adsorption performances of the specimens were evaluated using 20 L small chamber. Furthermore, the performance of the mortar adhesive, as indicated by the shear bond strength, length change rate, and water retention rate, was analyzed according to the required test method specified in the Korean standards. It was confirmed that for the mortar adhesives prepared using the xGnP C-500 as adsorbent material, the toluene adsorption performance was excellent and satisfied the required physical properties. PMID:28773214
[Micropore filters for measuring red blood cell deformability and their pore diameters].
Niu, X; Yan, Z
2001-09-01
Micropore filters are the most important components in micropore filtration testes for assessing red blood cell (RBC) deformability. With regard to their appearance and filtration behaviors, comparisons are made for different kinds of filters currently in use. Nickel filters with regular geometric characteristics are found to be more sensitive to the effects of physical, chemical, especially pathological factors on the RBC deformability. We have critically reviewed the following viewpoint that filters with 3 microns pore diameter are more sensitive to cell volume than to internal viscosity while filters with 5 microns pore diameter are just the opposite. After analyzing the experiment results with 3 microns and 5 microns filters, we point out that filters with smaller pore diameters are more suitable for assessing the RBC deformability.
Multi-scale modeling of multi-component reactive transport in geothermal aquifers
NASA Astrophysics Data System (ADS)
Nick, Hamidreza M.; Raoof, Amir; Wolf, Karl-Heinz; Bruhn, David
2014-05-01
In deep geothermal systems heat and chemical stresses can cause physical alterations, which may have a significant effect on flow and reaction rates. As a consequence it will lead to changes in permeability and porosity of the formations due to mineral precipitation and dissolution. Large-scale modeling of reactive transport in such systems is still challenging. A large area of uncertainty is the way in which the pore-scale information controlling the flow and reaction will behave at a larger scale. A possible choice is to use constitutive relationships relating, for example the permeability and porosity evolutions to the change in the pore geometry. While determining such relationships through laboratory experiments may be limited, pore-network modeling provides an alternative solution. In this work, we introduce a new workflow in which a hybrid Finite-Element Finite-Volume method [1,2] and a pore network modeling approach [3] are employed. Using the pore-scale model, relevant constitutive relations are developed. These relations are then embedded in the continuum-scale model. This approach enables us to study non-isothermal reactive transport in porous media while accounting for micro-scale features under realistic conditions. The performance and applicability of the proposed model is explored for different flow and reaction regimes. References: 1. Matthäi, S.K., et al.: Simulation of solute transport through fractured rock: a higher-order accurate finite-element finite-volume method permitting large time steps. Transport in porous media 83.2 (2010): 289-318. 2. Nick, H.M., et al.: Reactive dispersive contaminant transport in coastal aquifers: Numerical simulation of a reactive Henry problem. Journal of contaminant hydrology 145 (2012), 90-104. 3. Raoof A., et al.: PoreFlow: A Complex pore-network model for simulation of reactive transport in variably saturated porous media, Computers & Geosciences, 61, (2013), 160-174.
NASA Astrophysics Data System (ADS)
Cilona, A.; Arzilli, F.; Mancini, L.; Emanuele, T.
2014-12-01
Porous carbonates form important reservoirs for water and hydrocarbons. The fluid flow properties of carbonate reservoirs may be affected by post-depositional processes (e.g., mechanical and chemical), which need to be quantified. Field-based studies described bed-parallel compaction bands (CBs) within carbonates with a wide range of porosities. These burial-related structures accommodate volumetric strain by grain rotation, translation, pore collapse and pressure solution. Recently, the same structures have been reproduced for the first time in the laboratory by performing triaxial compaction experiments on porous grainstones. These laboratory studies characterized and compared the microstructures of natural and laboratory CBs, but no analysis of pore connectivity has been performed. In this paper, we use an innovative approach to characterize the pore networks (e.g. porosity, connectivity) of natural and laboratory CBs and compare them with the host rock one. We collected the data using the synchrotron X-ray computed microtomography technique at the SYRMEP beamline of the Elettra-Sincrotrone Trieste Laboratory (Italy). Quantitative analyses of the samples were performed with the Pore3D software library. The porosity was calculated from segmented 3D images of pristine and deformed carbonates. A process of skeletonization was then applied to quantify the number of connected pores within the rock volume. The analysis of the skeleton allowed us to highlight the differences between natural and laboratory CBs, and to investigate how pore connectivity evolves as a function of different deformation pathways. Both pore volume and connectivity are reduced within the CBs respect to the pristine rock and the natural CB has a lower porosity with respect to the laboratory one. The grain contacts in the natural CB are welded, whereas in the laboratory one they have more irregular shapes and grain crushing is the predominant process.
Kitt, Jay P; Harris, Joel M
2015-05-19
Octanol-water partitioning is one of the most widely used predictors of hydrophobicity and lipophilicity. Traditional methods for measuring octanol-water partition coefficients (K(ow)), including shake-flasks and generator columns, require hours for equilibration and milliliter quantities of sample solution. These challenges have led to development of smaller-scale methods for measuring K(ow). Recent advances in microfluidics have produced faster and smaller-volume approaches to measuring K(ow). As flowing volumes are reduced, however, separation of water and octanol prior to measurement and detection in small volumes of octanol phase are especially challenging. In this work, we reduce the receiver volume of octanol-water partitioning measurements from current practice by six-orders-of-magnitude, to the femtoliter scale, by using a single octanol-filled reversed-phase, octadecylsilane-modified (C18-silica) chromatographic particle as a collector. The fluid-handling challenges of working in such small volumes are circumvented by eliminating postequilibration phase separation. Partitioning is measured in situ within the pore-confined octanol phase using confocal Raman microscopy, which is capable of detecting and quantifying a wide variety of molecular structures. Equilibration times are fast (less than a minute) because molecular diffusion is efficient over distance scales of micrometers. The demonstrated amount of analyte needed to carry out a measurement is very small, less than 50 fmol, which would be a useful attribute for drug screening applications or testing of small quantities of environmentally sensitive compounds. The method is tested for measurements of pH-dependent octanol-water partitioning of naphthoic acid, and the results are compared to both traditional shake-flask measurements and sorption onto C18-modified silica without octanol present within the pores.
High rate capacitive performance of single-walled carbon nanotube aerogels
Van Aken, Katherine L.; Pérez, Carlos R.; Oh, Youngseok; ...
2015-05-30
Single-walled carbon nanotube (SWCNT) aerogels produced by critical-point-drying of wet-gel precursors exhibit unique properties, such as high surface-area-to-volume and strength-to-weight ratios. They are free-standing, are binder-free, and can be scaled to thicknesses of more than 1 mm. In this paper, we examine the electric double layer capacitive behavior of these materials using a common room temperature ionic liquid electrolyte, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMI-TFSI). Electrochemical performance is assessed through galvanostatic cycling, cyclic voltammetry and impedance spectroscopy. Results indicate stable capacitive performance over 10,000 cycles as well as an impressive performance at high charge and discharge rates, due to accessible pore networks andmore » enhanced electronic and ionic conductivities of SWCNT aerogels. Finally, these materials can find applications in mechanically compressible and flexible supercapacitor devices with high power requirements.« less
Porous-Hybrid Polymers as Platforms for Heterogeneous Photochemical Catalysis.
Haikal, Rana R; Wang, Xia; Hassan, Youssef S; Parida, Manas R; Murali, Banavoth; Mohammed, Omar F; Pellechia, Perry J; Fontecave, Marc; Alkordi, Mohamed H
2016-08-10
A number of permanently porous polymers containing Ru(bpy)n photosensitizer or a cobaloxime complex, as a proton-reduction catalyst, were constructed via one-pot Sonogashira-Hagihara (SH) cross-coupling reactions. This process required minimal workup to access porous platforms with control over the apparent surface area, pore volume, and chemical functionality from suitable molecular building blocks (MBBs) containing the Ru or Co complexes, as rigid and multitopic nodes. The cobaloxime molecular building block, generated through in situ metalation, afforded a microporous solid that demonstrated noticeable catalytic activity toward hydrogen-evolution reaction (HER) with remarkable recyclability. We further demonstrated, in two cases, the ability to affect the excited-state lifetime of the covalently immobilized Ru(bpy)3 complex attained through deliberate utilization of the organic linkers of variable dimensions. Overall, this approach facilitates construction of tunable porous solids, with hybrid composition and pronounced chemical and physical stability, based on the well-known Ru(bpy)nor the cobaloxime complexes.
Rapid subsidence over oil fields measured by SAR
NASA Technical Reports Server (NTRS)
Fielding, E. J.; Blom, R. G.; Goldstein, R. M.
1998-01-01
The Lost Hills and Belridge oil felds are in the San Joaquin Valley, California. The major oil reservoir is high porosity and low permeability diatomite. Extraction of large volumes from shallow depths causes reduction in pore pressure and subsequent compaction, forming a surface subsidence bowl. We measure this subsidence from space using interferometric analysis of SAR (Synthetic Aperture Radar) data collected by the European Space Agency Remote Sensing Satellites (ERS-1 and ERS-2). Maximum subsidence rates are as high as 40 mm in 35 days or > 400 mm/yr, measured from interferograms with time separations ranging from one day to 26 months. The 8- and 26-month interferograms contain areas where the subsidence gradient exceeds the measurement possible with ERS SAR, but shows increased detail in areas of less rapid subsidence. Synoptic mapping of subsidence distribution from satellite data powerfully complements ground-based techniques, permits measurements where access is difficult, and aids identification of underlying causes.
Constant, Sandra; Barakat, Abdellatif; Robitzer, Mike; Di Renzo, Francesco; Dumas, Claire; Quignard, Françoise
2016-09-01
Cellulosic pulps have been successfully isolated from wheat straw through a Lewis acids organosolv treatment. The use of Lewis acids with different hardness produced pulps with different delignification degrees. The cellulosic residue was characterised by chemical composition, X-ray diffraction, FT-IR spectroscopy, N2 physisorption, scanning electron microscopy and potential for anaerobic digestibility. Surface area and pore volume increased with the hardness of the Lewis acid, in correspondence with the decrease of the amount of lignin and hemicellulose in the pulp. The non linearity of the correlation between porosity and composition suggests that an agglomeration of cellulose fibrils occurs in the early stages of pulping. All organosolv pulps presented a significantly higher methane potential than the parent straw. A methane evolution of 295Ncm(3)/g OM was reached by a moderate improvement of the accessibility of the native straw. Copyright © 2016 Elsevier Ltd. All rights reserved.
Saturation-dependent solute dispersivity in porous media: Pore-scale processes
NASA Astrophysics Data System (ADS)
Raoof, A.; Hassanizadeh, S. M.
2013-04-01
It is known that in variably saturated porous media, dispersion coefficient depends on Darcy velocity and water saturation. In one-dimensional flow, it is commonly assumed that the dispersion coefficient is a linear function of velocity. The coefficient of proportionality, called the dispersivity, is considered to depend on saturation. However, there is not much known about its dependence on saturation. In this study, we investigate, using a pore network model, how the longitudinal dispersivity varies nonlinearly with saturation. We schematize the porous medium as a network of pore bodies and pore throats with finite volumes. The pore space is modeled using the multidirectional pore-network concept, which allows for a distribution of pore coordination numbers. This topological property together with the distribution of pore sizes are used to mimic the microstructure of real porous media. The dispersivity is calculated by solving the mass balance equations for solute concentration in all network elements and averaging the concentrations over a large number of pores. We have introduced a new formulation of solute transport within pore space, where we account for different compartments of residual water within drained pores. This formulation makes it possible to capture the effect of limited mixing due to partial filling of the pores under variably saturated conditions. We found that dispersivity increases with the decrease in saturation, it reaches a maximum value, and then decreases with further decrease in saturation. To show the capability of our formulation to properly capture the effect of saturation on solute dispersion, we applied it to model the results of a reported experimental study.
Pore Fluid Pressure Development in Compacting Fault Gouge in Theory, Experiments, and Nature
NASA Astrophysics Data System (ADS)
Faulkner, D. R.; Sanchez-Roa, C.; Boulton, C.; den Hartog, S. A. M.
2018-01-01
The strength of fault zones is strongly dependent on pore fluid pressures within them. Moreover, transient changes in pore fluid pressure can lead to a variety of slip behavior from creep to unstable slip manifested as earthquakes or slow slip events. The frictional properties of low-permeability fault gouge in nature and experiment can be affected by pore fluid pressure development through compaction within the gouge layer, even when the boundaries are drained. Here the conditions under which significant pore fluid pressures develop are analyzed analytically, numerically, and experimentally. Friction experiments on low-permeability fault gouge at different sliding velocities show progressive weakening as slip rate is increased, indicating that faster experiments are incapable of draining the pore fluid pressure produced by compaction. Experiments are used to constrain the evolution of the permeability and pore volume needed for numerical modeling of pore fluid pressure build up. The numerical results are in good agreement with the experiments, indicating that the principal physical processes have been considered. The model is used to analyze the effect of pore fluid pressure transients on the determination of the frictional properties, illustrating that intrinsic velocity-strengthening behavior can appear velocity weakening if pore fluid pressure is not given sufficient time to equilibrate. The results illustrate that care must be taken when measuring experimentally the frictional characteristics of low-permeability fault gouge. The contribution of compaction-induced pore fluid pressurization leading to weakening of natural faults is considered. Cyclic pressurization of pore fluid within fault gouge during successive earthquakes on larger faults may reset porosity and hence the capacity for compaction weakening.
NASA Astrophysics Data System (ADS)
Grathoff, Georg H.; Peltz, Markus; Enzmann, Frieder; Kaufhold, Stephan
2016-07-01
The goal of this study is to better understand the porosity and permeability in shales to improve modelling fluid and gas flow related to shale diagenesis. Two samples (WIC and HAD) were investigated, both mid-Jurassic organic-rich Posidonia shales from Hils area, central Germany of different maturity (WIC R0 0.53 % and HAD R0 1.45 %). The method for image collection was focused ion beam (FIB) microscopy coupled with scanning electron microscopy (SEM). For image and data analysis Avizo and GeoDict was used. Porosity was calculated from segmented 3-D FIB based images and permeability was simulated by a Navier Stokes-Brinkman solver in the segmented images. Results show that the quantity and distribution of pore clusters and pores (≥ 40 nm) are similar. The largest pores are located within carbonates and clay minerals, whereas the smallest pores are within the matured organic matter. Orientation of the pores calculated as pore paths showed minor directional differences between the samples. Both samples have no continuous connectivity of pore clusters along the axes in the x, y, and z direction on the scale of 10 to 20 of micrometer, but do show connectivity on the micrometer scale. The volume of organic matter in the studied volume is representative of the total organic carbon (TOC) in the samples. Organic matter does show axis connectivity in the x, y, and z directions. With increasing maturity the porosity in organic matter increases from close to 0 to more than 5 %. These pores are small and in the large organic particles have little connection to the mineral matrix. Continuous pore size distributions are compared with mercury intrusion porosimetry (MIP) data. Differences between both methods are caused by resolution limits of the FIB-SEM and by the development of small pores during the maturation of the organic matter. Calculations show no permeability when only considering visible pores due to the lack of axis connectivity. Adding the organic matter with a background permeability of 1 × 10-21 m2 to the calculations, the total permeability increased by up to 1 order of magnitude for the low mature and decreases slightly for the overmature sample from the gas window. Anisotropy of permeability was observed. Permeability coefficients increase by 1 order of magnitude if simulations are performed parallel to the bedding. Our results compare well with experimental data from the literature suggesting that upscaling may be possible in the future as soon as maturity dependent organic matter permeability coefficients can be determined.
Synthesis of polybenzoxazine based nitrogen-rich porous carbons for carbon dioxide capture
NASA Astrophysics Data System (ADS)
Wan, Liu; Wang, Jianlong; Feng, Chong; Sun, Yahui; Li, Kaixi
2015-04-01
Nitrogen-rich porous carbons (NPCs) were synthesized from 1,5-dihydroxynaphthalene, urea, and formaldehyde based on benzoxazine chemistry by a soft-templating method with KOH chemical activation. They possess high surface areas of 856.8-1257.8 m2 g-1, a large pore volume of 0.15-0.65 cm3 g-1, tunable pore structure, high nitrogen content (5.21-5.32 wt%), and high char yields. The amount of the soft-templating agent F127 has multiple influences on the textural and chemical properties of the carbons, affecting the surface area and pore structure, impacting the compositions of nitrogen species and resulting in an improvement of the CO2 capture performance. At 1 bar, high CO2 uptake of 4.02 and 6.35 mmol g-1 at 25 and 0 °C was achieved for the sample NPC-2 with a molar ratio of F127 : urea = 0.010 : 1. This can be attributed to its well-developed micropore structure and abundant pyridinic nitrogen, pyrrolic nitrogen and pyridonic nitrogen functionalities. The sample NPC-2 also exhibits a remarkable selectivity for CO2/N2 separation and a fast adsorption/desorption rate and can be easily regenerated. This suggests that the polybenzoxazine-based NPCs are desirable for CO2 capture because of possessing a high micropore surface area, a large micropore volume, appropriate pore size distribution, and a large number of basic nitrogen functionalities.Nitrogen-rich porous carbons (NPCs) were synthesized from 1,5-dihydroxynaphthalene, urea, and formaldehyde based on benzoxazine chemistry by a soft-templating method with KOH chemical activation. They possess high surface areas of 856.8-1257.8 m2 g-1, a large pore volume of 0.15-0.65 cm3 g-1, tunable pore structure, high nitrogen content (5.21-5.32 wt%), and high char yields. The amount of the soft-templating agent F127 has multiple influences on the textural and chemical properties of the carbons, affecting the surface area and pore structure, impacting the compositions of nitrogen species and resulting in an improvement of the CO2 capture performance. At 1 bar, high CO2 uptake of 4.02 and 6.35 mmol g-1 at 25 and 0 °C was achieved for the sample NPC-2 with a molar ratio of F127 : urea = 0.010 : 1. This can be attributed to its well-developed micropore structure and abundant pyridinic nitrogen, pyrrolic nitrogen and pyridonic nitrogen functionalities. The sample NPC-2 also exhibits a remarkable selectivity for CO2/N2 separation and a fast adsorption/desorption rate and can be easily regenerated. This suggests that the polybenzoxazine-based NPCs are desirable for CO2 capture because of possessing a high micropore surface area, a large micropore volume, appropriate pore size distribution, and a large number of basic nitrogen functionalities. Electronic supplementary information (ESI) available: Elemental and XPS analyses and XPS peak positions and relative content of N species in the NPCs. See DOI: 10.1039/c4nr07409b
DOE Office of Scientific and Technical Information (OSTI.GOV)
Litvinova, Larisa, E-mail: larisalitvinova@yandex.ru, E-mail: vshupletsova@mail.ru, E-mail: leitsin@mail.ru; Shupletsova, Valeria, E-mail: larisalitvinova@yandex.ru, E-mail: vshupletsova@mail.ru, E-mail: leitsin@mail.ru; Leitsin, Vladimir, E-mail: larisalitvinova@yandex.ru, E-mail: vshupletsova@mail.ru, E-mail: leitsin@mail.ru
The work studies ZrO{sub 2}(Me{sub x}O{sub y})-based porous ceramics produced from the powders consisting of hollow spherical particles. It was shown that the structure is represented by a cellular framework with bimodal porosity consisting of sphere-like large pores and pores that were not filled with the powder particles during the compaction. For such ceramics, the increase of pore volume is accompanied by the increased strain in an elastic area. It was also shown that the porous ZrO{sub 2} ceramics had no acute or chronic cytotoxicity. At the same time, ceramics possess the following osteoconductive properties: adhesion support, spreading, proliferation andmore » osteogenic differentiation of MSCs.« less
Influence of the doping type and level on the morphology of porous Si formed by galvanic etching
DOE Office of Scientific and Technical Information (OSTI.GOV)
Pyatilova, O. V., E-mail: 5ilova87@gmail.com; Gavrilov, S. A.; Shilyaeva, Yu. I.
The formation of porous silicon (por-Si) layers by the galvanic etching of single-crystal Si samples (doped with boron or phosphorus) in an HF/C{sub 2}H{sub 5}OH/H{sub 2}O{sub 2} solution is investigated. The por-Si layers are analyzed by the capillary condensation of nitrogen and scanning electron microscopy (SEM). The dependences of the morphological characteristics of por-Si (pore diameter, specific surface area, pore volume, and thickness of the pore walls), which determine the por-Si combustion kinetics, on the dopant type and initial wafer resistivity are established.
Magnetic resonance studies of dissolving particulate solids.
Johns, M L; Gladden, L F
2003-01-01
Magnetic resonance methods have been used to elucidate the internal pore structure of particulate solids, in particular detergent tablets. Such information is essential to a comprehensive understanding of the dissolution characteristics of these materials and how this property is related to processing conditions during tablet formation. In particular 3-D images of porosity are produced and 2-D self-diffusion maps are acquired as a function of observation time, which enables pore size to be quantified as a function of position via the extracted surface-to-volume ratio of the pore space. These properties are determined as a function of processing parameters, in particular the compression force used in tablet formation.
Micromechanics of cataclastic pore collapse in limestone
NASA Astrophysics Data System (ADS)
Zhu, Wei; Baud, Patrick; Wong, Teng-Fong
2010-04-01
The analysis of compactant failure in carbonate formations hinges upon a fundamental understanding of the mechanics of inelastic compaction. Microstructural observations indicate that pore collapse in a limestone initiates at the larger pores, and microcracking dominates the deformation in the periphery of a collapsed pore. To capture these micromechanical processes, we developed a model treating the limestone as a dual porosity medium, with the total porosity partitioned between macroporosity and microporosity. The representative volume element is made up of a large pore which is surrounded by an effective medium containing the microporosity. Cataclastic yielding of this effective medium obeys the Mohr-Coulomb or Drucker-Prager criterion, with failure parameters dependent on porosity and pore size. An analytic approximation was derived for the unconfined compressive strength associated with failure due to the propagation and coalescence of pore-emanated cracks. For hydrostatic loading, identical theoretical results for the pore collapse pressure were obtained using the Mohr-Coulomb or Drucker-Prager criterion. For nonhydrostatic loading, the stress state at the onset of shear-enhanced compaction was predicted to fall on a linear cap according to the Mohr-Coulomb criterion. In contrast, nonlinear caps in qualitative agreement with laboratory data were predicted using the Drucker-Prager criterion. Our micromechanical model implies that the effective medium is significantly stronger and relatively pressure-insensitive in comparison to the bulk sample.
Highly tunable porous organic polymer (POP) supports for metallocene-based ethylene polymerization
NASA Astrophysics Data System (ADS)
Wang, Xiong; Li, Zhenyou; Han, Xiaoyu; Han, Zhengang; Bai, Yongxiao
2017-10-01
Porous organic Polymers (POPs) can not only exhibit high specific surface area and pore volume, but also tunable pore size distribution. Herein, copolymers of 2-hydroxyethylmethylacrylate (HEMA) and divinylbenzene (DVB) with specific pore structure were synthesized via a dispersion polymerization strategy, and then immobilized metallocene catalysts with well-defined pore structure were obtained on the produced POP supports. The nitrogen sorption and Gel permeation chromatography (GPC) results demonstrate that the pore structure of the immobilized metallocene catalyst is highly dependent on the pore structure of the POPs, and the pore structure of metallocene catalysts or the POPs has a significant influence on the molecular chain growth of the produced polyethylene. By tuning the distribution of the active species scattered in the micro- and the narrow meso-pore range (roughly ≤4 nm), the chain growth of the polyolefin can be tailored effectively during the polymerization process, although differential scanning calorimetry (DSC) and temperature rising elution fractionation (TREF) results show that the chemical composition distributions (CCDs) of produced PE from the POPs-supported metallocene catalysts are not determined by polymerization activity or molecule chain length, but mainly by the active site species scattered in the supported catalysts. Scanning electron micrograph (SEM) shows that the produced polyethylene has highly porous fabric which consists of nanofiber and spherical beads of micron dimension.
Modeling failure in brittle porous ceramics
NASA Astrophysics Data System (ADS)
Keles, Ozgur
Brittle porous materials (BPMs) are used for battery, fuel cell, catalyst, membrane, filter, bone graft, and pharmacy applications due to the multi-functionality of their underlying porosity. However, in spite of its technological benefits the effects of porosity on BPM fracture strength and Weibull statistics are not fully understood--limiting a wider use. In this context, classical fracture mechanics was combined with two-dimensional finite element simulations not only to account for pore-pore stress interactions, but also to numerically quantify the relationship between the local pore volume fraction and fracture statistics. Simulations show that even the microstructures with the same porosity level and size of pores differ substantially in fracture strength. The maximum reliability of BPMs was shown to be limited by the underlying pore--pore interactions. Fracture strength of BMPs decreases at a faster rate under biaxial loading than under uniaxial loading. Three different types of deviation from classic Weibull behavior are identified: P-type corresponding to a positive lower tail deviation, N-type corresponding to a negative lower tail deviation, and S-type corresponding to both positive upper and lower tail deviations. Pore-pore interactions result in either P-type or N-type deviation in the limit of low porosity, whereas S-type behavior occurs when clusters of low and high fracture strengths coexist in a fracture data.
Effect of Micro Porous Shape on Mechanical Properties in Polypropylene Syntactic Foams
NASA Astrophysics Data System (ADS)
Mae, Hiroyuki; Omiya, Masaki; Kishimoto, Kikuo
The objective is to characterize the effect of the microstructure of the micro pores inside the matrix on the mechanical properties of the thermoplastic syntactic polypropylene (PP) foams at the intermediate and high strain rates. Tensile tests are conducted at the nominal strain rates from 3 x 10-1 to 102 s-1. In addition, the dart impact tests are conducted at the impact velocities of 0.1, 1 and 10 m/s. Then, the constitutive law with craze evolution is modified by introducing the relative density, the stress concentration coefficient and the volume fraction of cell edge, and then applied to the dart impact test mode for simulating the macroscopic load displacement history of the dart impact process. Moreover, the microstructural finite element analysis is conducted to characterize the local stress states in the microstructure. In the tensile loading, the elastic modulus is not influenced by the shape of the micro pores in the PP matrix while the yield stress and the strain energy up to failure are relatively influenced by the shape of micro pores. The microstructural finite element analysis shows that the magnitudes of the localized stresses at the edges and the ligaments of the elliptical-shape micro pores are larger than those at the spherical micro pores, leading to the early yielding and the small material ductility. In the case of the dart impact loading, the microstructure of pores has strong effect on the absorbed energy. This is because the elliptical-shape micro pores are very sensitive to the shear deformation, which is revealed by the microstructural finite element analysis. The modified constitutive law with the stress concentration coefficient and the volume fraction of the cell edges successfully predicts the load-displacement curve of the dart impact loading in the spherical micro-porous PP foam. It is concluded that the micro porous shape has strong effect on the material ductility especially in the dart impact test, leading to the possibility to control the material ductility by the shape of the micro pores in the polymeric foams.
NASA Astrophysics Data System (ADS)
Ramsburg, C. A.; Muller, K.; Gill, J.
2012-12-01
Many current approaches to managing groundwater contamination rely on further advances in amendment delivery in order to initiate and sustain contaminant degradation or immobilization. In fact, limited or ineffective delivery is often cited when treatment objectives are not attained. Emulsions, specifically oil-in-water emulsions, have demonstrated potential to aid delivery of remediation amendments. Emulsions also afford opportunities to control the release of active ingredients encapsulated within the droplets. Our research is currently focused on the controlled release of nanoparticle-based buffering agents using oil-in-water emulsions. This interest is motivated by the fact that chemical and biological processes employed for the remediation and stewardship of contaminated sites often necessitate control of pH during treatment and, in some cases, long thereafter. Alkalinity-release nanoparticles (e.g., CaCO3, MgO) were suspended within soybean oil and subsequently encapsulated by through the creation of oil-in-water emulsions. These oil-in-water emulsions are designed to have physical properties which are favorable for subsurface delivery (nominal properties: 1 g/mL density; 10 cP viscosity; and 1.5 μm droplet diameter). Buffer capacity titrations suggest that MgO particles are moderately more accessible within the oil phase and nearly twice as effective (on a per mass basis) at releasing alkalinity (as compared to the CaCO3 particles). Results from experiments designed to assess the release kinetics suggest that a linear driving force model is capable of describing the release process and mass transfer coefficients are constant through the reactive life of the emulsion. The release kinetics in emulsions containing MgO particles were found to be three orders of magnitude faster than those quantified for emulsions containing CaCO3. The slower release kinetics of the emulsions containing CaCO3 particles may prove beneficial when considering pH control at sites where acid fluxes are lower. The ability of emulsions to sustain alkalinity release within porous media was preliminarily examined using a series of 1-D column experiments. Emulsions were introduced for 2 pore volumes in a medium sand at Darcy velocities of approximately 0.8 cm/hr. Following the emulsion pulse, a pH 4 solution (adjusted with HCl) was introduced into the column and the effluent was monitored for pH, oil content, and droplet size distributions. All un-retained emulsion (~20% wt. was retained) was flushed from the column within approximately 2 pore volumes of terminating the emulsion pulse. The effluent pH at quasi-steady state and the reactive life of the emulsion depended on the retention characteristics, as well as the type and loading of nanoparticles employed within the emulsion. For the scenarios considered here, quasi-steady effluent pHs were observed to be between 6.5 and 10, and reactive lifetimes (i.e., the number of pore volumes for which the retained emulsion resulted in the effluent pH exceeding that of the influent) were between 15 and 100 pore volumes. These results demonstrate the ability of the emulsion to offer longer-term release and highlight the ability to tune the alkalinity release rate to match site characteristics by adjusting the emulsion content. Current research is directed toward evaluation release properties in heterogeneous aquifer cell experiments.
Bimodal activated carbons derived from resorcinol-formaldehyde cryogels
Szczurek, Andrzej; Amaral-Labat, Gisele; Fierro, Vanessa; Pizzi, Antonio; Celzard, Alain
2011-01-01
Resorcinol-formaldehyde cryogels prepared at different dilution ratios have been activated with phosphoric acid at 450 °C and compared with their carbonaceous counterparts obtained by pyrolysis at 900 °C. Whereas the latter were, as expected, highly mesoporous carbons, the former cryogels had very different pore textures. Highly diluted cryogels allowed preparation of microporous materials with high surface areas, but activation of initially dense cryogels led to almost non-porous carbons, with much lower surface areas than those obtained by pyrolysis. The optimal acid concentration for activation, corresponding to stoichiometry between molecules of acid and hydroxyl groups, was 2 M l−1, and the acid–cryogel contact time also had an optimal value. Such optimization allowed us to achieve surface areas and micropore volumes among the highest ever obtained by activation with H3PO4, close to 2200 m2 g−1 and 0.7 cm3 g−1, respectively. Activation of diluted cryogels with a lower acid concentration of 1.2 M l−1 led to authentic bimodal activated carbons, having a surface area as high as 1780 m2 g−1 and 0.6 cm3 g−1 of microporous volume easily accessible through a widely developed macroporosity. PMID:27877405
Determination of pore-scale hydrate phase equilibria in sediments using lab-on-a-chip technology.
Almenningen, Stian; Flatlandsmo, Josef; Kovscek, Anthony R; Ersland, Geir; Fernø, Martin A
2017-11-21
We present an experimental protocol for fast determination of hydrate stability in porous media for a range of pressure and temperature (P, T) conditions. Using a lab-on-a-chip approach, we gain direct optical access to dynamic pore-scale hydrate formation and dissociation events to study the hydrate phase equilibria in sediments. Optical pore-scale observations of phase behavior reproduce the theoretical hydrate stability line with methane gas and distilled water, and demonstrate the accuracy of the new method. The procedure is applicable for any kind of hydrate transitions in sediments, and may be used to map gas hydrate stability zones in nature.
Extravasation of adhering vesicles
NASA Astrophysics Data System (ADS)
Tordeux, C.; Fournier, J.-B.
2002-12-01
We study how the passage of lipid vesicles through a small pore can be induced by the difference in non-specific adhesion energy between the two sides of the substrate bearing the pore. This process is inspired from the extravasation of cells or liposomes from blood vessels, which involves adhesion binders. We study the adhesion-dominated regime and we show that the passage of a vesicle of volume V and area A is selective in terms of the reduced volume v ~ V/A3/2. Extravasation occurs for adhesion ratios of order unity. We also consider the possibility of pressure-induced extravasation in the presence of adhesion. Finally, we propose a micro-device based on adhesion-induced extravasation, which is designed to sort vesicles according to their deflatedness.
Zeolites with Continuously Tuneable Porosity**
Wheatley, Paul S; Chlubná-Eliášová, Pavla; Greer, Heather; Zhou, Wuzong; Seymour, Valerie R; Dawson, Daniel M; Ashbrook, Sharon E; Pinar, Ana B; McCusker, Lynne B; Opanasenko, Maksym; Čejka, Jiří; Morris, Russell E
2014-01-01
Zeolites are important materials whose utility in industry depends on the nature of their porous structure. Control over microporosity is therefore a vitally important target. Unfortunately, traditional methods for controlling porosity, in particular the use of organic structure-directing agents, are relatively coarse and provide almost no opportunity to tune the porosity as required. Here we show how zeolites with a continuously tuneable surface area and micropore volume over a wide range can be prepared. This means that a particular surface area or micropore volume can be precisely tuned. The range of porosity we can target covers the whole range of useful zeolite porosity: from small pores consisting of 8-rings all the way to extra-large pores consisting of 14-rings. PMID:25284344
Synthesis and characterization of pore size-tunable magnetic mesoporous silica nanoparticles.
Zhang, Jixi; Li, Xu; Rosenholm, Jessica M; Gu, Hong-chen
2011-09-01
Magnetic mesoporous silica nanoparticles (M-MSNs) are emerging as one of the most appealing candidates for theranostic carriers. Herein, a simple synthesis method of M-MSNs with a single Fe(3)O(4) nanocrystal core and a mesoporous shell with radially aligned pores was elaborated using tetraethyl orthosilicate (TEOS) as silica source, cationic surfactant CTAB as template, and 1,3,5-triisopropylbenzene (TMB)/decane as pore swelling agents. Due to the special localization of TMB during the synthesis process, the pore size was increased with added TMB amount within a limited range, while further employment of TMB lead to severe particle coalescence and not well-developed pore structure. On the other hand, when a proper amount of decane was jointly incorporated with limited amounts of TMB, effective pore expansion of M-MSNs similar to that of analogous mesoporous silica nanoparticles was realized. The resultant M-MSN materials possessed smaller particle size (about 40-70 nm in diameter), tunable pore sizes (3.8-6.1 nm), high surface areas (700-1100 m(2)/g), and large pore volumes (0.44-1.54 cm(3)/g). We also demonstrate their high potential in conventional DNA loading. Maximum loading capacity of salmon sperm DNA (375 mg/g) was obtained by the use of the M-MSN sample with the largest pore size of 6.1 nm. Copyright © 2011 Elsevier Inc. All rights reserved.
Heat of capillary condensation in nanopores: new insights from the equation of state.
Tan, Sugata P; Piri, Mohammad
2017-02-15
Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) coupled with the Young-Laplace equation is a recently developed equation of state (EOS) that successfully presents not only the capillary condensation but also the pore critical phenomena. The development of this new EOS allows further investigation of the heats involved in condensation. Compared to the conventional approaches, the EOS calculations present the temperature-dependent behavior of the heat of capillary condensation as well as that of the contributing effects. The confinement effect was found to be the strongest at the pore critical point. Therefore, contrary to the bulk heat condensation that vanishes at the critical point, the heat of capillary condensation in small pores shows a minimum and then increases with temperature when approaching the pore critical temperature. Strong support for the existence of the pore critical point is also discussed as the volume expansivity of the condensed phase in confinement was found to increase dramatically near the pore critical temperature. At high reduced temperatures, the Clausius-Clapeyron equation was found to apply better for confined fluids than it does for bulk fluids.
Effect of confinement in nano-porous materials on the solubility of a supercritical gas
NASA Astrophysics Data System (ADS)
Hu, Yaofeng; Huang, Liangliang; Zhao, Shuangliang; Liu, Honglai; Gubbins, Keith E.
2016-11-01
By combining Gibbs Ensemble Monte Carlo simulations and density functional theory, we investigate the influence of confinement in a slit-shaped carbon pore on the solubility of a supercritical solute gas in a liquid solvent. In the cases studied here, competing adsorption of the solvent and solute determines whether the solubility is enhanced or suppressed for larger pores. We find that the solubility in the confined system is strongly dependent on pore width, and that molecular packing effects are important for small pore widths. In addition, the solubility decreases on increase in the temperature, as for the bulk mixture, but the rate of decrease is greater in the pore due to a decrease in the partial molar enthalpy of the solute in the pore; this effect becomes greater as pore width is decreased. The solubility is increased on increasing the bulk pressure of the gas in equilibrium with the pore, and obeys Henry's law at lower pressures. However, the Henry constant differs significantly from that for the bulk mixture, and the range of pressure over which Henry's law applies is reduced relative to that for the bulk mixture. The latter observation indicates that solute-solute interactions become more important in the pore than for the bulk at a given bulk pressure. Finally, we note that different authors use different definitions of the solubility in pores, leading to some confusion over the reported phenomenon of 'oversolubility'. We recommend that solubility be defined as the overall mole fraction of solute in the pores, since it takes into account the increase in density of the solvent in the pores, and avoids ambiguity in the definition of the pore volume.
Relationship between mineralogy and porosity in seals relevant to geologic CO2 Sequestration
DOE Office of Scientific and Technical Information (OSTI.GOV)
Swift, Alexander; Anovitz, Lawrence; Sheets, Julia
2014-01-01
Porosity and permeability are key petrophysical variables that link the thermal, hydrological, geochemical, and geomechanical properties of subsurface formations. The size, shape, distribution, and connectivity of rock pores dictate how fluids migrate into and through micro- and nano-environments, then wet and react with accessible solids. Three representative samples of cap rock from the Eau Claire Formation, the prospective sealing unit that overlies the Mount Simon Sandstone, a potential CO 2 storage formation, were interrogated with an array of complementary methods. neutron scattering, backscattered-electron imaging, energydispersive spectroscopy, and mercury porosimetry. Results are presented that detail variations between lithologic types in totalmore » and connected nano- to microporosity across more than five orders of magnitude. Pore types are identified and then characterized according to presence in each rock type, relative abundance, and surface area of adjacent minerals, pore and pore-throat diameters, and degree of connectivity. We observe a bimodal distribution of porosity as a function of both pore diameter and pore-throat diameter. The contribution of pores at the nano- and microscales to the total and the connected porosity is a distinguishing feature of each lithology observed. Pore:pore-throat ratios at each of these two scales diverge markedly, being almost unity at the nanoscale regime (dominated by illitic clay and micas), and varying by one and a half orders of magnitude at the microscale within a clastic mudstone.« less
NASA Astrophysics Data System (ADS)
Lin, Jie; Chen, Long; Liu, Tong; Xia, Changrong; Chen, Chusheng; Zhan, Zhongliang
2018-01-01
This study is aimed at improving the electrochemical performance of electrode-supported solid oxide electrolysis cells (SOECs) by optimizing the pore structure of the supports. Two planar NiO-8 mol% yttria-stabilized zirconia supports are prepared, one by the phase-inversion tape casting, and the other by conventional tape casting method using graphite as the pore former. The former contains finger-like straight open large pores, while the latter contains randomly distributed and tortuous pores. The steam electrolysis of the cells with different microstructure cathode supports is measured. The cell supported on the cathode with straight pores shows a high current density of 1.42 A cm-2 and a H2 production rate of 9.89 mL (STP) cm-2 min-1 at 1.3 V and 50 vol % humidity and 750 °C, while the cell supported on the cathode with tortuous pores shows a current density of only 0.91 A cm-2 and a H2 production rate of 6.34 mL cm-2min-1. It is concluded that the introduction of large straight open pores into the cathode support allows fast gas phase transport and thus minimizes the concentration polarization. Furthermore, the straight pores could provide better access to the reaction site (the electrode functional layer), thereby reducing the activation polarization as well.
Hydrogen Storage in Metal Hydrides
1990-08-01
TitlePage 1. Properties of Reticulated Carbon Foam 26 2. Hydrogen Storage Capacity of Various Metal Hydrides 27 iv INTRODUCTION This is the final technical...pores, and results in coating of only the surface. The substrate for the fabrication of the magnesium foam was a reticulated carbon foam. This...material is an open-pore foam composed solely of vitreous carbon . It has an exceptionally high void volume (97%) and a high surface area, combined with self
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhou Jian, E-mail: Jian.Zhou@tudelft.n; Ye Guang, E-mail: g.ye@tudelft.n; Magnel Laboratory for Concrete Research, Department of Structural Engineering, Ghent University, Technologiepark-Zwijnaarde 904 B-9052, Ghent
2010-07-15
Numerous mercury intrusion porosimetry (MIP) studies have been carried out to investigate the pore structure in cement-based materials. However, the standard MIP often results in an underestimation of large pores and an overestimation of small pores because of its intrinsic limitation. In this paper, an innovative MIP method is developed in order to provide a more accurate estimation of pore size distribution. The new MIP measurements are conducted following a unique mercury intrusion procedure, in which the applied pressure is increased from the minimum to the maximum by repeating pressurization-depressurization cycles instead of a continuous pressurization followed by a continuousmore » depressurization. Accordingly, this method is called pressurization-depressurization cycling MIP (PDC-MIP). By following the PDC-MIP testing sequence, the volumes of the throat pores and the corresponding ink-bottle pores can be determined at every pore size. These values are used to calculate pore size distribution by using the newly developed analysis method. This paper presents an application of PDC-MIP on the investigation of the pore size distribution in cement-based materials. The experimental results of PDC-MIP are compared with those measured by standard MIP. The PDC-MIP is further validated with the other experimental methods and numerical tool, including nitrogen sorption, backscanning electron (BSE) image analysis, Wood's metal intrusion porosimetry (WMIP) and the numerical simulation by the cement hydration model HYMOSTRUC3D.« less
Characterization of nanoporous shales with gas sorption
NASA Astrophysics Data System (ADS)
Joewondo, N.; Prasad, M.
2017-12-01
The understanding of the fluid flow in porous media requires the knowledge of the pore system involved. Fluid flow in fine grained shales falls under different regime than transport regime in conventional reservoir due to the different average pore sizes in the two materials; the average pore diameter of conventional sandstones is on the micrometer scale, while of shales can be as small as several nanometers. Mercury intrusion porosimetry is normally used to characterize the pores of conventional reservoir, however with increasingly small pores, the injection pressure required to imbibe the pores becomes infinitely large due to surface tension. Characterization of pores can be expressed by a pore size distribution (PSD) plot, which reflects distribution of pore volume or surface area with respect to pore size. For the case of nanoporous materials, the surface area, which serves as the interface between the rock matrix and fluid, becomes increasingly large and important. Physisorption of gas has been extensively studied as a method of nanoporous solid characterization (particularly for the application of catalysis, metal organic frameworks, etc). The PSD is obtained by matching the experimental result to the calculated theoretical result (using Density Functional Theory (DFT), a quantum mechanics based modelling method for molecular scale interactions). We present the challenges and experimental result of Nitrogen and CO2 gas sorption on shales with various mineralogy and the interpreted PSD obtained by DFT method. Our result shows significant surface area contributed by the nanopores of shales, hence the importance of surface area measurements for the characterization of shales.
NASA Astrophysics Data System (ADS)
Zhai, G.; Shirzaei, M.
2017-12-01
Across the Barnett Shale, Texas a noticeable increase in seismic activity was observed during 2007 and 2015, which was accompanied by high volume injection at several nearby disposal wells. Many studies focused on the positive correlation between injection rate at individual wells and the adjacent seismicity, suggesting that seismicity is triggered or induced due to increased pore fluid pressure associated with fluid injection in hydraulically connected geological units. However, investigating temporal evolution of total volume of injected fluid and concurrent earthquakes in a larger area indicates more complex patterns, requiring a more comprehensive analysis of the spatiotemporal evolution of coupled poroelastic stress and pore fluid pressure. In this study, we created a coupled poroelastic model to simulate large scale spatiotemporal evolution of pore pressure, poroelastic stresses, and Coulomb failure stress in the Barnett Shale using injection time series of 96 high-volume injection wells spanning from 2007 to 2015. We additionally account for a layered poroelastic medium, where its parameters are set up using geological maps and seismic tomographic data sets. Fault orientations and relevant frictional properties are also extracted from published literatures. We further integrate observation of surface deformation obtained from interferometric processing of 16 ALOS L-Band SAR images to optimize rock hydraulic diffusivity and constrain the extent to which fluid may migrate. The preliminary modeling result shows that poroelastic stress is only 10% of pore pressure. However, the superimposition of these two effects is spatially and temporally responsible for the occurrence of earthquakes in the Barnett Shale. Also, not all area with increased Coulomb failure stress experiences elevated seismicity, suggesting possible heterogeneous background tectonic stresses, lacking pre-existing faults, and/or heterogeneous fault orientations.
Multi-scale Pore Imaging Techniques to Characterise Heterogeneity Effects on Flow in Carbonate Rock
NASA Astrophysics Data System (ADS)
Shah, S. M.
2017-12-01
Digital rock analysis and pore-scale studies have become an essential tool in the oil and gas industry to understand and predict the petrophysical and multiphase flow properties for the assessment and exploitation of hydrocarbon reserves. Carbonate reservoirs, accounting for majority of the world's hydrocarbon reserves, are well known for their heterogeneity and multiscale pore characteristics. The pore sizes in carbonate rock can vary over orders of magnitudes, the geometry and topology parameters of pores at different scales have a great impact on flow properties. A pore-scale study is often comprised of two key procedures: 3D pore-scale imaging and numerical modelling techniques. The fundamental problem in pore-scale imaging and modelling is how to represent and model the different range of scales encountered in porous media, from the pore-scale to macroscopic petrophysical and multiphase flow properties. However, due to the restrictions of image size vs. resolution, the desired detail is rarely captured at the relevant length scales using any single imaging technique. Similarly, direct simulations of transport properties in heterogeneous rocks with broad pore size distributions are prohibitively expensive computationally. In this study, we present the advances and review the practical limitation of different imaging techniques varying from core-scale (1mm) using Medical Computed Tomography (CT) to pore-scale (10nm - 50µm) using Micro-CT, Confocal Laser Scanning Microscopy (CLSM) and Focussed Ion Beam (FIB) to characterise the complex pore structure in Ketton carbonate rock. The effect of pore structure and connectivity on the flow properties is investigated using the obtained pore scale images of Ketton carbonate using Pore Network and Lattice-Boltzmann simulation methods in comparison with experimental data. We also shed new light on the existence and size of the Representative Element of Volume (REV) capturing the different scales of heterogeneity from the pore-scale imaging.
Morris, Eric A; Kirk, Donald W; Jia, Charles Q; Morita, Kazuki
2012-07-17
This work addresses the discrepancy in the literature regarding the effects of sulfuric acid (H(2)SO(4)) on elemental Hg uptake by activated carbon (AC). H(2)SO(4) in AC substantially increased Hg uptake by absorption particularly in the presence of oxygen. Hg uptake increased with acid amount and temperature exceeding 500 mg-Hg/g-AC after 3 days at 200 °C with AC treated with 20% H(2)SO(4). In the absence of other strong oxidizers, oxygen was able to oxidize Hg. Upon oxidation, Hg was more readily soluble in the acid, greatly enhancing its uptake by acid-treated AC. Without O(2), S(VI) in H(2)SO(4) was able to oxidize Hg, thus making it soluble in H(2)SO(4). Consequently, the presence of a bulk H(2)SO(4) phase within AC pores resulted in an orders of magnitude increase in Hg uptake capacity. However, the bulk H(2)SO(4) phase lowered the AC pore volume and could block the access to the active surface sites and potentially hinder Hg uptake kinetics. AC treated with SO(2) at 700 °C exhibited a much faster rate of Hg uptake attributed to sulfur functional groups enhancing adsorption kinetics. SO(2)-treated carbon maintained its fast uptake kinetics even after impregnation by 20% H(2)SO(4).
Tan, Yih Horng; Schallom, John R.; Ganesh, N. Vijaya; Fujikawa, Kohki; Demchenko, Alexei V.
2011-01-01
Nanoporous gold (NPG), made by dealloying low carat gold alloys, is a relatively new nanomaterial finding application in catalysis, sensing, and as a support for biomolecules. NPG has attracted considerable interest due to its open bicontinuous structure, high surface-to-volume ratio, tunable porosity, chemical stability and biocompatibility. NPG also has the attractive feature of being able to be modified by self-assembled monolayers. Here we use scanning electron microscopy (SEM) and atomic force microscopy (AFM) to characterize a highly efficient approach for protein immobilization on NPG using N-hydroxysuccinimide (NHS) ester functionalized self-assembled monolayers on NPG with pore sizes in the range of tens of nanometres. Comparison of coupling under static versus flow conditions suggests that BSA (Bovine Serum Albumin) and IgG (Immunoglobulin G) can only be immobilized onto the interior surfaces of free standing NPG monoliths with good coverage under flow conditions. AFM is used to examine protein coverage on both the exterior and interior of protein modified NPG. Access to the interior surface of NPG for AFM imaging is achieved using a special procedure for cleaving NPG. AFM is also used to examine BSA immobilized on rough gold surfaces as a comparative study. In principle, the general approach described should be applicable to many enzymes, proteins and protein complexes since both pore sizes and functional groups present on the NPG surfaces are controllable. PMID:21750834
Change of the human taste bud volume over time.
Srur, Ehab; Stachs, Oliver; Guthoff, Rudolf; Witt, Martin; Pau, Hans Wilhelm; Just, Tino
2010-08-01
The specific aim of this study is to measure the taste volume in healthy human subjects over a 2.5-month period and to demonstrate morphological changes of the peripheral taste organs. Eighteen human taste buds in four fungiform papillae (fPap) were examined over a 10-week period. The fungiform papillae investigated were selected based on the form of the papillae or the arrangement of surface taste pores. Measurements were performed over 10 consecutive weeks, with five scans in a day once a week. The following parameters were measured: height and diameter of the taste bud, diameter of the fungiform papilla and diameter of the taste pore. The findings of this exploratory study indicated that (1) taste bud volumes changed over a 10-week period, (2) the interval between two volume maxima within the 10-week period was 3-5 weeks, and (3) the diameter of the fPap did not correlate with the volume of a single taste bud or with the volume of all taste buds in the fPap within the 10-week period. This exploratory in vivo study revealed changes in taste bud volumes in healthy humans with age-related gustatory sensitivity. These findings need to be considered when studying the effect of denervation of fungiform papillae in vivo using confocal microscopy. Crown Copyright 2009. Published by Elsevier Ireland Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Fichtner, Thomas; Stefan, Catalin; Goersmeyer, Nora
2015-04-01
Rate and extent of the biological degradation of organic substances during transport through the unsaturated soil zone is decisively influenced by the chemical and physical properties of the pollutants such as water solubility, toxicity and molecular structure. Furthermore microbial degradation processes are also influenced by soil-specific properties. An important parameter is the soil grain size distribution on which the pore volume and the pore size depends. Changes lead to changes in air and water circulation as well as preferred flow paths. Transport capacity of water inclusive nutrients is lower in existing bad-drainable fine pores in soils with small grain size fractions than in well-drainable coarse pores in a soil with bigger grain size fractions. Because fine pores are saturated with water for a longer time than the coarse pores and oxygen diffusion in water is ten thousand times slower than in air, oxygen is replenished much slower in soils with small grain size fractions. As a result life and growth conditions of the microorganisms are negatively affected. This leads to less biological activity, restricted degradation/mineralization of pollutants or altered microbial processes. The aim of conducted laboratory column experiments was to study the correlation between the grain size fractions respectively pore sizes, the oxygen content and the biodegradation rate of infiltrated organic substances. Therefore two columns (active + sterile control) were filled with different grain size fractions (0,063-0,125 mm, 0,2-0,63 mm and 1-2 mm) of soils. The sterile soil was inoculated with a defined amount of a special bacteria culture (sphingobium yanoikuae). A solution with organic substances glucose, oxalic acid, sinaphylic alcohol and nutrients was infiltrated from the top in intervals. The degradation of organic substances was controlled by the measurement of dissolved organic carbon in the in- and outflow of the column. The control of different pore volumes respectively pore sizes in the soil samples occurred by air pycnometer measurement and determination of soil moisture characteristic by evaporation method according to Wind/Schindler. The present study results can be useful to find a correlation between various soil types with different grain size distributions and the suitability of these soils for example for the infiltration of treated wastewater in the context of managed aquifer recharge (MAR) measures.
NASA Astrophysics Data System (ADS)
Wang, Weiming; Wang, Zhixuan; Chen, Xuan; Long, Fei; Lu, Shuangfang; Liu, Guohong; Tian, Weichao; Su, Yue
In this paper, in a case study of Santanghu Basin in China, the morphological characteristics and size distribution of nanoscale pores in the volcanic rocks of the Haerjiawu Formation were investigated using the results of low temperature nitrogen adsorption experiments. This research showed that within the target layer, a large number of nanoscale, eroded pores showed an “ink bottle” morphology with narrow pore mouths and wide bodies. The fractal dimension of pores increases gradually with increasing depth. Moreover, as fractal dimension increases, BET-specific surface area gradually increases, average pore diameter decreases and total pore volume gradually increases. The deeper burial of the Haerjiawu volcanic rocks in the Santanghu Basin leads to more intense erosion by organic acids derived from the basin’s source rocks. Furthermore, the internal surface roughness of these corrosion pores results in poor connectivity. As stated above, the corrosion process is directly related to the organic acids generated by the source rock of the interbedded volcanic rocks. The deeper the reservoir, the more the organic acids being released from the source rock. However, due to the fact that the Haerjiawu volcanic rocks are tight reservoirs and have complicated pore-throat systems, while organic acids dissolve unstable minerals such as feldspars which improve the effective reservoir space; the dissolution of feldspars results in the formation of new minerals, which cannot be expelled from the tight reservoirs. They are instead precipitated in the fine pore throats, thereby reducing pore connectivity, while enhancing reservoir micro-preservation conditions.
X-ray CT analysis of pore structure in sand
NASA Astrophysics Data System (ADS)
Mukunoki, Toshifumi; Miyata, Yoshihisa; Mikami, Kazuaki; Shiota, Erika
2016-06-01
The development of microfocused X-ray computed tomography (CT) devices enables digital imaging analysis at the pore scale. The applications of these devices are diverse in soil mechanics, geotechnical and geoenvironmental engineering, petroleum engineering, and agricultural engineering. In particular, the imaging of the pore space in porous media has contributed to numerical simulations for single-phase and multiphase flows or contaminant transport through the pore structure as three-dimensional image data. These obtained results are affected by the pore diameter; therefore, it is necessary to verify the image preprocessing for the image analysis and to validate the pore diameters obtained from the CT image data. Moreover, it is meaningful to produce the physical parameters in a representative element volume (REV) and significant to define the dimension of the REV. This paper describes the underlying method of image processing and analysis and discusses the physical properties of Toyoura sand for the verification of the image analysis based on the definition of the REV. On the basis of the obtained verification results, a pore-diameter analysis can be conducted and validated by a comparison with the experimental work and image analysis. The pore diameter is deduced from Young-Laplace's law and a water retention test for the drainage process. The results from previous study and perforated-pore diameter originally proposed in this study, called the voxel-percolation method (VPM), are compared in this paper. In addition, the limitations of the REV, the definition of the pore diameter, and the effectiveness of the VPM for an assessment of the pore diameter are discussed.
Multi-Material Tissue Engineering Scaffold with Hierarchical Pore Architecture.
Morgan, Kathy Ye; Sklaviadis, Demetra; Tochka, Zachary L; Fischer, Kristin M; Hearon, Keith; Morgan, Thomas D; Langer, Robert; Freed, Lisa E
2016-08-23
Multi-material polymer scaffolds with multiscale pore architectures were characterized and tested with vascular and heart cells as part of a platform for replacing damaged heart muscle. Vascular and muscle scaffolds were constructed from a new material, poly(limonene thioether) (PLT32i), which met the design criteria of slow biodegradability, elastomeric mechanical properties, and facile processing. The vascular-parenchymal interface was a poly(glycerol sebacate) (PGS) porous membrane that met different criteria of rapid biodegradability, high oxygen permeance, and high porosity. A hierarchical architecture of primary (macroscale) and secondary (microscale) pores was created by casting the PLT32i prepolymer onto sintered spheres of poly(methyl methacrylate) (PMMA) within precisely patterned molds followed by photocuring, de-molding, and leaching out the PMMA. Pre-fabricated polymer templates were cellularized, assembled, and perfused in order to engineer spatially organized, contractile heart tissue. Structural and functional analyses showed that the primary pores guided heart cell alignment and enabled robust perfusion while the secondary pores increased heart cell retention and reduced polymer volume fraction.
Hearn, Elizabeth H.; Koltermann, Christine; Rubinstein, Justin R.
2018-01-01
We have developed groundwater flow models to explore the possible relationship between wastewater injection and the 12 November 2014 Mw 4.8 Milan, Kansas earthquake. We calculate pore pressure increases in the uppermost crust using a suite of models in which hydraulic properties of the Arbuckle Formation and the Milan earthquake fault zone, the Milan earthquake hypocenter depth, and fault zone geometry are varied. Given pre‐earthquake injection volumes and reasonable hydrogeologic properties, significantly increasing pore pressure at the Milan hypocenter requires that most flow occur through a conductive channel (i.e., the lower Arbuckle and the fault zone) rather than a conductive 3‐D volume. For a range of reasonable lower Arbuckle and fault zone hydraulic parameters, the modeled pore pressure increase at the Milan hypocenter exceeds a minimum triggering threshold of 0.01 MPa at the time of the earthquake. Critical factors include injection into the base of the Arbuckle Formation and proximity of the injection point to a narrow fault damage zone or conductive fracture in the pre‐Cambrian basement with a hydraulic diffusivity of about 3–30 m2/s. The maximum pore pressure increase we obtain at the Milan hypocenter before the earthquake is 0.06 MPa. This suggests that the Milan earthquake occurred on a fault segment that was critically stressed prior to significant wastewater injection in the area. Given continued wastewater injection into the upper Arbuckle in the Milan region, assessment of the middle Arbuckle as a hydraulic barrier remains an important research priority.
Nimmo, J.R.; Herkelrath, W.N.; Laguna, Luna A.M.
2007-01-01
Numerous models are in widespread use for the estimation of soil water retention from more easily measured textural data. Improved models are needed for better prediction and wider applicability. We developed a basic framework from which new and existing models can be derived to facilitate improvements. Starting from the assumption that every particle has a characteristic dimension R associated uniquely with a matric pressure ?? and that the form of the ??-R relation is the defining characteristic of each model, this framework leads to particular models by specification of geometric relationships between pores and particles. Typical assumptions are that particles are spheres, pores are cylinders with volume equal to the associated particle volume times the void ratio, and that the capillary inverse proportionality between radius and matric pressure is valid. Examples include fixed-pore-shape and fixed-pore-length models. We also developed alternative versions of the model of Arya and Paris that eliminate its interval-size dependence and other problems. The alternative models are calculable by direct application of algebraic formulas rather than manipulation of data tables and intermediate results, and they easily combine with other models (e.g., incorporating structural effects) that are formulated on a continuous basis. Additionally, we developed a family of models based on the same pore geometry as the widely used unsaturated hydraulic conductivity model of Mualem. Predictions of measurements for different suitable media show that some of the models provide consistently good results and can be chosen based on ease of calculations and other factors. ?? Soil Science Society of America. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Arifvianto, B., E-mail: b.arifvianto@tudelft.nl; L
The present research was aimed at gaining an understanding of the porous structure changes from the green body through water leaching and sintering to titanium scaffolds. Micro-computed tomography (micro-CT) was performed to generate 3D models of titanium scaffold preforms containing carbamide space-holding particles and sintered scaffolds containing macro- and micro-pores. The porosity values and structural parameters were determined by means of image analysis. The result showed that the porosity values, macro-pore sizes, connectivity densities and specific surface areas of the titanium scaffolds sintered at 1200 °C for 3 h did not significantly deviate from those of the green structures withmore » various volume fractions of the space holder. Titanium scaffolds with a maximum specific surface area could be produced with an addition of 60–65 vol% carbamide particles to the matrix powder. The connectivity of pores inside the scaffold increased with rising volume fraction of the space holder. The shrinkage of the scaffolds prepared with > 50 vol% carbamide space holder, occurring during sintering, was caused by the reductions of macro-pore sizes and micro-pore sizes as well as the thickness of struts. In conclusion, the final porous structural characteristics of titanium scaffolds could be estimated from those of the green body. - Highlights: •Porous structures of green body and sintered titanium scaffolds was studied. •Porous structures of both samples were quantitatively characterized with micro-CT. •Porous structures of scaffolds could be controlled from the green body. •Shrinkage mechanisms of titanium scaffolds during sintering was established.« less
NASA Astrophysics Data System (ADS)
Jeong, Tae-Gyung; Chun, Jinyong; Cho, Byung-Won; Lee, Jinwoo; Kim, Yong-Tae
2017-02-01
The porous carbon matrix is widely recognized to be a promising sulfur reservoir to improve the cycle life by suppressing the polysulfide dissolution in lithium sulfur batteries (LSB). Herein, we synthesized mesocellular carbon foam (MSUF-C) with bimodal mesopore (4 and 30 nm) and large pore volume (1.72 cm2/g) using MSUF silica as a template and employed it as both the sulfur reservoir and the conductive agent in the sulfur cathode. Sulfur was uniformly infiltrated into MSUF-C pores by a chemical solution deposition method (MSUF-C/S CSD) and the amount of sulfur loading was achieved as high as 73% thanks to the large pore volume with the CSD approach. MSUF-C/S CSD showed a high capacity (889 mAh/g after 100 cycles at 0.2 C), an improved rate capability (879 mAh/g at 1C and 420 mAh/g at 2C), and a good capacity retention with a fade rate of 0.16% per cycle over 100 cycles.
Jeong, Tae-Gyung; Chun, Jinyong; Cho, Byung-Won; Lee, Jinwoo; Kim, Yong-Tae
2017-01-01
The porous carbon matrix is widely recognized to be a promising sulfur reservoir to improve the cycle life by suppressing the polysulfide dissolution in lithium sulfur batteries (LSB). Herein, we synthesized mesocellular carbon foam (MSUF-C) with bimodal mesopore (4 and 30 nm) and large pore volume (1.72 cm2/g) using MSUF silica as a template and employed it as both the sulfur reservoir and the conductive agent in the sulfur cathode. Sulfur was uniformly infiltrated into MSUF-C pores by a chemical solution deposition method (MSUF-C/S CSD) and the amount of sulfur loading was achieved as high as 73% thanks to the large pore volume with the CSD approach. MSUF-C/S CSD showed a high capacity (889 mAh/g after 100 cycles at 0.2 C), an improved rate capability (879 mAh/g at 1C and 420 mAh/g at 2C), and a good capacity retention with a fade rate of 0.16% per cycle over 100 cycles. PMID:28165041
Preparation of modified semi-coke by microwave heating and adsorption kinetics of methylene blue.
Wang, Xin; Peng, Jin-Hui; Duan, Xin-Hui; Srinivasakannan, Chandrasekar
2013-01-01
Preparation of modified semi-coke has been achieved, using phosphoric acid as the modifying agent, by microwave heating from virgin semi-coke. Process optimization using a Central Composite Design (CCD) design of Response Surface Methodology (RSM) technique for the preparation of modifies semi-coke is presented in this paper. The optimum conditions for producing modified semi-coke were: concentration of phosphoric acid 2.04, heating time 20 minutes and temperature 587 degrees C, with the optimum iodine of 862 mg/g and yield of 47.48%. The textural characteristics of modified semi-coke were analyzed using scanning electron microscopy (SEM) and nitrogen adsorption isotherm. The BET surface area of modified semi-coke was estimated to be 989.60 m2/g, with the pore volume of 0.74 cm3/g and a pore diameter of 3.009 nm, with micro-pore volume contributing to 62.44%. The Methylene Blue monolayer adsorption capacity was found to be mg/g at K. The adsorption capacity of the modified semi-coke highlights its suitability for liquid phase adsorption application with a potential usage in waste water treatment.
Ibrahim, Abdul-Rauf; Li, Xiangyun; Zhou, Yulan; Huang, Yan; Chen, Wenwen; Wang, Hongtao; Li, Jun
2015-01-01
The use of cheaper and recyclable biomaterials (like eggshells) to synthesize high purity hydroxyapatite (HAp) with better properties (small particle size, large surface area and pore volume) for applications (in environmental remediation, bone augmentation and replacement, and drug delivery systems) is vital since high-purity synthetic calcium sources are expensive. In this work, pure and mesoporous HAp nanopowder with large pore volume (1.4 cm3/g) and surface area (284.1 m2/g) was produced from raw eggshells at room temperature using a simple two-step procedure. The control of precursor droplets could stabilize the pH value of the reaction solution, because of the size of the needle (of the syringe pump used for precursor additions) leading to production of HAp with high surface area and pore size. The as-produced HAp revealed high ibuprofen (as a model drug) loading (1.38 g/g HAp), enhanced dissolution and controllable release of the drug via solute-saturated supercritical carbon dioxide. PMID:25860950
Li, Hao; Mahyoub, Samah Awadh Ali; Liao, Wenjie; Xia, Shuqian; Zhao, Hechuan; Guo, Mengya; Ma, Peisheng
2017-01-01
The magnetic biochars were easily fabricated by thermal pyrolysis of Fe(NO 3 ) 3 and distillation residue derived from rice straw pyrolysis oil at 400, 600 and 800°C. The effects of pyrolysis temperature on characteristics of magnetic biochars as well as adsorption capacity for aromatic contaminants (i.e., anisole, phenol and guaiacol) were investigated carefully. The degree of carbonization of magnetic biochars become higher as pyrolysis temperature increasing. The magnetic biochar reached the largest surface area and pore volume at the pyrolysis temperature of 600°C due to pores blocking in biochar during pyrolysis at 800°C. Based on batch adsorption experiments, the used adsorbent could be magnetically separated and the adsorption capacity of anisole on magnetic biochars was stronger than that of phenol and guaiacol. The properties of magnetic biochar, including surface area, pore volume, aromaticity, grapheme-like-structure and iron oxide (γ-Fe 2 O 3 ) particles, showed pronounced effects on the adsorption performance of aromatic contaminants. Copyright © 2016 Elsevier Ltd. All rights reserved.
Pore water sampling in acid sulfate soils: a new peeper method.
Johnston, Scott G; Burton, Edward D; Keene, Annabelle F; Bush, Richard T; Sullivan, Leigh A; Isaacson, Lloyd
2009-01-01
This study describes the design, deployment, and application of a modified equilibration dialysis device (peeper) optimized for sampling pore waters in acid sulfate soils (ASS). The modified design overcomes the limitations of traditional-style peepers, when sampling firm ASS materials over relatively large depth intervals. The new peeper device uses removable, individual cells of 25 mL volume housed in a 1.5 m long rigid, high-density polyethylene rod. The rigid housing structure allows the device to be inserted directly into relatively firm soils without requiring a supporting frame. The use of removable cells eliminates the need for a large glove-box after peeper retrieval, thus simplifying physical handling. Removable cells are easily maintained in an inert atmosphere during sample processing and the 25-mL sample volume is sufficient for undertaking multiple analyses. A field evaluation of equilibration times indicates that 32 to 38 d of deployment was necessary. Overall, the modified method is simple and effective and well suited to acquisition and processing of redox-sensitive pore water profiles>1 m deep in acid sulfate soil or any other firm wetland soils.
Reza, M Toufiq; Rottler, Erwin; Herklotz, Laureen; Wirth, Benjamin
2015-04-01
In this study, influence of feedwater pH (2-12) was studied for hydrothermal carbonization (HTC) of wheat straw at 200 and 260°C. Acetic acid and KOH were used as acidic and basic medium, respectively. Hydrochars were characterized by elemental and fiber analyses, SEM, surface area, pore volume and size, and ATR-FTIR, while HTC process liquids were analyzed by HPLC and GC. Both hydrochar and HTC process liquid qualities vary with feedwater pH. At acidic pH, cellulose and elemental carbon increase in hydrochar, while hemicellulose and pseudo-lignin decrease. Hydrochars produced at pH 2 feedwater has 2.7 times larger surface area than that produced at pH 12. It also has the largest pore volume (1.1 × 10(-1) ml g(-1)) and pore size (20.2 nm). Organic acids were increasing, while sugars were decreasing in case of basic feedwater, however, phenolic compounds were present only at 260°C and their concentrations were increasing in basic feedwater. Copyright © 2015 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Zemke, K.; Kummmerow, J.; Wandrey, M.; Co2SINK Group
2009-04-01
Since June of 2008 carbon dioxide has been injected into a saline aquifer at the Ketzin test site [Würdemann et al., this volume]. The food grade CO2 is injected into a sandstone zone of the Stuttgart formation at ca. 650 m depth at 35°C reservoir temperature and 62 bar reservoir pressure. With the injection of CO2 into the geological formation, chemical and physical reservoir characteristics are changed depending on pressure, temperature, fluid chemistry and rock composition. Fluid-rock interaction could comprise dissolution of non-resistant minerals in CO2-bearing pore fluids, cementing of the pore space by precipitating substances from the pore fluid, drying and disintegration of clay minerals and thus influence of the composition and activities of the deep biosphere. To testing the injection behaviour of CO2 in water saturated rock and to evaluate the geophysical signature depending on the thermodynamic conditions, flow experiments with water and CO2 have been performed on cores of the Stuttgart formation from different locations including new wells of ketzin test site. The studied core material is an unconsolidated fine-grained sandstone with porosity values from 15 to 32 %. Permeability, electrical resistivity, and sonic wave velocities and their changes with pressure, saturation and time have been studied under simulated in situ conditions. The flow experiments conducted over several weeks with brine and CO2 showed no significant changes of resistivity and velocity and a slightly decreasing permeability. Pore fluid analysis showed mobilization of clay and some other components. A main objective of the CO2Sink laboratory program is the assessment of the effect of long-term CO2 exposure on reservoir rocks to predict the long-term behaviour of geological CO2 storage. For this CO2 exposure experiments reservoir rock samples were exposed to CO2 saturated reservoir fluid in corrosion-resistant high pressure vessels under in situ temperature and pressure conditions over a period of several months. Before and after the CO2 exposure experiment cyclic measurements of physical properties were carried out on these cores in a mechanical testing system. After experimental runs of up to 3 months no significant changes in flow and petrophysical data were observed. [For the microbilogical studies see Wandrey et al., this volume.] To study the impact of fluid-rock interactions on petrophysical parameters, porosity and pore radii distribution have been investigated before and after the experiment by NMR relaxation and mercury-injection. NMR measurements on rock core plugs saturated with brine may return valuable information on the porous structure of the rock core. The distribution of NMR-T2 values (CPMG) reflects the pore sizes within the rock core. NMR pore size is a derivative of the ratio pore surface/volume. The mercury injection pore size is an area-equivalent diameter of the throats connecting the pore system. Most of the tested samples show in the NMR measurements a slightly increasing porosity and a higher part of large pores. The mercury measurements and thin- section for microstructural characterisation after the CO2 exposure will be done at a later date.
Skibinski, Bertram; Götze, Christoph; Worch, Eckhard; Uhl, Wolfgang
2018-04-01
Overall apparent reaction rates for the removal of monochloramine (MCA) in granular activated carbon (GAC) beds were determined using a fixed-bed reactor system and under conditions typical for swimming pool water treatment. Reaction rates dropped and quasi-stationary conditions were reached quickly. Diffusional mass transport in the pores was shown to be limiting the overall reaction rate. This was reflected consistently in the Thiele modulus, in the effect of temperature, pore size distribution and of grain size on the reaction rates. Pores <2.5 times the diameter of the monochloramine molecule were shown to be barely accessible for the monochloramine conversion reaction. GACs with a significant proportion of large mesopores were found to have the highest overall reactivity for monochloramine removal. Copyright © 2017 Elsevier Ltd. All rights reserved.
Investigations in Producing Porous NiAl by Combustion Synthesis
NASA Astrophysics Data System (ADS)
Zhong, Songming
In recent years, nickel aluminide (NiAl) intermetallic foam, which combines the advantages of nickel-based alloy and metallic foam, has attracted great attention due to its extraordinary properties. In this present work, nickel aluminide (NiAl) foam has been reactively processed from elemental powder (nickel and aluminium) with different types and percentage of volume of a foaming agent (TiH2 or CaCO3), using a combustion synthesis (CS) approach. Most of the previous research has focused on producing close-cell NiAl intermetallic foam; however, this paper presents a new combustion synthesis process to fabricate a hybrid open-cell and close-cell NiAl intermetallic foam. Mixed elemental powder was compacted at moderate pressure generating closed and open porosity with green compact; as a result, part of the liberated gas could escape from the sample, which resulted in producing open-cell pores, in addition, closed cell pores in the product. The effect of foaming agent type and volume percentage on the product is discussed. An increase in volume percentage of TiH2 was found to have beneficial effects on increasing porosity; however, with the increase of volume percentage of CaCO3, there is a big drop in porosity because the low viscosity under high temperature makes more liberated gas escape and pores collapse. According to XRD and EDX analysis, despite the present of multiple phases in samples, NiAl was still the major phase. Hardness measurement shows that high hardness value was obtained at sample of low grain size, hardness value increases with decreasing grain size.
NASA Astrophysics Data System (ADS)
Chang, W.; Kim, J.; Zhu, N.; McBeth, J. M.
2015-12-01
Microbial hydrocarbon degradation is environmentally significant and applicable to contaminated site remediation practices only when hydrocarbons (substrates) are physically bioaccessible to bacteria in soil matrices. Powerful X-rays are produced by synchrotron radiation, allowing for bioaccessible pores in soil (larger than 4 microns), where bacteria can be accommodated, colonize and remain active, can be visualized at a much higher resolution. This study visualized and quantified such bioaccessible pores in intact field-aged, oil-contaminated unsaturated soil fractions, and examined the relationship between the abundance of bioaccessible pores and hydrocarbon biodegradation. Using synchrotron-based X-ray Computed Tomography (CT) at the Canadian Light Source, a large dataset of soil particle characteristics, such as pore volumes, surface areas, number of pores and pore size distribution, was generated. Duplicate samples of five different soil fractions with different soil aggregate sizes and water contents (13, 18 and 25%) were examined. The method for calculating the number and distribution of bioaccessible pores using CT images was validated using the known porosity of Ottawa sand. This study indicated that the distribution of bioaccessible pore sizes in soil fractions are very closely related to microbial enhancement. A follow-up aerobic biodegradation experiment for the soils at 17 °C (average site temperature) over 90 days confirmed that a notable decrease in hydrocarbon concentrations occurred in soils fractions with abundant bioaccessible pores and with a larger number of pores between 10 and 100 μm. The hydrocarbon degradation in bioactive soil fractions was extended to relatively high-molecular-weight hydrocarbons (C16-C34). This study provides quantitative information about how internal soil pore characteristics can influence bioremediation performance.
An investigation into the effects of pore connectivity on T2 NMR relaxation
NASA Astrophysics Data System (ADS)
Ghomeshi, Shahin; Kryuchkov, Sergey; Kantzas, Apostolos
2018-04-01
Nuclear Magnetic Resonance (NMR) is a powerful technique used to characterize fluids and flow in porous media. The NMR relaxation curves are closely related to pore geometry, and the inversion of the NMR relaxometry data is known to give useful information with regards to pore size distribution (PSD) through the relative amplitudes of the fluids stored in the small and large pores. While this information is crucial, the main challenge for the successful use of the NMR measurements is the proper interpretation of the measured signals. Natural porous media patterns consist of complex pore structures with many interconnected or "coupled" regions, as well as isolated pores. This connectivity along the throats changes the relaxation distribution and in order to properly interpret this data, a thorough understanding of the effects of pore connectivity on the NMR relaxation distribution is warranted. In this paper we address two main points. The first pertains to the fact that there is a discrepancy between the relaxation distribution obtained from experiments, and the ones obtained from solving the mathematical models of diffusion process in the digitized images of the pore space. There are several reasons that may attribute to this such as the lack of a proper incorporation of surface roughness into the model. However, here we are more interested in the effects of pore connectivity and to understand why the typical NMR relaxation distribution obtained from experiments are wider, while the numerical simulations predict that a wider NMR relaxation distribution may indicate poor connectivity. Secondly, by not taking into account the pore coupling effects, from our experience in interpreting the data, we tend to underestimate the pore volume of small pores and overestimate the amplitudes in the large pores. The role of pore coupling becomes even more prominent in rocks with small pore sizes such as for example in shales, clay in sandstones, and in the microstructures of carbonates.
3-D Distribution of Retained Colloids in Unsaturated Porous Media
NASA Astrophysics Data System (ADS)
Morales, V. L.; Perez-Reche, F. J.; Holzner, M.; Kinzelbach, W. K.; Otten, W.
2013-12-01
It is well accepted that colloid transport processes in porous media differ substantially between water saturated and unsaturated conditions. Differences are frequently ascribed to colloid immobilization by association with interfaces with the gas, as well as to restrictions of the liquid medium through which colloids are transported. Such factors depend on interfacial conditions provided by the water saturation of the porous medium. Yet, the current understanding of the importance of colloid retention at gas interfaces is based on observations of single pores or two-dimensional pore network representations, leaving open the question of their statistical significance when all pores in the medium are considered. In order to address this question, column experiments were performed using a model porous medium of glass beads through which colloidal silver particles were transported for conditions of varying water content. X-ray microtomography was subsequently employed as a non-destructive imaging technique to obtain pore-scale information of the entire column regarding: i) the presence and distribution of the four main locations where colloids can become retained (interfaces with the liquid-solid, gas-liquid and gas-solid, and the bulk liquid), ii) deposition profiles of colloids along the column classified by the available retention location, iii) morphological characteristics of the deposited colloidal aggregates, and iv) channel widths of 3-dimensional pore-water network representations. The results presented provide, for the first time, a direct statistical evaluation on the significance of colloid retention by attachment to the liquid-solid, gas-liquid, gas-solid interfaces, and by straining in the bulk liquid. Additionally, an effective-pore structure characteristic is proposed to improve predictions of mass removal by straining under various water saturations. A) Unsaturated conditions. B) Saturated conditions. Left: Tomograph slice illustrating with false coloring Regions Of Interest corresponding to retention locations at the gas-liquid (purple), gas-solid (white) and solid-liquid interface (blue), and the bulk liquid (teal). Right: Deposition profiles of silver colloids (Ag) per retention location (T: total, GLI: gas-liquid interface, GSI: gas-solid interface, SLI: solid-liquid interface, L: bulk liquid) (Top). Depth profiles of the volume occupied by each retention location (Middle). Normalized deposition profiles of silver volume retained by its corresponding retention-location volume (Bottom).
Use of adjuvants to minimize leaching of herbicides in soil
NASA Astrophysics Data System (ADS)
Alva, Ashok K.; Singh, Megh
1991-03-01
Excessive leaching of herbicides affects their efficacy against target weeds and results in contamination of groundwater. Use of adjuvants that can weakly bind herbicides and in turn release them slowly is a valuable technique to prolong the efficacy of herbicides and to minimize their leaching into groundwater. Effects of activated charcoal, three humic substances (Enersol SP 85%, Enersol 12%, and Agroliz), or a synthetic polymer (Hydrosorb) on the leaching of bromacil, dicamba, and simazine were investigated in leaching columns using a Candler fine sand (Typic Quartzipsamment). The addition of adjuvants had no harmful effects on physical properties of the soil as evident from lack of its affects on water percolation. When no adjuvants were used, 69%, 37%, and 4% of applied dicamba, bromacil, and simazine, respectively, were leached in the first pore volume of leachate (⋍3.2 cm rainfall). With five pore volumes of leachate (⋍16 cm rainfall), bromacil and dicamba were leached completely and only 80% of simazine was leached. Using Enersol 12% adjuvant resulted in a 13%-18% reduction in leaching of dicamba and bromacil in five pore volumes of leachate. The leaching of simazine was significantly decreased when any of the five adjuvants mentioned above were used. However, the decrease in leaching was significantly greater when using Enersol SP 85% or Enersol 12% (24%-28%) than when using the other adjuvants (12%-16%).
NASA Astrophysics Data System (ADS)
Zhang, Dongdong; Zhao, Jianghong; Feng, Chong; Zhao, Rijie; Sun, Yahui; Guan, Taotao; Han, Baixin; Tang, Nan; Wang, Jianlong; Li, Kaixi; Qiao, Jinli; Zhang, Jiujun
2017-02-01
A scalable inverse-microemulsion-polymerization-phase-separation coupling method is applied to successfully prepare hierarchical macropore-rich activated carbon microspheres (ACS) using a phenolic resin (PR) precursor followed by carbonization and KOH activation for the first time. The formed ACS materials are assembled by carbon nanoparticles (CNPs). The macropores interspersed among the component CNPs are formed after removing the non-reactive solvent phase in the course of the polymerization of the reactive PR phase, which occupies ∼64% of the total pore volume (∼2.779 cm3 g-1) of the optimized ACS. In combination with mesopores (∼18% of the total pore volume), the ACS possesses meso/macropores approaching 82% of the total pore volume. Micropores are created in the component CNPs via KOH activation, showing shortened ion transport distances in the nanoscale dimension. Both the hierarchical micro/meso/macroporous structure and the inner nanoparticle morphology (short ion diffusion pathways) can significantly contribute to the rapid transport of electrolyte ions throughout the carbonaceous matrix, resulting in superior rate performance of ACS-based supercapacitors. More importantly, the energy densities of the ACS supercapacitors operating in both aqueous and organic electrolyte retain steady over a wide range of power densities varying dramatically from 0.25 to 14.5 kW kg-1 and to 7.0 kW kg-1, respectively.
NASA Astrophysics Data System (ADS)
Bailey, Austin
Amplitude Variation with Angle and Azimuth (AVAZ) is a method that examines the azimuthal change in seismic amplitude to calculate the anisotropy of a horizontally transverse isotropic (HTI) formation. Anisotropy is generally indicative of heterogeneity in the rock fabric, be it fractures, crack-like pores, or local stress changes. The aim of this study as a whole is to examine the relationship between AVAZ anisotropy magnitude from seismic data and pore pressure gradient from wells. Pore pressure is an important reservoir metric that is often used to understand the production variations within a hydrocarbon reservoir. Predicting pore pressure from seismic data can be extremely useful in not only estimating production, but also in predicting the completion and development strategies that may be most effective. However, seismic-based pore pressure prediction methods have not evolved much in the past decade, with the industry standard to rely on the Bowers (1995) or Eaton (1987) method of converting seismic velocities to pore pressure volumes. These methods may fall short as a predictive tool in many cases, due to their lack of spatial resolution and dependency on a stable velocity model, which may not always be available. Therefore, this study was begun in order to examine if an alternative method of detecting pore pressure variations could be found using AVAZ. The AVAZ methodology was applied to a merged 3D seismic dataset in the Anadarko Basin, Oklahoma provided by Cimarex Energy, in order to examine the Woodford Shale. The Woodford has been a key player in hydrocarbon production from the Anadarko Basin for decades, mainly serving as a source rock until the mid-2000's during the "unconventional revolution''. Throughout its extent, the Woodford Formation shows significant heterogeneity due to both the structure and faults of the basin, as well as changes in the rock fabric. This study aims to use the AVAZ methodology to examine heterogeneity in the Woodford and to relate its anisotropy to pore pressure. Before examining the AVAZ effect in the seismic data, forward modeling from well logs was completed to conceptualize a relationship between pore pressure and anisotropy. Theoretically, at higher pore pressures the reservoir fluid may be effectively propping the fractures open, thus having a greater effect on any pressure wave traveling through the fluid. At lower pore pressure, the overburden pressure dominates the fluid-filled fractures and closes them down. Therefore, at higher pore pressure the AVAZ anisotropy would be greater than at lower pore pressure. The forward modeling from dipole sonic well logs confirms this conceptual model by showing a positive relationship between pore pressure and AVAZ anisotropy. Before the results of the AVAZ workflow were obtained, a variety of pre-processing steps and quality controls were done on the merged 3D seismic dataset. Although the pore pressure - anisotropy relationship appears robust in modeling, the AVAZ results from the seismic data do not appear to correlate with pore pressure. It is likely that acquisition-related artifacts in the seismic data, as well as small magnitude of change in pore pressure, contribute to this lack of correlation. However, further interpretation of the AVAZ volumes shows local stress variations near faults as well as a potential secondary stress trend striking to the north-east. Such information has implications for completion and overall development of the Woodford as an unconventional resource play.
George, David L.; Iverson, Richard M.
2014-01-01
We evaluate a new depth-averaged mathematical model that is designed to simulate all stages of debris-flow motion, from initiation to deposition. A companion paper shows how the model’s five governing equations describe simultaneous evolution of flow thickness, solid volume fraction, basal pore-fluid pressure, and two components of flow momentum. Each equation contains a source term that represents the influence of state-dependent granular dilatancy. Here we recapitulate the equations and analyze their eigenstructure to show that they form a hyperbolic system with desirable stability properties. To solve the equations we use a shock-capturing numerical scheme with adaptive mesh refinement, implemented in an open-source software package we call D-Claw. As tests of D-Claw, we compare model output with results from two sets of large-scale debris-flow experiments. One set focuses on flow initiation from landslides triggered by rising pore-water pressures, and the other focuses on downstream flow dynamics, runout, and deposition. D-Claw performs well in predicting evolution of flow speeds, thicknesses, and basal pore-fluid pressures measured in each type of experiment. Computational results illustrate the critical role of dilatancy in linking coevolution of the solid volume fraction and pore-fluid pressure, which mediates basal Coulomb friction and thereby regulates debris-flow dynamics.
Characterizing TPS Microstructure: A Review of Some techniques
NASA Technical Reports Server (NTRS)
Gasch, Matthew; Stackpole, Mairead; Agrawal, Parul; Chavez-Garcie, Jose
2011-01-01
I. When seeking to understand ablator microstructure and morphology there are several useful techniques A. SEM 1) Visual characteriza3on at various length scales. 2) Chemical mapping by backscatter or x-ray highlights areas of interest. 3) Combined with other techniques (density, weight change, chemical analysis) SEM is a powerful tool to aid in explaining thermo/structural data. B. ASAP. 1) Chemical characteriza3on at various length scales. 2) Chemical mapping of pore structure by gas adsorption. 3) Provides a map of pore size vs. pore volume. 4) Provided surface area of exposed TPS. II. Both methods help characterize and understand how ablators react with other chemical species and provides insight into how they oxidize.
Das, Sumanta; Yang, Pu; Singh, Sudhanshu S.; ...
2015-09-02
Microstructural and micromechanical investigation of a fly ash-based geopolymer using: (i) synchrotron x-ray tomography (XRT) to determine the volume fraction and tortuosity of pores that are influential in fluid transport, (ii) mercury intrusion porosimetry (MIP) to capture the volume fraction of smaller pores, (iii) scanning electron microscopy (SEM) combined with multi-label thresholding to identify and characterize the solid phases in the microstructure, and (iv) nanoindentation to determine the component phase elastic properties using statistical deconvolution, is reported in this paper. The phase volume fractions and elastic properties are used in multi-step mean field homogenization (Mori- Tanaka and double inclusion) modelsmore » to determine the homogenized macroscale elastic modulus of the composite. The homogenized elastic moduli are in good agreement with the flexural elastic modulus determined on macroscale paste beams. As a result, the combined use of microstructural and micromechanical characterization tools at multiple scales provides valuable information towards the material design of fly ash geopolymers.« less
The influence of extraction procedure on ion concentrations in sediment pore water
Winger, P.V.; Lasier, P.J.; Jackson, B.P.
1998-01-01
Sediment pore water has the potential to yield important information on sediment quality, but the influence of isolation procedures on the chemistry and toxicity are not completely known and consensus on methods used for the isolation from sediment has not been reached. To provide additional insight into the influence of collection procedures on pore water chemistry, anion (filtered only) and cation concentrations were measured in filtered and unfiltered pore water isolated from four sediments using three different procedures: dialysis, centrifugation and vacuum. Peepers were constructed using 24-cell culture plates and cellulose membranes, and vacuum extractors consisted of fused-glass air stones attached with airline tubing to 60cc syringes. Centrifugation was accomplished at two speeds (2,500 and 10,000 x g) for 30 min in a refrigerated centrifuge maintained at 4?C. Only minor differences in chemical characteristics and cation and anion concentrations were found among the different collecting methods with differences being sediment specific. Filtering of the pore water did not appreciably reduce major cation concentrations, but trace metals (Cu and Pb) were markedly reduced. Although the extraction methods evaluated produced pore waters of similar chemistries, the vacuum extractor provided the following advantages over the other methods: (1) ease of extraction, (2) volumes of pore water isolated, (3) minimal preparation time and (4) least time required for extraction of pore water from multiple samples at one time.
NASA Astrophysics Data System (ADS)
Zhang, Liehui; Li, Jianchao; Jia, Du; Zhao, Yulong; Xie, Chunyu; Tao, Zhengwu
As one of the key status of gas in shale reservoir, adsorption gas accounts for considerable percentage of total gas amount. Due to the complexity and nanostructure of shale gas reservoir, it is very challenging to represent adsorption gas through traditional methods. However, the integration of the fractal theory and molecular dynamics (MD) simulation may provide a new perspective of understanding such nanostructure and the micro-phenomenon happening in it. The key purpose of this paper is to investigate the adsorption phenomenon in shale kerogen. By using MD simulation and grand canonical Monte Carlo (GCMC) algorithm, the adsorption of methane in 2, 5 and 10nm slit-like pores is simulated for different temperature and pressure status. According to the results, the average gas density in smaller pores is higher than that in bigger pores, and multilayer adsorption presents on some areas of pore surfaces. Then, the simulation results are analyzed using the multilayer fractal adsorption model. The analysis indicates that the number of adsorption layer increases with pressure increase: four-layer adsorption presents in 10nm pores while three-layer adsorption shows up in 2nm and 5nm pores due to pore volume limit. Fractal dimension of pore wall surface generated in this study is in the range of 2.31-2.63. Moreover, high temperature could decrease the adsorption behavior in reservoir condition.
Comparison of thermal compatibility between atomized and comminuted U{sub 3}Si dispersion fuels
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ryu, Woo-Seog; Park, Jong-Man; Kim, Chang-Kyu
1997-08-01
Thermal compatibility of atomized U{sub 3}Si dispersion fuels were evaluated up to 2600 hours in the temperature range from 250 to 500{degrees}C, and compared with that of comminuted U{sub 3}Si. Atomized U{sub 3}Si showed better performance in terms of volume expansion of fuel meats. The reaction zone of U{sub 3}Si and Al occurred along the grain boundaries and deformation bands in U{sub 3}Si particles. Pores around fuel particles appeared at high temperature or after long-term annealing tests to remain diffusion paths over the trench of the pores. The constraint effects of cladding on fuel rod suppressed the fuel meat, andmore » reduced the volume expansion.« less
Thermoporometry characterization of silica microparticles and nanowires.
Wu, Jiaxin; Zheng, Han; Cheng, He; Zhou, L; Leong, K C; Rajagopalan, R; Too, H P; Choi, W K
2014-03-04
We present the results of a systematic study on the porosity of silica microparticles and nanowires prepared by glancing angle deposition-metal-assisted chemical etching (GLAD-MACE) and interference lithography-metal-assisted chemical etching (IL-MACE) techniques using the thermoporometry (TPM) method. Good agreement was obtained between our TPM results and published data provided by the suppliers of silica microparticles. TPM characterization of the GLAD-MACE and IL-MACE nanowires was carried out on the basis of parameters obtained from TPM experiments on microparticles. Our nanowires showed a similar trend but lower values of the pore volume and surface area than nanowires prepared by MACE with AgNO3 solution. We attribute the enhanced bioanalysis performance of the GLAD-MACE nanowires based devices to the increased pore volume and total surface area of the nanowires.
Physical parameters of Fluvisols on flooded and non-flooded terraces
NASA Astrophysics Data System (ADS)
Kercheva, Milena; Sokołowska, Zofia; Hajnos, Mieczysław; Skic, Kamil; Shishkov, Toma
2017-01-01
The heterogeneity of soil physical properties of Fluvisols, lack of large pristine areas, and different moisture regimes on non-flooded and flooded terraces impede the possibility to find a soil profile which can serve as a baseline for estimating the impact of natural or anthropogenic factors on soil evolution. The aim of this study is to compare the pore size distribution of pristine Fluvisols on flooded and non-flooded terraces using the method of the soil water retention curve, mercury intrusion porosimetry, nitrogen adsorption isotherms, and water vapour sorption. The pore size distribution of humic horizons of pristine Fluvisols on the non-flooded terrace differs from pore size distribution of Fluvisols on the flooded terrace. The peaks of textural and structural pores are higher in the humic horizons under more humid conditions. The structural characteristics of subsoil horizons depend on soil texture and evolution stage. The peaks of textural pores at about 1 mm diminish with lowering of the soil organic content. Structureless horizons are characterized by uni-modal pore size distribution. Although the content of structural pores of the subsoil horizons of Fluvisols on the non-flooded terrace is low, these pores are represented by biopores, as the coefficient of filtration is moderately high. The difference between non-flooded and flooded profiles is well expressed by the available water storage, volume and mean radius of pores, obtained by mercury intrusion porosimetry and water desorption, which are higher in the surface horizons of frequently flooded Fluvisols.
Cuticular gas exchange by Antarctic sea spiders.
Lane, Steven J; Moran, Amy L; Shishido, Caitlin M; Tobalske, Bret W; Woods, H Arthur
2018-04-25
Many marine organisms and life stages lack specialized respiratory structures, like gills, and rely instead on cutaneous respiration, which they facilitate by having thin integuments. This respiratory mode may limit body size, especially if the integument also functions in support or locomotion. Pycnogonids, or sea spiders, are marine arthropods that lack gills and rely on cutaneous respiration but still grow to large sizes. Their cuticle contains pores, which may play a role in gas exchange. Here, we examined alternative paths of gas exchange in sea spiders: (1) oxygen diffuses across pores in the cuticle, a common mechanism in terrestrial eggshells, (2) oxygen diffuses directly across the cuticle, a common mechanism in small aquatic insects, or (3) oxygen diffuses across both pores and cuticle. We examined these possibilities by modeling diffusive oxygen fluxes across all pores in the body of sea spiders and asking whether those fluxes differed from measured metabolic rates. We estimated fluxes across pores using Fick's law parameterized with measurements of pore morphology and oxygen gradients. Modeled oxygen fluxes through pores closely matched oxygen consumption across a range of body sizes, which means the pores facilitate oxygen diffusion. Furthermore, pore volume scaled hypermetrically with body size, which helps larger species facilitate greater diffusive oxygen fluxes across their cuticle. This likely presents a functional trade-off between gas exchange and structural support, in which the cuticle must be thick enough to prevent buckling due to external forces but porous enough to allow sufficient gas exchange. © 2018. Published by The Company of Biologists Ltd.
Variational-based segmentation of bio-pores in tomographic images
NASA Astrophysics Data System (ADS)
Bauer, Benjamin; Cai, Xiaohao; Peth, Stephan; Schladitz, Katja; Steidl, Gabriele
2017-01-01
X-ray computed tomography (CT) combined with a quantitative analysis of the resulting volume images is a fruitful technique in soil science. However, the variations in X-ray attenuation due to different soil components keep the segmentation of single components within these highly heterogeneous samples a challenging problem. Particularly demanding are bio-pores due to their elongated shape and the low gray value difference to the surrounding soil structure. Recently, variational models in connection with algorithms from convex optimization were successfully applied for image segmentation. In this paper we apply these methods for the first time for the segmentation of bio-pores in CT images of soil samples. We introduce a novel convex model which enforces smooth boundaries of bio-pores and takes the varying attenuation values in the depth into account. Segmentation results are reported for different real-world 3D data sets as well as for simulated data. These results are compared with two gray value thresholding methods, namely indicator kriging and a global thresholding procedure, and with a morphological approach. Pros and cons of the methods are assessed by considering geometric features of the segmented bio-pore systems. The variational approach features well-connected smooth pores while not detecting smaller or shallower pores. This is an advantage in cases where the main bio-pores network is of interest and where infillings, e.g., excrements of earthworms, would result in losing pore connections as observed for the other thresholding methods.
Improved capacitance characteristics of electrospun ACFs by pore size control and vanadium catalyst.
Im, Ji Sun; Woo, Sang-Wook; Jung, Min-Jung; Lee, Young-Seak
2008-11-01
Nano-sized carbon fibers were prepared by using electrospinning, and their electrochemical properties were investigated as a possible electrode material for use as an electric double-layer capacitor (EDLC). To improve the electrode capacitance of EDLC, we implemented a three-step optimization. First, metal catalyst was introduced into the carbon fibers due to the excellent conductivity of metal. Vanadium pentoxide was used because it could be converted to vanadium for improved conductivity as the pore structure develops during the carbonization step. Vanadium catalyst was well dispersed in the carbon fibers, improving the capacitance of the electrode. Second, pore-size development was manipulated to obtain small mesopore sizes ranging from 2 to 5 nm. Through chemical activation, carbon fibers with controlled pore sizes were prepared with a high specific surface and pore volume, and their pore structure was investigated by using a BET apparatus. Finally, polyacrylonitrile was used as a carbon precursor to enrich for nitrogen content in the final product because nitrogen is known to improve electrode capacitance. Ultimately, the electrospun activated carbon fibers containing vanadium show improved functionality in charge/discharge, cyclic voltammetry, and specific capacitance compared with other samples because of an optimal combination of vanadium, nitrogen, and fixed pore structures.
Nayak, Nadiya B.; Nayak, Bibhuti B.
2016-01-01
Development of in-born porous nature of zirconium hydroxide nanopowders through a facile hydrogen (H2) gas-bubbles assisted borohydride synthesis route using sodium borohydride (NaBH4) and novel information on the temperature-mediated phase transformation, pore geometry as well as pore hysteresis transformation of in-born porous zirconium hydroxide nanopowders with the help of X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) isotherm and Transmission Electron Microscopy (TEM) images are the main theme of this research work. Without any surfactants or pore forming agents, the borohydride derived amorphous nature of porous powders was stable up to 500 °C and then the seed crystals start to develop within the loose amorphous matrix and trapping the inter-particulate voids, which led to develop the porous nature of tetragonal zirconium oxide at 600 °C and further sustain this porous nature as well as tetragonal phase of zirconium oxide up to 800 °C. The novel hydrogen (H2) gas-bubbles assisted borohydride synthesis route led to develop thermally stable porous zirconium hydroxide/oxide nanopowders with an adequate pore size, pore volume, and surface area and thus these porous materials are further suggested for promising use in different areas of applications. PMID:27198738
Conserved Aromatic Residue Confers Cation Selectivity in Claudin-2 and Claudin-10b*
Li, Jiahua; Zhuo, Min; Pei, Lei; Yu, Alan S. L.
2013-01-01
In tight junctions, both claudin-2 and claudin-10b form paracellular cation-selective pores by the interaction of the first ECL 1 with permeating ions. We hypothesized that a highly conserved aromatic residue near the pore selectivity filter of claudins contributes to cation selectivity by cation-π interaction with the permeating cation. To test this, we generated MDCK I Tet-off cells stably transfected with claudin-2 Tyr67 mutants. The Y67L mutant showed reduced cation selectivity compared with wild-type claudin-2 due to a decrease in Na+ permeability, without affecting the Cl− permeability. The Y67A mutant enlarged the pore size and further decreased the charge selectivity due to an increase in Cl− permeability. The Y67F mutant restored the Na+ permeability, Cl− permeability, and pore size back to wild-type. The accessibility of Y67C to methanethiosulfonate modification indicated that its side chain faces the lumen of the pore. In claudin-10b, the F66L mutant reduced cation selectivity, and the F66A mutant lost pore conductance. We conclude that the conserved aromatic residue near the cation pore domain of claudins contributes to cation selectivity by a dual role of cation-π interaction and a luminal steric effect. Our findings provide new insight into how ion selectivity is achieved in the paracellular pore. PMID:23760508
Zhao, Jin; Wen, Dongsheng
2017-08-27
For enhanced oil recovery (EOR) applications, the oil/water flow characteristics during the flooding process was numerically investigated with the volume-of-fluid method at the pore scale. A two-dimensional pore throat-body connecting structure was established, and four scenarios were simulated in this paper. For oil-saturated pores, the wettability effect on the flooding process was studied; for oil-unsaturated pores, three effects were modelled to investigate the oil/water phase flow behaviors, namely the wettability effect, the interfacial tension (IFT) effect, and the combined wettability/IFT effect. The results show that oil saturated pores with the water-wet state can lead to 25-40% more oil recovery than with the oil-wet state, and the remaining oil mainly stays in the near wall region of the pore bodies for oil-wet saturated pores. For oil-unsaturated pores, the wettability effects on the flooding process can help oil to detach from the pore walls. By decreasing the oil/water interfacial tension and altering the wettability from oil-wet to water-wet state, the remaining oil recovery rate can be enhanced successfully. The wettability-IFT combined effect shows better EOR potential compared with decreasing the interfacial tension alone under the oil-wet condition. The simulation results in this work are consistent with previous experimental and molecular dynamics simulation conclusions. The combination effect of the IFT reducation and wettability alteration can become an important recovery mechanism in future studies for nanoparticles, surfactant, and nanoparticle-surfactant hybrid flooding process.
Zhao, Jin
2017-01-01
For enhanced oil recovery (EOR) applications, the oil/water flow characteristics during the flooding process was numerically investigated with the volume-of-fluid method at the pore scale. A two-dimensional pore throat-body connecting structure was established, and four scenarios were simulated in this paper. For oil-saturated pores, the wettability effect on the flooding process was studied; for oil-unsaturated pores, three effects were modelled to investigate the oil/water phase flow behaviors, namely the wettability effect, the interfacial tension (IFT) effect, and the combined wettability/IFT effect. The results show that oil saturated pores with the water-wet state can lead to 25–40% more oil recovery than with the oil-wet state, and the remaining oil mainly stays in the near wall region of the pore bodies for oil-wet saturated pores. For oil-unsaturated pores, the wettability effects on the flooding process can help oil to detach from the pore walls. By decreasing the oil/water interfacial tension and altering the wettability from oil-wet to water-wet state, the remaining oil recovery rate can be enhanced successfully. The wettability-IFT combined effect shows better EOR potential compared with decreasing the interfacial tension alone under the oil-wet condition. The simulation results in this work are consistent with previous experimental and molecular dynamics simulation conclusions. The combination effect of the IFT reducation and wettability alteration can become an important recovery mechanism in future studies for nanoparticles, surfactant, and nanoparticle–surfactant hybrid flooding process. PMID:29308190
White, Claire E.; Olds, Daniel P.; Hartl, Monika; ...
2017-02-01
The long-term durability of cement-based materials is influenced by the pore structure and associated permeability at the sub-micrometre length scale. With the emergence of new types of sustainable cements in recent decades, there is a pressing need to be able to predict the durability of these new materials, and therefore nondestructive experimental techniques capable of characterizing the evolution of the pore structure are increasingly crucial for investigating cement durability. Here, small-angle neutron scattering is used to analyze the evolution of the pore structure in alkali-activated materials over the initial 24 h of reaction in order to assess the characteristic poremore » sizes that emerge during these short time scales. By using a unified fitting approach for data modeling, information on the pore size and surface roughness is obtained for a variety of precursor chemistries and morphologies (metakaolin- and slag-based pastes). Furthermore, the impact of activator chemistry is elucidatedviathe analysis of pastes synthesized using hydroxide- and silicate-based activators. It is found that the main aspect influencing the size of pores that are accessible using small-angle neutron scattering analysis (approximately 10–500 Å in diameter) is the availability of free silica in the activating solution, which leads to a more refined pore structure with smaller average pore size. Furthermore, as the reaction progresses the gel pores visible using this scattering technique are seen to increase in size.« less
A practical extension of hydrodynamic theory of porous transport for hydrophilic solutes.
Bassingthwaighte, James B
2006-03-01
The equations for transport of hydrophilic solutes through aqueous pores provide a fundamental basis for examining capillary-tissue exchange and water and solute flux through transmembrane channels, but the theory remains incomplete for ratios, alpha, of sphere diameters to pore diameters greater than 0.4. Values for permeabilities, P, and reflection coefficients, sigma, from Lewellen, working with Lightfoot et al., at alpha = 0.5 and 0.95, were combined with earlier values for alpha < 0.4, and the physically required values at alpha = 1.0, to provide accurate expressions over the whole range of 0 < alpha < 1. The "data" were the long-accepted theory for alpha < 0.2 and the computational results from Lewellen and Lightfoot et al. on hard spheres (of 5 different alpha's) moving by convection and diffusion through a tight cylindrical pore, accounting for molecular exclusion, viscous forces, pressure drop, torque and rotation of spheres off the center line (averaging across all accessible radial positions), and the asymptotic values at alpha = 1.0. Coefficients for frictional hindrance to diffusion, F(alpha), and drag, G(alpha), and functions for sigma(alpha) and P(alpha), were represented by power law functions and the parameters optimized to give best fits to the combined "data." The reflection coefficient sigma = {1 - [1 - (1 - phi)2]G'(alpha)} + 2alpha2 phi F'(alpha), and the relative permeability P/Pmax = phi F '(alpha)[1 + 9alpha5.5 x (1.0 - alpha5)0.02], where phi is the partition coefficient or volume fraction of the pore available to solute. The new expression for the diffusive hindrance is F'(alpha) = (1 - alpha2)(3/2) phi/[1 + 0.2 x alpha2 x (1 - alpha2)16], and for the drag factor is G'(alpha) = (1 - 2alpha(2)/3 - 0.20217 alpha5)/(1 - 0.75851 alpha5) - 0.0431[1 - (1 - alpha10)]. All of these converge monotonically to the correct limits at alpha = 1. These are the first expressions providing hydrodynamically based estimates of sigma(alpha) and P(alpha) over 0 < alpha < 1 They should be accurate to within 1-2%.
Archetypal sandwich-structured CuO for high performance non-enzymatic sensing of glucose.
Meher, Sumanta Kumar; Rao, G Ranga
2013-03-07
In the quest to enhance the selectivity and sensitivity of novel structured metal oxides for electrochemical non-enzymatic sensing of glucose, we report here a green synthesis of unique sandwich-structured CuO on a large scale under microwave mediated homogeneous precipitation conditions. The physicochemical studies carried out by XRD and BET methods show that the monoclinic CuO formed via thermal decomposition of Cu(2)(OH)(2)CO(3) possesses monomodal channel-type pores with largely improved surface area (~43 m(2) g(-1)) and pore volume (0.163 cm(3) g(-1)). The fascinating surface morphology and pore structure of CuO is formulated due to homogeneous crystallization and microwave induced self assembly during synthesis. The cyclic voltammetry and chronoamperometry studies show diffusion controlled glucose oxidation at ~0.6 V (vs. Ag/AgCl) with extremely high sensitivity of 5342.8 μA mM(-1) cm(-2) and respective detection limit and response time of ~1 μM and ~0.7 s, under a wide dynamic concentration range of glucose. The chronoamperometry measurements demonstrate that the sensitivity of CuO to glucose is unaffected by the absence of dissolved oxygen and presence of poisoning chloride ions in the reaction medium, which essentially implies high poison resistance activity of the sandwich-structured CuO. The sandwich-structured CuO also shows insignificant interference/significant selectivity to glucose, even in the presence of high concentrations of other sugars as well as reducing species. In addition, the sandwich-structured CuO shows excellent reproducibility (relative standard deviation of ~2.4% over ten identically fabricated electrodes) and outstanding long term stability (only ~1.3% loss in sensitivity over a period of one month) during non-enzymatic electrochemical sensing of glucose. The unique microstructure and suitable channel-type pore architecture provide structural stability and maximum accessible electroactive surface for unimpeded mobility of glucose as well as the product molecules, which result in the excellent sensitivity and selectivity of sandwich-structured CuO for glucose under non-enzymatic milieu.
Methane hydrate formation in partially water-saturated Ottawa sand
Waite, W.F.; Winters, W.J.; Mason, D.H.
2004-01-01
Bulk properties of gas hydrate-bearing sediment strongly depend on whether hydrate forms primarily in the pore fluid, becomes a load-bearing member of the sediment matrix, or cements sediment grains. Our compressional wave speed measurements through partially water-saturated, methane hydrate-bearing Ottawa sands suggest hydrate surrounds and cements sediment grains. The three Ottawa sand packs tested in the Gas Hydrate And Sediment Test Laboratory Instrument (GHASTLI) contain 38(1)% porosity, initially with distilled water saturating 58, 31, and 16% of that pore space, respectively. From the volume of methane gas produced during hydrate dissociation, we calculated the hydrate concentration in the pore space to be 70, 37, and 20% respectively. Based on these hydrate concentrations and our measured compressional wave speeds, we used a rock physics model to differentiate between potential pore-space hydrate distributions. Model results suggest methane hydrate cements unconsolidated sediment when forming in systems containing an abundant gas phase.
Determining the Size of Pores in a Partially Transparent Ceramics from Total-Reflection Spectra
NASA Astrophysics Data System (ADS)
Mironov, R. A.; Zabezhailov, M. O.; Georgiu, I. F.; Cherepanov, V. V.; Rusin, M. Yu.
2018-03-01
A technique is proposed for determining the pore-size distribution based on measuring the dependence of total reflectance in the domain of partial transparency of a material. An assumption about equality of scattering-coefficient spectra determined by solving the inverse radiation transfer problem and by theoretical calculation with the Mie theory is used. The technique is applied to studying a quartz ceramics. The poresize distribution is also determined using mercury and gas porosimetry. All three methods are shown to produce close results for pores with diameters of <180 nm, which occupy 90% of the void volume. In the domain of pore dimensions of >180 nm, the methods show differences that might be related to both specific procedural features and the structural properties of ceramics. The spectral-scattering method has a number of advantages over traditional porosimetry, and it can be viewed as a routine industrial technique.
Pore Water Transport of Enterococci out of Beach Sediments
Phillips, Matthew C.; Solo-Gabriele, Helena M.; Reniers, Adrianus J. H. M.; Wang, John D.; Kiger, Russell T.; Abdel-Mottaleb, Noha
2011-01-01
Enterococci are used to evaluate the safety of beach waters and studies have identified beach sands as a source of these bacteria. In order to study and quantify the release of microbes from beach sediments, flow column systems were built to evaluate flow of pore water out of beach sediments. Results show a peak in enterococci (average of 10% of the total microbes in core) released from the sand core within one pore water volume followed by a marked decline to below detection. These results indicate that few enterococci are easily removed and that factors other than simple pore water flow control the release of the majority of enterococci within beach sediments. A significantly larger quantity and release of enterococci were observed in cores collected after a significant rain event suggesting the influx of fresh water can alter the release pattern as compared to cores with no antecedent rainfall. PMID:21945015
NASA Astrophysics Data System (ADS)
Wahyuningsih, S.; Ramelan, A. H.; Wardoyo, D. T.; Ichsan, S.; Kristiawan, Y. R.
2018-03-01
The utilization and modification of silica from rice straw as the main ingredient of adsorbent has been studied. The aim of this study was to determine the optimum composition of PVA (polyvinyl alcohol): silica to produce adsorbents with excellent pore characteristics, optimum adsorption efficiency and optimum pH for methyl yellow adsorptions. X-Ray Fluorescence (XRF) analysis results showed that straw ash contains 82.12 % of silica (SiO2). SAA (Surface Area Analyzer) analysis showed optimum composition ratio 5:5 of PVA: silica with surface area of 1.503 m2/g. Besides, based on the pore size distribution of PVA: silica (5:5) showed the narrow pore size distribution with the largest pore cumulative volume of 2.8 x 10-3 cc/g. The optimum pH for Methanyl Yellow adsorption is pH 2 with adsorption capacity = 72.1346%.
NASA Astrophysics Data System (ADS)
Niu, Qifei; Zhang, Chi
2018-02-01
The empirical Archie's law has been widely used in geosciences and engineering to explain the measured electrical resistivity of many geological materials, but its physical basis has not been fully understood yet. In this study, we use a pore-scale numerical approach combining discrete element-finite difference methods to study Archie's porosity exponent m of granular materials over a wide porosity range. Numerical results reveal that at dilute states (e.g., porosity ϕ > 65%), m is exclusively related to the particle shape and orientation. As the porosity decreases, the electric flow in pore space concentrates progressively near particle contacts and m increases continuously in response to the intensified nonuniformity of the local electrical field. It is also found that the increase in m is universally correlated with the volume fraction of pore throats for all the samples regardless of their particle shapes, particle size range, and porosities.
Fractal Characteristics of Pores in Taiyuan Formation Shale from Hedong Coal Field, China
NASA Astrophysics Data System (ADS)
Li, Kunjie; Zeng, Fangui; Cai, Jianchao; Sheng, Guanglong; Xia, Peng; Zhang, Kun
For the purpose of investigating the fractal characteristics of pores in Taiyuan formation shale, a series of qualitative and quantitative experiments were conducted on 17 shale samples from well HD-1 in Hedong coal field of North China. The results of geochemical experiments show that Total organic carbon (TOC) varies from 0.67% to 5.32% and the organic matters are in the high mature or over mature stage. The shale samples consist mainly of clay minerals and quartz with minor pyrite and carbonates. The FE-SEM images indicate that three types of pores, organic-related pores, inorganic-related pores and micro-fractures related pores, are developed well, and a certain number of intragranular pores are found inside quartz and carbonates formed by acid liquid corrosion. The pore size distributions (PSDs) broadly range from several to hundreds nanometers, but most pores are smaller than 10nm. As the result of different adsorption features at relative pressure (0-0.5) and (0.5-1) on the N2 adsorption isotherm, two fractal dimensions D1 and D2 were obtained with the Frenkel-Halsey-Hill (FHH) model. D1 and D2 vary from 2.4227 to 2.6219 and from 2.6049 to 2.7877, respectively. Both TOC and brittle minerals have positive effect on D1 and D2, whereas clay minerals, have a negative influence on them. The fractal dimensions are also influenced by the pore structure parameters, such as the specific surface area, BJH pore volume, etc. Shale samples with higher D1 could provide more adsorption sites leading to a greater methane adsorption capacity, whereas shale samples with higher D2 have little influence on methane adsorption capacity.
Increased Cortical Porosity in Type-2 Diabetic Postmenopausal Women with Fragility Fractures
Patsch, Janina M.; Burghardt, Andrew J.; Yap, Samuel P.; Baum, Thomas; Schwartz, Ann V.; Joseph, Gabby B.; Link, Thomas M.
2012-01-01
The primary goal of this study was to assess peripheral bone microarchitecture and strength in diabetic postmenopausal women with fragility fractures (DMFx) and to compare them with diabetic women without fracture (DM). Secondary goals were to assess differences in non-diabetic women with (Fx) and without fragility fractures (Co) and in women with (DM) and without diabetes (Co). Eighty women (mean age 61.3±5.7 yrs) were recruited into these groups (n=20 per group). Participants underwent DXA and high-resolution peripheral quantitative computed tomography (HR-pQCT) of the ultradistal and distal radius and tibia. In the HR-pQCT images volumetric bone mineral density, cortical and trabecular structure measures, including cortical porosity, were calculated. Bone strength was estimated using micro-finite element analysis (μFEA). Differential strength estimates were obtained with and without open cortical pores. At the ultradistal and distal tibia, DMFx had greater intracortical pore volume (+52.6%, p=0.009; +95.4%, p=0.020), relative porosity (+58.1%; p=0.005; +87.9%, p=0.011) and endocortical bone surface (+10.9%, p=0.031; +11.5%, 0.019) than DM. At the distal radius DMFx had 4.7-fold greater relative porosity (p=0.000) than DM. At the ultradistal radius, intracortical pore volume was significantly higher in DMFx than DM (+67.8%, p=0.018). DMFx also displayed larger trabecular heterogeneity (ultradistal radius; +36.8%, p=0.035), and lower total and cortical BMD (ultradistal tibia: −12.6%, p=0.031; −6.8%, p=0.011) than DM. DMFx exhibited significantly higher pore-related deficits in stiffness, failure load and cortical load fraction at the ultradistal and distal tibia, and the distal radius than DM. Comparing non-diabetic Fx and Co, we only found a non-significant trend with increase in pore volume (+38.9%, p=0.060) at the ultradistal radius. The results of our study suggest that severe deficits in cortical bone quality are responsible for fragility fractures in postmenopausal diabetic women. PMID:22991256
Biochar from Coffee Residues: A New Promising Sorbent
NASA Astrophysics Data System (ADS)
Fotopoulou, Kalliopi; Karapanagioti, Hrissi; Manariotis, Ioannis
2014-05-01
Biochar is a carbon-rich material produced by heating biomass in an oxygen-limited environment. Biochar is mainly used as an additive to soils to sequester carbon and improve soil fertility as well as a sorbent for environmental remediation processes. Surface properties such as point of zero charge, surface area and pore volume, surface topography, surface functional groups and acid-base behavior are important factors, which affect sorption efficiency. Understanding the surface alteration of biochars increases our understanding of the pollutant-sorbent interaction. The objective of the present study was to characterize the surface properties of biochar produced, and to investigate the effect of thermal treatment conditions on key characteristics that affect sorptive properties. The espresso coffee residue was obtained after the coffee was brewed through espresso machines in coffee shops. The coffee residue was dried and kept in an oven at 50oC until its pyrolysis at 850oC. Pyrolysis with different coffee mass and containers were tested in order to find optimum biochar characteristics. Detailed characterization techniques were carried out to determine the properties of the produced biochar. The surface area, the pore volume, and the average pore size of the biochars were determined using gas (N2) adsorption-desorption cycles using the Brunauer, Emmett, and Teller (BET) equation. Open surface area and micropore volume were determined using the t-plot method and the Harkins & Jura equation. Total organic carbon was also determined because it is an important factor that affects sorption. The results were compared with the corresponding properties of activated carbons. The biochar produced exhibited a wide range of surface area from 21 to 770 m2/g and open surface area from 21 to 65 m2/g. It is obvious that the surface area results from the formation of pores. Actually it was calculated that up to 90% of the porosity is due to the micropores. More specifically the average size of the pores for the high surface area biochars was 32 A. Finally, the organic carbon content of the produced biochar ranged from 45 to 75%.
Guard cells elongate: relationship of volume and surface area during stomatal movement.
Meckel, Tobias; Gall, Lars; Semrau, Stefan; Homann, Ulrike; Thiel, Gerhard
2007-02-01
Stomata in the epidermis of photosynthetically active plant organs are formed by pairs of guard cells, which create a pore, to facilitate CO2 and water exchange with the environment. To control this gas exchange, guard cells actively change their volume and, consequently, surface area to alter the aperture of the stomatal pore. Due to the limited elasticity of the plasma membrane, such changes in surface area require an exocytic addition or endocytic retrieval of membrane during stomatal movement. Using confocal microscopic data, we have reconstructed detailed three-dimensional models of open and closed stomata to precisely quantify the necessary area to be exo- and endocytosed by the guard cells. Images were obtained under a strong emphasis on a precise calibration of the method and by avoiding unphysiological osmotical imbalance, and hence osmocytosis. The data reveal that guard cells of Vicia faba L., whose aperture increases by 111.89+/-22.39%, increase in volume and surface area by 24.82+/-6.26% and 14.99+/-2.62%, respectively. In addition, the precise volume to surface area relationship allows quantitative modeling of the three-dimensional changes. While the major volume change is caused by a slight increase in the cross section of the cells, an elongation of the guard cells achieves the main aperture change.
Ring-Interferometric Sol-Gel Bio-Sensor
NASA Technical Reports Server (NTRS)
Bearman, Gregory (Inventor); Cohen, David (Inventor)
2006-01-01
A biosensor embodying the invention includes a sensing volume having an array of pores sized for immobilizing a first biological entity tending to bind to a second biological entity in such a manner as to change an index of refraction of the sensing volume. The biosensor further includes a ring interferometer, one volumetric section of the ring interferometer being the sensing volume, a laser for supplying light to the ring interferometer, and a photodetector for receiving light from the interferometer.
NASA Astrophysics Data System (ADS)
Beckingham, L. E.; Zhang, S.; Mitnick, E.; Cole, D. R.; Yang, L.; Anovitz, L. M.; Sheets, J.; Swift, A.; Kneafsey, T. J.; Landrot, G.; Mito, S.; Xue, Z.; Steefel, C. I.; DePaolo, D. J.; Ajo Franklin, J. B.
2014-12-01
Geologic sequestration of CO2 in deep sedimentary formations is a promising means of mitigating carbon emissions from coal-fired power plants but the long-term fate of injected CO2 is challenging to predict. Reactive transport models are used to gain insight over long times but rely on laboratory determined mineral reaction rates that have been difficult to extrapolate to field systems. This, in part, is due to a lack of understanding of mineral reactive surface area. Many models use an arbitrary approximation of reactive surface area, applying orders of magnitude scaling factors to measured BET or geometric surface areas. Recently, a few more sophisticated approaches have used 2D and 3D image analyses to determine mineral-specific reactive surface areas that account for the accessibility of minerals. However, the ability of these advanced surface area estimates to improve predictions of mineral reaction rates has yet to be determined. In this study, we fuse X-ray microCT, SEM QEMSCAN, XRD, SANS, and SEM-FIB analysis to determine mineral-specific accessible reactive surface areas for a core sample from the Nagaoka pilot CO2 injection site (Japan). This sample is primarily quartz, plagioclase, smectite, K-feldspar, and pyroxene. SEM imaging shows abundant smectite cement and grain coatings that decrease the fluid accessibility of other minerals. However, analysis of FIB-SEM images reveals that smectite nano-pores are well connected such that access to underlying minerals is not occluded by smectite coatings. Mineral-specific accessible surfaces are determined, accounting for the connectivity of the pore space with and without connected smectite nano-pores. The large-scale impact of variations in accessibility and dissolution rates are then determined through continuum scale modeling using grid-cell specific information on accessible surface areas. This approach will be compared with a traditional continuum scale model using mineral abundances and common surface area estimates. Ultimately, the effectiveness of advanced surface area characterization to improve mineral dissolution rates will be evaluated by comparison of model results with dissolution rates measured from a flow-through column experiment.
Bakhtiari, L; Rezaie, H R; Javadpour, J; Erfan, M; Shokrgozar, M A
2015-08-01
Mesoporous hydroxyapatite with different pore diameters and pore volumes were synthesized by the self-assembly method using Cetyltrimethylammonium bromide (CTAB) as the cationic surfactant and 1-dodecanethiol as the pore expander at different micellization pHs, solvent types and surfactant concentrations. Results of field emission scanning electron microscopy (FESEM) showed a decrease in length/diameter ratio of rod-like particles by an increase in micellization pH and also a sphere to rod transition in morphology by an increase in CTAB concentration. Brunauer-Emmett-Teller (BET) surface area and Low angle X-ray diffraction analysis revealed that the optimized mesoporous hydroxyapatite with controlled pore structure can be obtained under basic micellization pH (about 12, pH of complete ionization of 1-dodecanethiol) by using water as the solvent and a high content of cationic surfactant. The results also show that micellization pH has a strong effect on pore structure and changing the pH can shift the mesostructure to a macroporous structure with morphological changes. Copyright © 2015 Elsevier B.V. All rights reserved.
Hechenleitner, E Martín; Grellet-Tinner, Gerald; Foley, Matthew; Fiorelli, Lucas E; Thompson, Michael B
2016-03-01
The Cretaceous Sanagasta neosauropod nesting site (La Rioja, Argentina) was the first confirmed instance of extinct dinosaurs using geothermal-generated heat to incubate their eggs. The nesting strategy and hydrothermal activities at this site led to the conclusion that the surprisingly 7 mm thick-shelled eggs were adapted to harsh hydrothermal microenvironments. We used micro-CT scans in this study to obtain the first three-dimensional microcharacterization of these eggshells. Micro-CT-based analyses provide a robust assessment of gas conductance in fossil dinosaur eggshells with complex pore canal systems, allowing calculation, for the first time, of the shell conductance through its thickness. This novel approach suggests that the shell conductance could have risen during incubation to seven times more than previously estimated as the eggshell erodes. In addition, micro-CT observations reveal that the constant widening and branching of pore canals form a complex funnel-like pore canal system. Furthermore, the high density of pore canals and the presence of a lateral canal network in the shell reduce the risks of pore obstruction during the extended incubation of these eggs in a relatively highly humid and muddy nesting environment. © 2016 The Author(s).
Modeling the Pore Formation Mechanism in UMo/AL Dispersion Fuel
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kim, Yeon Soo; Jamison, L.; Hofman, G.
In UMo/Al dispersion fuel meat, pores formed in the ILs or at IL-Al interfaces tend to increase in size with irradiation, potentially limiting performance of this fuel. There has been no universally accepted mechanism for the formation and growth of this type of pore. However, there is a consensus that the stress state determined by meat swelling and fission- induced creep is one of the determinants, and fission gas availability at the pore site is another. Five dispersion RERTR miniplates that have well defined irradiation conditions and PIE data were selected for examination. Meat swelling and pore volume were measuredmore » in each plate. ABAQUS finite element analysis (FEA) package was utilized to obtain the time-dependent evolution of mechanical states in the plates while matching the measured meat swelling and creep. Interpretation of these results give insights on how to model a failure function – a predictor for large pore formation – using variables such as meat swelling, interaction layer growth, stress, and creep. This model can be used for optimizing fuel design parameters to reach the desired goal: meeting high power and performance reactor demand.« less
Modeling of submicrometer aerosol penetration through sintered granular membrane filters.
Marre, Sonia; Palmeri, John; Larbot, André; Bertrand, Marielle
2004-06-01
We present a deep-bed aerosol filtration model that can be used to estimate the efficiency of sintered granular membrane filters in the region of the most penetrating particle size. In this region the capture of submicrometer aerosols, much smaller than the filter pore size, takes place mainly via Brownian diffusion and direct interception acting in synergy. By modeling the disordered sintered grain packing of such filters as a simple cubic lattice, and mapping the corresponding 3D connected pore volume onto a discrete cylindrical pore network, the efficiency of a granular filter can be estimated, using new analytical results for the efficiency of cylindrical pores. This model for aerosol penetration in sintered granular filters includes flow slip and the kinetics of particle capture by the pore surface. With a unique choice for two parameters, namely the structural tortuosity and effective kinetic coefficient of particle adsorption, this semiempirical model can account for the experimental efficiency of a new class of "high-efficiency particulate air" ceramic membrane filters as a function of particle size over a wide range of filter thickness and texture (pore size and porosity) and operating conditions (face velocity).
Tailoring pore properties of MCM-48 silica for selective adsorption of CO2.
Kim, Sangil; Ida, Junichi; Guliants, Vadim V; Lin, Jerry Y S
2005-04-07
Four different types of amine-attached MCM-48 silicas were prepared and investigated for CO(2) separation from N(2). Monomeric and polymeric hindered and unhindered amines were attached to the pore surface of the MCM-48 silica and characterized with respect to their CO(2) sorption properties. The pore structures and amino group content in these modified silicas were investigated by XRD, FT-IR, TGA, N(2) adsorption/desorption at 77 K and CHN/Si analysis, which confirmed that in all cases the amino groups were attached to the pore surface of MCM-48 at 1.5-5.2 mmol/g. The N(2) adsorption/desorption analysis showed a considerable decrease of the pore volume and surface area for the MCM-48 silica containing a polymeric amine (e.g., polyethyleneimine). The CO(2) adsorption rates and capacities of the amine-attached MCM-48 samples were studied employing a sorption microbalance. The results obtained indicated that in addition to the concentration of surface-attached amino groups, specific interactions between CO(2) and the surface amino groups, and the resultant pore structure after amine group attachment have a significant impact on CO(2) adsorption properties of these promising adsorbent materials.
Porosity in low dielectric constant SiOCH films depth profiled by positron annihilation spectroscopy
NASA Astrophysics Data System (ADS)
Brusa, R. S.; Spagolla, M.; Karwasz, G. P.; Zecca, A.; Ottaviani, G.; Corni, F.; Bacchetta, M.; Carollo, E.
2004-03-01
The 3γ annihilation of orthopositronium and the Doppler broadening of the positron annihilation line have been measured by implanting low energy positrons in low dielectric constant (low-k) SiOCH films. The evolution and stability of film porosity with thermal treatments in the 400-900 °C temperature range has been studied. The films have been produced by plasma enhanced chemical vapor deposition and after annealing in N2 atmospheres at 480 °C have been treated in N2+He plasma. The minimum free volume of the pores in the as-produced samples has been estimated to correspond to that of a sphere with radius r=0.6 nm. The treatment in the N2 plasma was found to seal the pores up to 45 nm depth. Both the composition of the films (as obtained by Rutherford backscattering spectroscopy and elastic recoil detection analysis) and the chemical environment of the pores probed by positrons were found to be very stable up to 600 °C thermal treatment. Above such a temperature a reduction of the hydrogen content accompanied by a change in the structure and in the chemical environment of the pores has been observed. In the samples thermal treated at 800-900 °C, the positronium formation is reduced by one-third respect with the as produced sample. In the annealed and as-produced films, a natural aging of 30 days in air was enough to contaminate the porosity, as pointed out by a strong reduction of the 3γ annihilations. The effect of contamination and the distribution of the pores were completely recovered after a thermal treatment at 400 °C. Artificial aging of SiOCH films in controlled atmospheres of H2, O2, H2O has shown that H2O is the more efficient contaminant in reducing the effective volume of the pores.
Impact of geometrical properties on permeability and fluid phase distribution in porous media
NASA Astrophysics Data System (ADS)
Lehmann, P.; Berchtold, M.; Ahrenholz, B.; Tölke, J.; Kaestner, A.; Krafczyk, M.; Flühler, H.; Künsch, H. R.
2008-09-01
To predict fluid phase distribution in porous media, the effect of geometric properties on flow processes must be understood. In this study, we analyze the effect of volume, surface, curvature and connectivity (the four Minkowski functionals) on the hydraulic conductivity and the water retention curve. For that purpose, we generated 12 artificial structures with 800 3 voxels (the units of a 3D image) and compared them with a scanned sand sample of the same size. The structures were generated with a Boolean model based on a random distribution of overlapping ellipsoids whose size and shape were chosen to fulfill the criteria of the measured functionals. The pore structure of sand material was mapped with X-rays from synchrotrons. To analyze the effect of geometry on water flow and fluid distribution we carried out three types of analysis: Firstly, we computed geometrical properties like chord length, distance from the solids, pore size distribution and the Minkowski functionals as a function of pore size. Secondly, the fluid phase distribution as a function of the applied pressure was calculated with a morphological pore network model. Thirdly, the permeability was determined using a state-of-the-art lattice-Boltzmann method. For the simulated structure with the true Minkowski functionals the pores were larger and the computed air-entry value of the artificial medium was reduced to 85% of the value obtained from the scanned sample. The computed permeability for the geometry with the four fitted Minkowski functionals was equal to the permeability of the scanned image. The permeability was much more sensitive to the volume and surface than to curvature and connectivity of the medium. We conclude that the Minkowski functionals are not sufficient to characterize the geometrical properties of a porous structure that are relevant for the distribution of two fluid phases. Depending on the procedure to generate artificial structures with predefined Minkowski functionals, structures differing in pore size distribution can be obtained.
Molecular accessibility in solvent swelled coal
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kispert, L.D.
1991-08-01
Research continued on the determination of pore size and number distribution changes after swelling the coal samples with various solvents. A paper has just been submitted to the journal Fuel on the Low temperature Swelling of Argonne Premium Coal samples using solvents of varying polarity. The variation in the shape of the pore was followed as a function of temperature and swelling solvent polarity. This change in pore structure was attributed to break-up of the hydrogen bonding network in coal by polar solvents. The modification in pore shape from spherical to cylindrical was attributed to anisotropy in hydrogen bond densities.more » A copy of this paper has been attached to this report. Wojciech Sady has determine the structural changes in the pores that occur when APCS coal is dehydrated prior to swelling with polar solvents. These changes are different from those that occur in the absence of prior dehydration. He has also completed a study on the variation in the hydrogen bonding character of the pore wall as the coals are swelled with various polar solvents. A statistical analysis of the data is currently underway to determine important trends in his data. 9 refs.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Liu, X.; Magnel Laboratory for Concrete Research, Department of Structural Engineering, Ghent University, Technologiepark-Zwijnaarde 904 B-9052, Ghent; Ye, G.
2008-04-15
With the increasing application of self-compacting concrete (SCC) in construction and infrastructure, the fire spalling behavior of SCC has been attracting due attention. In high performance concrete (HPC), addition of polypropylene fibers (PP fibers) is widely used as an effective method to prevent explosive spalling. Hence, it would be useful to investigate whether the PP fibers are also efficient in SCC to avoid explosive spalling. However, no universal agreement exists concerning the fundamental mechanism of reducing the spalling risk by adding PP fiber. For SCC, the reduction of flowability should be considered when adding a significant amount of fibres. Inmore » this investigation, both the micro-level and macro-level properties of pastes with different fiber contents were studied in order to investigate the role of PP fiber at elevated temperature in self-compacting cement paste samples. The micro properties were studied by backscattering electron microscopy (BSE) and mercury intrusion porosimetry (MIP) tests. The modification of the pore structure at elevated temperature was investigated as well as the morphology of the PP fibers. Some macro properties were measured, such as the gas permeability of self-compacting cement paste after heating at different temperatures. The factors influencing gas permeability were analyzed. It is shown that with the melting of PP fiber, no significant increase in total pore volume is obtained. However, the connectivity of isolated pores increases, leading to an increase of gas permeability. With the increase of temperature, the addition of PP fibers reduces the damage of cement pastes, as seen from the total pore volume and the threshold pore diameter changes. From this investigation, it is concluded that the connectivity of pores as well as the creation of micro cracks are the major factors which determine the gas permeability after exposure to high temperatures. Furthermore, the connectivity of the pores acts as a dominant factor for temperatures below 300 deg. C. For higher temperatures micro cracks are becoming the major factor which influences the gas permeability.« less
Numerical Modeling of the 2014 Oso, Washington, Landslide.
NASA Astrophysics Data System (ADS)
George, D. L.; Iverson, R. M.
2014-12-01
Numerical simulations of alternative scenarios that could have transpired during the Oso, Washington, landslide of 22 March 2014 provide insight into factors responsible for the landslide's devastating high-speed runout.We performed these simulations using D-Claw, a numerical model we recently developed to simulate landslide and debris-flow motion from initiation to deposition. D-Claw solves a hyperbolic system of five partial differential equations that describe simultaneous evolution of the thickness,solid volume fraction, basal pore-fluid pressure, and two components of momentum of the moving mass. D-Claw embodies the concept ofstate-dependent dilatancy, which causes the solid volume fraction m to evolve toward a value that is equilibrated to the ambient stress state andshear rate. As the value of m evolves, basal pore-fluid pressure coevolves,and thereby causes an evolution in frictional resistance to motion. Our Oso simulations considered alternative scenarios in which values of all model parameters except the initial solid volume fraction m0 were held constant.These values were: basal friction angle = 36°; static critical-state solidvolume fraction = 0.64; initial sediment permeability = 10-8 m2; pore-fluid density = 1100 kg/m3; sediment grain density = 2700 kg/m3; pore-fluid viscosity = 0.005 Pa-s; and dimensionless sediment compressibility coefficient = 0.03. Simulations performed using these values and m0 = 0.62 produced widespread landslide liquefaction, runaway acceleration, andlandslide runout distances, patterns and speeds similar to those observed or inferred for the devastating Oso event. Alternative simulations that usedm0 = 0.64 produced a much slower landslide that did not liquefy and that traveled only about 100 m before stopping. This relatively benign behavioris similar to that of several landslides at the Oso site prior to 2014. Our findings illustrate a behavioral bifurcation that is highly sensitive to the initial solid volume fraction. They suggest that the destructiveness of the2014 Oso event may have resulted in part from prior slope deformation that produced a dilated sediment state that made the sediment susceptible to contraction and liquefaction as it began to fail on March 22.
Anderson, David Ebo; Balapangu, Srinivasan; Fleischer, Heidimarie N A; Viade, Ruth A; Krampa, Francis D; Kanyong, Prosper; Awandare, Gordon A; Tiburu, Elvis K
2017-08-08
Temperature-dependent zeolite synthesis has revealed a unique surface morphology, surface area and pore size which influence the immobilization of urease on gold electrode supports for biosensor fabrication. XRD characterization has identified zeolite X (Na) at all crystallization temperatures tested. However, N₂ adsorption and desorption results showed a pore size and pore volume of zeolite X (Na) 60 °C, zeolite X (Na) 70 °C and zeolite X (Na) 90 °C to range from 1.92 nm to 2.45 nm and 0.012 cm³/g to 0.061 cm³/g, respectively, with no significant differences. The specific surface area of zeolite X (Na) at 60, 70 and 90 °C was 64 m²/g, 67 m²/g and 113 m²/g, respectively. The pore size, specific surface area and pore volumes of zeolite X (Na) 80 °C and zeolite X (Na) 100 °C were dramatically increased to 4.21 nm, 295 m²/g, 0.762 cm³/g and 4.92 nm, 389 m²/g, 0.837 cm³/g, in that order. The analytical performance of adsorbed urease on zeolite X (Na) surface was also investigated using cyclic voltammetry measurements, and the results showed distinct cathodic and anodic peaks by zeolite X (Na) 80 °C and zeolite X (Na) 100 °C. These zeolites' molar conductance was measured as a function of urea concentration and gave an average polynomial regression fit of 0.948. The findings in this study suggest that certain physicochemical properties, such as crystallization temperature and pH, are critical parameters for improving the morphological properties of zeolites synthesized from natural sources for various biomedical applications.
Anderson, David Ebo; Balapangu, Srinivasan; Fleischer, Heidimarie N. A.; Viade, Ruth A.; Awandare, Gordon A.; Tiburu, Elvis K.
2017-01-01
Temperature-dependent zeolite synthesis has revealed a unique surface morphology, surface area and pore size which influence the immobilization of urease on gold electrode supports for biosensor fabrication. XRD characterization has identified zeolite X (Na) at all crystallization temperatures tested. However, N2 adsorption and desorption results showed a pore size and pore volume of zeolite X (Na) 60 °C, zeolite X (Na) 70 °C and zeolite X (Na) 90 °C to range from 1.92 nm to 2.45 nm and 0.012 cm3/g to 0.061 cm3/g, respectively, with no significant differences. The specific surface area of zeolite X (Na) at 60, 70 and 90 °C was 64 m2/g, 67 m2/g and 113 m2/g, respectively. The pore size, specific surface area and pore volumes of zeolite X (Na) 80 °C and zeolite X (Na) 100 °C were dramatically increased to 4.21 nm, 295 m2/g, 0.762 cm3/g and 4.92 nm, 389 m2/g, 0.837 cm3/g, in that order. The analytical performance of adsorbed urease on zeolite X (Na) surface was also investigated using cyclic voltammetry measurements, and the results showed distinct cathodic and anodic peaks by zeolite X (Na) 80 °C and zeolite X (Na) 100 °C. These zeolites’ molar conductance was measured as a function of urea concentration and gave an average polynomial regression fit of 0.948. The findings in this study suggest that certain physicochemical properties, such as crystallization temperature and pH, are critical parameters for improving the morphological properties of zeolites synthesized from natural sources for various biomedical applications. PMID:28786961
Farid, Ramy; Day, Tyler; Friesner, Richard A; Pearlstein, Robert A
2006-05-01
We created a homology model of the homo-tetrameric pore domain of HERG using the crystal structure of the bacterial potassium channel, KvAP, as a template. We docked a set of known blockers with well-characterized effects on channel function into the lumen of the pore between the selectivity filter and extracellular entrance using a novel docking and refinement procedure incorporating Glide and Prime. Key aromatic groups of the blockers are predicted to form multiple simultaneous ring stacking and hydrophobic interactions among the eight aromatic residues lining the pore. Furthermore, each blocker can achieve these interactions via multiple docking configurations. To further interpret the docking results, we mapped hydrophobic and hydrophilic potentials within the lumen of each refined docked complex. Hydrophilic iso-potential contours define a 'propeller-shaped' volume at the selectivity filter entrance. Hydrophobic contours define a hollow 'crown-shaped' volume located above the 'propeller', whose hydrophobic 'rim' extends along the pore axis between Tyr652 and Phe656. Blockers adopt conformations/binding orientations that closely mimic the shapes and properties of these contours. Blocker basic groups are localized in the hydrophilic 'propeller', forming electrostatic interactions with Ser624 rather than a generally accepted pi-cation interaction with Tyr652. Terfenadine, cisapride, sertindole, ibutilide, and clofilium adopt similar docked poses, in which their N-substituents bridge radially across the hollow interior of the 'crown' (analogous to the hub and spokes of a wheel), and project aromatic/hydrophobic portions into the hydrophobic 'rim'. MK-499 docks with its longitudinal axis parallel to the axis of the pore and 'crown', and its hydrophobic groups buried within the hydrophobic 'rim'.
NASA Astrophysics Data System (ADS)
Soldatov, A. P.
2017-05-01
As part of ongoing studies aimed at designing the next generation of nanosized membrane reactors (NMRs) with accumulated hydrogen, the noncatalytic hydrogenation of naphthalene in pores of ceramic membranes (TRUMEM ultrafiltration membranes with D av = 50 and 90 nm) is performed for the first time, using hydrogen preadsorbed in a hybrid carbon nanostructure: mono- and multilayered oriented carbon nanotubes with graphene walls (OCNTGs) that form on inner pore surfaces. In this technique, the reaction proceeds in the temperature range of 330-390°C at contact times of 10-16 h. The feedstock is an 8% naphthalene solution in decane. The products are analyzed via chromatography on a quartz capillary column coated with polydimethylsiloxane (SE-30). It is established for the first time that in NMRs, the noncatalytic hydrogenation of naphthalene occurs at 370-390°C, forming 1,2,3,4-tetrahydronaphthalene in amounts of up to 0.61%. The rate constants and activation energy (123.5 kJ/mol) of the noncatalytic hydrogenation reaction are determined for the first time. The possibility of designing an NMR with an adjustable reaction zone volume is explored. Changes in the pore structure of the membranes after their modification with pyrocarbon nanosized crystallites (PNCs) are therefore studied as well. It is shown that lengthening the process time reduces pore size: within 23 h after the deposition of PNCs, the average pore radius ( r av) falls from 25 to 3.1 nm. The proposed approach would allow us to design nanoreactors of molecular size and conduct hydrogenation reactions within certain guidelines to synthesize new chemical compounds.
Morrow, C.A.; Byerlee, J.D.
1989-01-01
Transient strength changes are observed in fault gouge materials when the velocity of shearing is varied. A transient stress peak is produced when the strain rate in the gouge is suddenly increased, whereas a transient stress drop results from a sudden change to a slower strain rate. We have studied the mechanism responsible for these observations by performing frictional sliding experiments on sawcut granite samples filled with a layer of several different fault gouge types. Changes in pore volume and strength were monitored as the sliding velocity alternated between fast and slow rates. Pore volume increased at the faster strain rate, indicating a dilation of the gouge layer, whereas volume decreased at the slower rate indicating compaction. These results verify that gouge dilation is a function of strain rate. Pore volume changed until an equilibrium void ratio of the granular material was reached for a particular rate of strain. Using arguments from soil mechanics, we find that the dense gouge was initially overconsolidated relative to the equilibrium level, whereas the loose gouge was initially underconsolidated relative to this level. Therefore, the transient stress behavior must be due to the overconsolidated state of the gouge at the new rate when the velocity is increased and to the underconsolidated state when the velocity is lowered. Time-dependent compaction was also shown to cause a transient stress response similar to the velocity-dependent behavior. This may be important in natural fault gouges as they become consolidated and stronger with time. In addition, the strain hardening of the gouge during shearing was found to be a function of velocity, rendering it difficult to quantify the change in equilibrium shear stress when velocity is varied under certain conditions. ?? 1989.
Carey, John B.; Pearson, Frances E.; Vrdoljak, Anto; McGrath, Marie G.; Crean, Abina M.; Walsh, Patrick T.; Doody, Timothy; O'Mahony, Conor; Hill, Adrian V. S.; Moore, Anne C.
2011-01-01
Background Vaccine delivery into the skin has received renewed interest due to ease of access to the immune system and microvasculature, however the stratum corneum (SC), must be breached for successful vaccination. This has been achieved by removing the SC by abrasion or scarification or by delivering the vaccine intradermally (ID) with traditional needle-and-syringes or with long microneedle devices. Microneedle patch-based transdermal vaccine studies have predominantly focused on antibody induction by inactivated or subunit vaccines. Here, our principal aim is to determine if the design of a microneedle patch affects the CD8+ T cell responses to a malaria antigen induced by a live vaccine. Methodology and Findings Recombinant modified vaccinia virus Ankara (MVA) expressing a malaria antigen was percutaneously administered to mice using a range of silicon microneedle patches, termed ImmuPatch, that differed in microneedle height, density, patch area and total pore volume. We demonstrate that microneedle arrays that have small total pore volumes induce a significantly greater proportion of central memory T cells that vigorously expand to secondary immunization. Microneedle-mediated vaccine priming induced significantly greater T cell immunity post-boost and equivalent protection against malaria challenge compared to ID vaccination. Notably, unlike ID administration, ImmuPatch-mediated vaccination did not induce inflammatory responses at the site of immunization or in draining lymph nodes. Conclusions/Significance This study demonstrates that the design of microneedle patches significantly influences the magnitude and memory of vaccine-induced CD8+ T cell responses and can be optimised for the induction of desired immune responses. Furthermore, ImmuPatch-mediated delivery may be of benefit to reducing unwanted vaccine reactogenicity. In addition to the advantages of low cost and lack of pain, the development of optimised microneedle array designs for the induction of T cell responses by live vaccines aids the development of solutions to current obstacles of immunization programmes. PMID:21799855
NASA Astrophysics Data System (ADS)
Yeck, William L.; Block, Lisa V.; Wood, Christopher K.; King, Vanessa M.
2015-01-01
The Paradox Valley Unit (PVU), a salinity control project in southwest Colorado, disposes of brine in a single deep injection well. Since the initiation of injection at the PVU in 1991, earthquakes have been repeatedly induced. PVU closely monitors all seismicity in the Paradox Valley region with a dense surface seismic network. A key factor for understanding the seismic hazard from PVU injection is the maximum magnitude earthquake that can be induced. The estimate of maximum magnitude of induced earthquakes is difficult to constrain as, unlike naturally occurring earthquakes, the maximum magnitude of induced earthquakes changes over time and is affected by injection parameters. We investigate temporal variations in maximum magnitudes of induced earthquakes at the PVU using two methods. First, we consider the relationship between the total cumulative injected volume and the history of observed largest earthquakes at the PVU. Second, we explore the relationship between maximum magnitude and the geometry of individual seismicity clusters. Under the assumptions that: (i) elevated pore pressures must be distributed over an entire fault surface to initiate rupture and (ii) the location of induced events delineates volumes of sufficiently high pore-pressure to induce rupture, we calculate the largest allowable vertical penny-shaped faults, and investigate the potential earthquake magnitudes represented by their rupture. Results from both the injection volume and geometrical methods suggest that the PVU has the potential to induce events up to roughly MW 5 in the region directly surrounding the well; however, the largest observed earthquake to date has been about a magnitude unit smaller than this predicted maximum. In the seismicity cluster surrounding the injection well, the maximum potential earthquake size estimated by these methods and the observed maximum magnitudes have remained steady since the mid-2000s. These observations suggest that either these methods overpredict maximum magnitude for this area or that long time delays are required for sufficient pore-pressure diffusion to occur to cause rupture along an entire fault segment. We note that earthquake clusters can initiate and grow rapidly over the course of 1 or 2 yr, thus making it difficult to predict maximum earthquake magnitudes far into the future. The abrupt onset of seismicity with injection indicates that pore-pressure increases near the well have been sufficient to trigger earthquakes under pre-existing tectonic stresses. However, we do not observe remote triggering from large teleseismic earthquakes, which suggests that the stress perturbations generated from those events are too small to trigger rupture, even with the increased pore pressures.
Liu, Xuehong; Dawson, David C
2011-11-29
Cysteine scanning has been widely used to identify pore-lining residues in mammalian ion channels, including the cystic fibrosis transmembrane conductance regulator (CFTR). These studies, however, have been typically conducted at room temperature rather than human body temperature. Reports of substantial effects of temperature on gating and anion conduction in CFTR channels as well as an unexpected pattern of cysteine reactivity in the sixth transmembrane segment (TM6) prompted us to investigate the effect of temperature on the reactivity of cysteines engineered into TM6 of CFTR. We compared reaction rates at temperatures ranging from 22 to 37 °C for cysteines placed on either side of an apparent size-selective accessibility barrier previously defined by comparing reactivity toward channel-permeant and channel-impermeant, thiol-directed reagents. The results indicate that the reactivity of cysteines at three positions extracellular to the position of the accessibility barrier, 334, 336, and 337, is highly temperature-dependent. At 37 °C, cysteines at these positions were highly reactive toward MTSES(-), whereas at 22 °C, the reaction rates were 2-6-fold slower to undetectable. An activation energy of 157 kJ/mol for the reaction at position 337 is consistent with the hypothesis that, at physiological temperature, the extracellular portion of the CFTR pore can adopt conformations that differ significantly from those that can be accessed at room temperature. However, the position of the accessibility barrier defined empirically by applying channel-permeant and channel-impermeant reagents to the extracellular aspect of the pore is not altered. The results illuminate previous scanning results and indicate that the assay temperature is a critical variable in studies designed to use chemical modification to test structural models for the CFTR anion conduction pathway.
Theoretical Analysis of Pore Pressure Diffusion in Some Basic Rock Mechanics Experiments
NASA Astrophysics Data System (ADS)
Braun, Philipp; Ghabezloo, Siavash; Delage, Pierre; Sulem, Jean; Conil, Nathalie
2018-05-01
Non-homogeneity of the pore pressure field in a specimen is an issue for characterization of the thermo-poromechanical behaviour of low-permeability geomaterials, as in the case of the Callovo-Oxfordian claystone ( k < 10-20 m2), a possible host rock for deep radioactive waste disposal in France. In tests with drained boundary conditions, excess pore pressure can result in significant errors in the measurement of material parameters. Analytical solutions are presented for the change in time of the pore pressure field in a specimen submitted to various loading paths and different rates. The pore pressure field in mechanical and thermal undrained tests is simulated with a 1D finite difference model taking into account the dead volume of the drainage system of the triaxial cell connected to the specimen. These solutions provide a simple and efficient tool for the estimation of the conditions that must hold for reliable determination of material parameters and for optimization of various test conditions to minimize the experimental duration, while keeping the measurement errors at an acceptable level.
Hu, Haiyan; Zhang, Tongwei; Wiggins-Camacho, Jaclyn D.; Ellis, Geoffrey S.; Lewan, Michael D.; Zhang, Xiayong
2014-01-01
This study quantifies the effects of organic-matter (OM) thermal maturity on methane (CH4) sorption, on the basis of five samples that were artificially matured through hydrous pyrolysis achieved by heating samples of immature Woodford Shale under five different time–temperature conditions. CH4-sorption isotherms at 35 °C, 50 °C, and 65 °C, and pressures up to 14 MPa on dry, solvent-extracted samples of the artificially matured Woodford Shale were measured. The results showed that CH4-sorption capacity, normalized to TOC, varied with thermal maturity, following the trend: maximum oil (367 °C) > oil cracking (400 °C) > maximum bitumen/early oil (333 °C) > early bitumen (300 °C) > immature stage (130 °C). The Langmuir constants for the samples at maximum-oil and oil-cracking stages are larger than the values for the bitumen-forming stages. The total pore volume, determined by N2 physisorption at 77 K, increases with increased maturation: mesopores, 2–50 nm in width, were created during the thermal conversion of organic-matter and a dramatic increase in porosity appeared when maximum-bitumen and maximum-oil generation stages were reached. A linear relationship between thermal maturity and Brunauer–Emmett–Teller (BET) surface area suggests that the observed increase in CH4-sorption capacity may be the result of mesopores produced during OM conversion. No obvious difference is observed in pore-size distribution and pore volume for samples with pores 2 physisorption at 273 K. The isosteric heat of adsorption and the standard entropy for artificially matured samples ranged from 17.9 kJ mol−1 to 21.9 kJ mol−1 and from −85.4 J mol−1 K−1 to −101.8 J mol−1 K−1, respectively. These values are similar to the values of immature Woodford kerogen concentrate previously observed, but are larger than naturally matured organic-rich shales. High-temperature hydrous pyrolysis might have induced Lewis acid sites on both organic and mineral surfaces, resulting to some extent, in chemical interactions between the adsorption site and the methane C–H bonds. The formation of abundant mesopores (2–50 nm) within organic matter during organic-matter thermal maturation makes a great contribution to the increase in both BET surface area and pore volume, and a significant increase in 2–6 nm pores occurs at maximum-oil-generation and oil-cracking to gas, ultimately controlling the methane-adsorption capacity. Therefore, consideration of pore-size effects and thermal maturity is very important for gas in place (GIP) prediction in organic-rich shales.
Self-activation of biochar from furfural residues by recycled pyrolysis gas.
Yin, Yulei; Gao, Yuan; Li, Aimin
2018-04-17
Biochar samples with controllable specific surface area and mesopore ratio were self-activated from furfural residues by recycled pyrolysis gas. The objective of this study was to develop a new cyclic utilization method for the gas produced by pyrolysis. The influences of preparation parameters on the resulting biochar were studied by varying the pyrolysis-gas flow rate, activation time and temperature. Structural characterization of the produced biochar was performed by analysis of nitrogen adsorption isotherms at 77 K and scanning electron microscope (SEM). The pyrolysis gas compositions before and after activation were determined by a gas chromatograph. The results indicated that the surface area of the biochar was increased from 167 m 2 /g to 567 m 2 /g, the total pore volume increased from 0.121 cm 3 /g to 0.380 cm 3 /g, and the ratio of the mesopore pore volume to the total pore volume increased 17-39.7%. The CO volume fraction of the pyrolysis gas changed from 34.66 to 62.29% and the CO 2 volume fraction decreased from 48.26% to 12.17% under different conditions of pyrolysis-gas flow rate, activation time and temperature. The calorific values of pyrolysis gas changed from 8.82 J/cm 3 to 14.00 J/cm 3 , which were higher than those of conventional pyrolysis gases. The slower pyrolysis-gas flow rate and higher activation time increased the efficiency of the reaction between carbon and pyrolysis gas. These results demonstrated the feasibility of treatment of the furfural residues to produce microporous and mesoporous biochar. The pyrolysis gas that results from the activation process could be used as fuel. Overall, this new self-activation method meets the development requirements of cyclic economy and cleaner production. Copyright © 2018. Published by Elsevier Ltd.
Men, Shaojie; Wong, Jennifer Manyu; Welch, Emily J; Xu, Jingjiang; Song, Shaozhen; Deegan, Anthony J; Ravichander, Aarthi; Casavant, Benjamin; Berthier, Erwin; Wang, Ruikang K
2018-05-25
To measure and compare microvascular responses within the skin of the upper arm to local stimuli, such as heating or rubbing, through the use of optical coherence tomography angiography (OCTA), and to investigate its impact on blood volume collection. With the use of heat packs or rubbing, local stimulation was applied to the skin of either the left or right upper arm. Data from the stimulated sites were obtained using OCTA comparing pre- and post-stimulation microvascular parameters, such as vessel density, mean vessel diameter, and mean avascular pore size. Additionally, blood was collected using a newly designed collection device and volume was recorded to evaluate the effect of the skin stimulation. Nineteen subjects were recruited for local stimulation study (including rubbing and heating) and 21 subjects for blood drawn study. Of these subjects, 14 agreed to participate in both studies. OCTA was successful in monitoring and measuring minute changes in the microvasculature of the stimulated skin. Compared to baseline, significant changes after local heating and rubbing were respectively found in vessel density (16% [P = 0.0004] and 33% [P < 0.0001] increase), mean vessel diameter (14% and 11% increase) and mean avascular pore size (5% [P = 0.0068] and 8% [P = 0.0005] decrease) after stimulations. A gradual recovery was recorded for each parameter, with no difference being measured after 30 minutes. Blood collection volumes significantly increased after stimulations of heating (48% increase; P = 0.049) and rubbing (78% increase; P = 0.048). Significant correlations were found between blood volume and microvascular parameters except mean avascular pore size under the heating condition. OCTA can provide important information regarding microvascular adaptations to local stimuli. With that, both heating and rubbing of the skin have positive effects on blood collection capacity, with rubbing having the most significant effect. Lasers Surg. Med. © 2018 Wiley Periodicals, Inc. © 2018 Wiley Periodicals, Inc.
NASA Astrophysics Data System (ADS)
Jung, Hojung; Singh, Gurpreet; Espinoza, D. Nicolas; Wheeler, Mary F.
2018-02-01
Subsurface CO2 injection and storage alters formation pressure. Changes of pore pressure may result in fault reactivation and hydraulic fracturing if the pressure exceeds the corresponding thresholds. Most simulation models predict such thresholds utilizing relatively homogeneous reservoir rock models and do not account for CO2 dissolution in the brine phase to calculate pore pressure evolution. This study presents an estimation of reservoir capacity in terms of allowable injection volume and rate utilizing the Frio CO2 injection site in the coast of the Gulf of Mexico as a case study. The work includes laboratory core testing, well-logging data analyses, and reservoir numerical simulation. We built a fine-scale reservoir model of the Frio pilot test in our in-house reservoir simulator IPARS (Integrated Parallel Accurate Reservoir Simulator). We first performed history matching of the pressure transient data of the Frio pilot test, and then used this history-matched reservoir model to investigate the effect of the CO2 dissolution into brine and predict the implications of larger CO2 injection volumes. Our simulation results -including CO2 dissolution- exhibited 33% lower pressure build-up relative to the simulation excluding dissolution. Capillary heterogeneity helps spread the CO2 plume and facilitate early breakthrough. Formation expansivity helps alleviate pore pressure build-up. Simulation results suggest that the injection schedule adopted during the actual pilot test very likely did not affect the mechanical integrity of the storage complex. Fault reactivation requires injection volumes of at least about sixty times larger than the actual injected volume at the same injection rate. Hydraulic fracturing necessitates much larger injection rates than the ones used in the Frio pilot test. Tested rock samples exhibit ductile deformation at in-situ effective stresses. Hence, we do not expect an increase of fault permeability in the Frio sand even in the presence of fault reactivation.
NASA Astrophysics Data System (ADS)
Wang, Yang; Wu, Caifang; Zhu, Yanming; Chen, Shangbin; Liu, Shimin; Zhang, Rui
Lacustrine shale gas has received considerable attention and has been playing an important role in unconventional natural gas production in China. In this study, multiple techniques, including total organic carbon (TOC) analysis, X-ray diffraction (XRD) analysis, field emission scanning electron microscopy (FE-SEM), helium pycnometry and low-pressure N2 adsorption have been applied to characterize the pore structure of lacustrine shale of Upper Triassic Yanchang Formation from the Ordos Basin. The results show that organic matter (OM) pores are the most important type dominating the pore system, while interparticle (interP) pores, intraparticle (intraP) and microfractures are also usually observed between or within different minerals. The shapes of OM pores are less complex compared with the other two pore types based on the Image-Pro Plus software analysis. In addition, the specific surface area ranges from 2.76m2/g to 10.26m2/g and the pore volume varies between 0.52m3/100g and 1.31m3/100g. Two fractal dimensions D1 and D2 were calculated using Frenkel-Halsey-Hill (FHH) method, with D1 varying between 2.510 and 2.632, and D2 varying between 2.617 and 2.814. Further investigation indicates that the fractal dimensions exhibit positive correlations with TOC contents, whereas there is no definite relationship observed between fractal dimensions and clay minerals. Meanwhile, the fractal dimensions increase with the increase in specific surface area, and is negatively correlated with the pore size.
Liu, Ruili; Shi, Yifeng; Wan, Ying; Meng, Yan; Zhang, Fuqiang; Gu, Dong; Chen, Zhenxia; Tu, Bo; Zhao, Dongyuan
2006-09-06
Highly ordered mesoporous polymer-silica and carbon-silica nanocomposites with interpenetrating networks have been successfully synthesized by the evaporation-induced triconstituent co-assembly method, wherein soluble resol polymer is used as an organic precursor, prehydrolyzed TEOS is used as an inorganic precursor, and triblock copolymer F127 is used as a template. It is proposed for the first time that ordered mesoporous nanocomposites have "reinforced concrete"-structured frameworks. By adjusting the initial mass ratios of TEOS to resol, we determined the obtained nanocomposites possess continuous composition with the ratios ranging from zero to infinity for the two constituents that are "homogeneously" dispersed inside the pore walls. The presence of silicates in nanocomposites dramatically inhibits framework shrinkage during the calcination, resulting in highly ordered large-pore mesoporous carbon-silica nanocomposites. Combustion in air or etching in HF solution can remove carbon or silica from the carbon-silica nanocomposites and yield ordered mesoporous pure silica or carbon frameworks. The process generates plenty of small pores in carbon or/and silica pore walls. Ordered mesoporous carbons can then be obtained with large pore sizes of approximately 6.7 nm, pore volumes of approximately 2.0 cm(3)/g, and high surface areas of approximately 2470 m(2)/g. The pore structures and textures can be controlled by varying the sizes and polymerization degrees of two constituent precursors. Accordingly, by simply tuning the aging time of TEOS, ordered mesoporous carbons with evident bimodal pores at 2.6 and 5.8 nm can be synthesized.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhong, Wei; Jiang, Ting; Jafari, Tahereh
In this work, mesoporous aluminas (MAs) with uniform and monomodal pores were fabricated via a modified inverse micelle synthesis method, using a non-polar solvent (to minimize the effect of water content) and short reaction time (for a fast evaporation process). The effects of reaction times (4–8 h), surfactant chain lengths (non-ionic surfactants), and calcination temperatures and hold times (450–600 °C; 1–4 h) on the textural properties of MA were studied. Additionally, the targeted pore sizes of MA were obtained in the range of 3.1–5.4 nm by adjusting the surfactant and reaction time. The surface area and pore volume were controlledmore » by the calcination temperature and hold time while maintaining the thermal stability of the materials. The tuned MA of the large mesopore volume achieved 168 mg/g octamethylcyclotetrasiloxane (D4 siloxane) adsorption capacity, a 32% improvement compared to commercially activated alumina. Finally, after three adsorption recycles, the synthesized MA still maintained approximate 85% of its original adsorption capacity, demonstrating a sustainable adsorption performance and high potential for related industrial applications.« less
Zhong, Wei; Jiang, Ting; Jafari, Tahereh; ...
2016-10-18
In this work, mesoporous aluminas (MAs) with uniform and monomodal pores were fabricated via a modified inverse micelle synthesis method, using a non-polar solvent (to minimize the effect of water content) and short reaction time (for a fast evaporation process). The effects of reaction times (4–8 h), surfactant chain lengths (non-ionic surfactants), and calcination temperatures and hold times (450–600 °C; 1–4 h) on the textural properties of MA were studied. Additionally, the targeted pore sizes of MA were obtained in the range of 3.1–5.4 nm by adjusting the surfactant and reaction time. The surface area and pore volume were controlledmore » by the calcination temperature and hold time while maintaining the thermal stability of the materials. The tuned MA of the large mesopore volume achieved 168 mg/g octamethylcyclotetrasiloxane (D4 siloxane) adsorption capacity, a 32% improvement compared to commercially activated alumina. Finally, after three adsorption recycles, the synthesized MA still maintained approximate 85% of its original adsorption capacity, demonstrating a sustainable adsorption performance and high potential for related industrial applications.« less
NASA Astrophysics Data System (ADS)
Han, Tongcheng
2018-07-01
Understanding the electrical properties of rocks under varying pressure is important for a variety of geophysical applications. This study proposes an approach to modelling the pressure-dependent electrical properties of porous rocks based on an effective medium model. The so-named Textural model uses the aspect ratios and pressure-dependent volume fractions of the pores and the aspect ratio and electrical conductivity of the matrix grains. The pores were represented by randomly oriented stiff and compliant spheroidal shapes with constant aspect ratios, and their pressure-dependent volume fractions were inverted from the measured variation of total porosity with differential pressure using a dual porosity model. The unknown constant stiff and compliant pore aspect ratios and the aspect ratio and electrical conductivity of the matrix grains were inverted by best fitting the modelled electrical formation factor to the measured data. Application of the approach to three sandstone samples covering a broad porosity range showed that the pressure-dependent electrical properties can be satisfactorily modelled by the proposed approach. The results demonstrate that the dual porosity concept is sufficient to explain the electrical properties of porous rocks under pressure through the effective medium model scheme.
NASA Technical Reports Server (NTRS)
Whitson, Peggy A. (Inventor); Clift, Vaughan L. (Inventor)
1997-01-01
The present invention provides an apparatus for separating a relatively large volume of blood into cellular and acellular fractions without the need for centrifugation. The apparatus comprises a housing divided by a fibrous filter into a blood sample collection chamber having a volume of at least about 1 milliliter and a serum sample collection chamber. The fibrous filter has a pore size of less than about 3 microns, and is coated with a mixture of mannitol and plasma fraction protein (or an animal or vegetable equivalent thereof). The coating causes the cellular fraction to be trapped by the small pores, leaving the cellular fraction intact on the fibrous filter while the acellular fraction passes through the filter for collection in unaltered form from the serum sample collection chamber.
Moisture sorption by cellulose powders of varying crystallinity.
Mihranyan, Albert; Llagostera, Assumpcio Piñas; Karmhag, Richard; Strømme, Maria; Ek, Ragnar
2004-01-28
Moisture in microcrystalline cellulose may cause stability problems for moisture sensitive drugs. The aim of this study was to investigate the influence of crystallinity and surface area on the uptake of moisture in cellulose powders. Powders of varying crystallinity were manufactured, and the uptake of moisture was investigated at different relative humidities. The structure of the cellulose powders was characterized by X-ray diffraction, BET surface area analysis, and scanning electron microscopy. Moisture uptake was directly related to the cellulose crystallinity and pore volume: Cellulose powders with higher crystallinity showed lower moisture uptake at relative humidities below 75%, while at higher humidities the moisture uptake could be associated with filling of the large pore volume of the cellulose powder of highest crystallinity. In conclusion, the structure of cellulose should be thoroughly considered when manufacturing low moisture grades of MCC.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jonker, G.H.; Veldsink, J.W.; Beenackers, A.A.C.M.
1998-12-01
Intraparticle diffusion limitation in the hydrogenation and isomerization of fatty acid methyl esters (FAMEs) and edible oils (triacylglycerol, TAG) in porous nickel catalyst was investigated both under reactive and under inert conditions. Under reactive conditions, the diffusion coefficients were determined from the best fits of the model simulations applying the intrinsic reacting kinetics of monounsaturated FAME hydrogenation to experiments under diffusion limited conditions. Due to the absence of reaction (hydrogenation of double bonds), the obtained effective H{sub z} diffusion coefficient (D{sub e}) with the HPLC technique is volume averaged and thereby determined by the larger intercrystalline pores (<30% of themore » total pore volume) only. Moreover, D{sub e} measured under reaction conditions reflected the influence of the micropores, resulting in a 10-fold lower value.« less
Dunlap, C J; Carr, P W
1996-10-11
Porous zirconia particles made by the oil emulsion (OE) method and the polymerization-induced colloid aggregation (PICA) method have been coated with a small, carboxymethylated (approximately 5%) dextran polymer and crosslinked in place. The parameters of the coating process (dextran concentration, adsorption time and crosslinker concentration) have all been examined and an optimum value for each determined. The coated and uncoated materials were characterized by nitrogen sorptometry and size-exclusion chromatography (SEC) using solutes (polystyrenes and dextrans) of well-defined molecular masses. Nitrogen sorptometry results show that the PICA material has a much lower pore volume and smaller pore diameter than do the OE materials. Despite this, the elution volumes of the SEC probes change very little upon polymer coating the PICA material while the OE material shows a very large change upon coating.
Rehman, Adeela; Park, Soo-Jin
2018-04-17
In the present work, mixture of melamine and isophthalaldehyde undergo simultaneous polymerization, carbonization, and in situ activation in the presence of molten salt media through a single all-in-one route to design microporous carbons with high specific surface areas (~3000 m 2 /g). The effect of the activation temperature and molten salts on the polymerization process and final texture of the carbon was explored. Carbon materials prepared at 700 °C, in the presence of KOH (referred as MIK-700), exhibited a narrower pore-size distribution ~1.05 nm than those prepared in the presence of the eutectic KOH-NaOH mixture (MIKN). Additionally, MIK-700 possesses an optimum micropore volume (1.33 cm 3 /g) along with a high nitrogen content (2.66 wt%), resulting in the excellent CO 2 adsorption capacity of 9.7 mmol/g at 273 K and 1 bar. Similarly, the high specific area and highest total pore volume play an important role in H 2 storage at 77 K, with 4.0 wt% uptake by MIKN-800 (specific surface area and pore volume of 2984 m 2 /g and 1.98 cm 3 /g, respectively.) Thus, the facile one-step solvent-free synthesis and activation strategy is an economically favorable avenue for designing microporous carbons as an efficient gas adsorbents.
Reeve, A.S.; Glaser, P.H.; Rosenberry, Donald O.
2013-01-01
Northern peatlands appear to hold large volumes of free-phase gas (e.g., CH4 and CO2), which has been detected by surface deformations, pore pressure profiles, and electromagnetic surveys. Determining the gas content and its impact in peat is challenging because gas storage depends on both the elastic properties of the peat matrix and the buoyant forces exerted by pore fluids. We therefore used a viscoelastic deformation model to estimate these variables by adjusting model runs to reproduce observed changes in peat surface elevation within a 1300 km2 peatland. A local GPS network documented significant changes in surface elevations throughout the year with the greatest vertical displacements associated with rapid changes in peat water content and unloadings due to melting of the winter snowpack. These changes were coherent with changes in water table elevation and also abnormal pore pressure changes measured by nests of instrumented piezometers. The deformation model reproduced these changes when the gas content was adjusted to 10% of peat volume, and Young's modulus was varied between 5 and 100 kPa as the peat profile shifted from tension to compression. In contrast, the model predicted little peat deformation when the gas content was 3% or lower. These model simulations are consistent with previous estimates of gas volume in northern peatlands and suggest an upper limit of gas storage controlled by the elastic moduli of the peat fabric.
Definitions of differences and changes in peritoneal membrane water transport properties.
Widerøe, T E; Smeby, L C; Dahl, K; Jörstad, S
1988-06-01
A survey is given comparing measurements of transperitoneal water transport in different clinical situations with analyses based on the so-called "pore theory." This model links the measured changes to physical alterations of the peritoneal membrane. The calculations include "equivalent pore radius," effective "membrane area" and diffusive length, the transport resistance of the unstirred dialysate layer, and the residual intraperitoneal volume after dialysate drainage. The clinical appearances include individual differences in transperitoneal transport characteristics, changes in transperitoneal transport over time on continuous ambulatory peritoneal dialysis (CAPD) and during peritonitis, the pharmacological effect on the transport properties, and the effect of peritoneal catheter dislocation on ultrafiltration capacity. The main conclusions are as follow: During CAPD treatment the measurement of intraperitoneal solute equilibration and "mass-transfer-area coefficients" for urea and creatinine is less sensitive than the measurement of ultrafiltration volume in revealing peritoneal membrane changes. Differences and changes found have mostly a combined physical explanation, but one is more or less dominant. Changes in peritoneal membrane area seem to be the most dominant cause of changes in transperitoneal transport during time on CAPD and when sodium nitroprusside was added to the peritoneal dialysate. Changes during peritonitis can be explained by changes in pore radius and depth. Individual differences can be explained by differences in "membrane" area and in resistance of the unstirred dialysate fluid. High residual dialysate volume can give rise to clinical problems and should be considered when placing the catheter in the peritoneal cavity.
Niasar, Hojatallah Seyedy; Li, Hanning; Das, Sreejon; Kasanneni, Tirumala Venkateswara Rao; Ray, Madhumita B; Xu, Chunbao Charles
2018-04-01
This study employed Box-Behnken design and response surface methodology to optimize activation parameters for the production of activated petroleum coke (APC) adsorbent from petroleum coke (PC) to achieve highest adsorption capacity for three model naphthenic acids. Activated petroleum coke (APC) adsorbent with a BET surface area of 1726 m 2 /g and total pore volume of 0.85 cc/g was produced at the optimum activation conditions (KOH/coke mass ratio) of 3.0, activation temperature 790 °C, and activation time 3.47 h). Effects of the activation parameters on the adsorption pefromances (adsortion capaciy and kinetics) were investigated. With the APC obtained at the optimum activation condition, the maximum adsorption capacity of 451, 362, and 320 (mg/g) was achieved for 2-naphthoic acid, diphenylacetic acid and cyclohexanepentanoic acid (CP), respectively. Although, generally APC adsorbents with a higher specific surface area and pore volume provide better adsorption capacity, the textural properties (surface areas and pore volume) are not the only parameters determining the APC adsorbents' adsorption capacity. Other parameters such as surface functionalities play effective roles on the adsorption capacity of the produced APC adsorbents for NAs. The KOH activation process, in particular the acid washing step, distinctly reduced the sulfur and metals contents in the raw PC, decreasing the leaching potential of metals from APC adsorbents during adsorption. Copyright © 2018 Elsevier Ltd. All rights reserved.
Rakhmatia, Yunia Dwi; Ayukawa, Yasunori; Furuhashi, Akihiro; Koyano, Kiyoshi
2014-01-01
The objective of this study was to evaluate the optimal thickness and porosity of novel titanium mesh membranes to enhance bone augmentation, prevent soft tissue ingrowth, and prevent membrane exposure. Six types of novel titanium meshes with different thicknesses and pore sizes, along with three commercially available membranes, were used to cover surgically created calvarial defects in 6-week-old Sprague-Dawley rats. The animals were killed after 4 or 8 weeks. Microcomputed tomographic analyses were performed to analyze the three-dimensional bone volume and bone mineral density. Soft tissue ingrowth was also evaluated histologically and histomorphometrically. The novel titanium membranes used in this study were as effective at augmenting bone in the rat calvarial defect model as the commercially available membranes. The greatest bone volume was observed on 100-μm-thick membranes with larger pores, although these membranes promoted growth of bone with lower mineral density. Soft tissue ingrowth when 100-μm membranes were used was increased at 4 weeks but decreased again by 8 weeks to a level not statistically significantly different from other membranes. Membrane thickness affects the total amount of new bone formation, and membrane porosity is an essential factor for guided bone regeneration, especially during the initial healing period, although the final bone volume obtained is essentially the same. Newly developed titanium mesh membranes of 100 μm in thickness and with large pores appear to be optimal for guided bone regeneration.
Zadaka, Dikla; Nir, Shlomo; Radian, Adi; Mishael, Yael G
2009-02-01
Atrazine removal from water by two polycations pre-adsorbed on montmorillonite was studied. Batch experiments demonstrated that the most suitable composite poly (4-vinylpyridine-co-styrene)-montmorillonite (PVP-co-S90%-mont.) removed 90-99% of atrazine (0.5-28 ppm) within 20-40 min at 0.367% w/w. Calculations employing Langmuir's equation could simulate and predict the kinetics and final extents of atrazine adsorption. Column filter experiments (columns 20x1.6 cm) which included 2g of the PVP-co-S90%-mont. composite mixed with excess sand removed 93-96% of atrazine (800 ppb) for the first 800 pore volumes, whereas the same amount of granular activated carbon (GAC) removed 83-75%. In the presence of dissolved organic matter (DOM; 3.7 ppm) the efficiency of the GAC filter to remove atrazine decreased significantly (68-52% removal), whereas the corresponding efficiency of the PVP-co-S90%-mont. filter was only slightly influenced by DOM. At lower atrazine concentration (7 ppb) the PVP-co-S90%-mont. filter reduced even after 3000 pore volumes the emerging atrazine concentration below 3 ppb (USEPA standard). In the case of the GAC filter the emerging atrazine concentration was between 2.4 and 5.3 microg/L even for the first 100 pore volumes. Thus, the PVP-co-S90%-mont. composite is a new efficient material for the removal of atrazine from water.
Understanding fluid transport through the multiscale pore network of a natural shale
NASA Astrophysics Data System (ADS)
Davy, Catherine A.; Nguyen Kim, Thang; Song, Yang; Troadec, David; Blanchenet, Anne-Marie; Adler, Pierre M.
2017-06-01
The pore structure of a natural shale is obtained by three imaging means. Micro-tomography results are extended to provide the spatial arrangement of the minerals and pores present at a voxel size of 700 nm (the macroscopic scale). FIB/SEM provides a 3D representation of the porous clay matrix on the so-called mesoscopic scale (10-20 nm); a connected pore network, devoid of cracks, is obtained for two samples out of five, while the pore network is connected through cracks for two other samples out of five. Transmission Electron Microscopy (TEM) is used to visualize the pore space with a typical pixel size of less than 1 nm and a porosity ranging from 0.12 to 0.25. On this scale, in the absence of 3D images, the pore structure is reconstructed by using a classical technique, which is based on truncated Gaussian fields. Permeability calculations are performed with the Lattice Boltzmann Method on the nanoscale, on the mesoscale, and on the combination of the two. Upscaling is finally done (by a finite volume approach) on the bigger macroscopic scale. Calculations show that, in the absence of cracks, the contribution of the nanoscale pore structure on the overall permeability is similar to that of the mesoscale. Complementarily, the macroscopic permeability is measured on a centimetric sample with a neutral fluid (ethanol). The upscaled permeability on the macroscopic scale is in good agreement with the experimental results.
NASA Astrophysics Data System (ADS)
Taina, I. A.; Heck, R. J.; Scaiff, N. T.
2009-05-01
One of the most important applications of X-ray computed tomography (CT) for the study of soil is the characterization of the shape and spatial distribution of pores. Analysis of 3D X-ray CT image data, related to different pore categories, can provide insight to soil structural changes, which have implications in water infiltration and soil aeration, resulting from agricultural practices. The aim of this study was to evaluate changes in the spatial characteristics of voids, due to tillage practices, in the Ap horizon of an Orthic Grey- Brown Luvisol (located at the Elora Research Station of the University of Guelph). Undisturbed oriented soil samples were collected from ten plots representing different tillage treatments: spring moldboard plow, spring moldboard plow, cultivate and pack, fall moldboard plow, cultivate and pack, spring tandem disc, no cultivator, fall offset disc, fall offset disc, cultivate and pack, fall chisel plow, cultivate and pack, zero zone till (soys twin rows), zero tillage (long term), and zero tillage (corn residue removed in row, soys twin rows). Since the utilization of standardized classes, in the quantification of similar features, proved to be necessary in order to obtain comparable results, categories of pores, separated according to their size, circularity and orientation were considered in the interpretation of data. Total volume of pores and volume percentage of each class were calculated, revealing substantial differences among the analyzed soil samples.
NASA Astrophysics Data System (ADS)
Vollet, D. R.; Torres, R. R.; Donatti, D. A.; Ibañez Ruiz, A.
2005-11-01
Silica gels were preparated from fixed proportion mixtures of tetraethoxysilane, water and hydrocloric acid, using either ultrasound stimulation (US) or conventional method (CO) in the hydrolysis step of the process. Wet gels were obtained with the same silica volume concentration and density. According to small-angle X-ray scattering, the structure of the wet gels can be described as mass fractal structures with mass fractal dimension D = 2.20 in a length scale = 7.9 nm, in the case of wet gels US, and D = 2.26 in a length scale = 6.9 nm, in the case of wet gels CO. The mass fractal characteristics of the wet gels US and CO account for the different structures evolved in the drying of the gels US and CO in the obtaining of xerogels and aerogels. The pore structure of the dried gels was studied by nitrogen adsorption as a function of the temperature. Aerogels (US and CO) present high porosity with pore size distribution (PSD) curves in the mesopore region while xerogels (US and CO) present minor porosity with PSD curves mainly in the micropore region. The dried gels US (aerogels and xerogels) generally present pore volume and specific surface area greater than the dried gels CO. The mass fractal structure of the aerogels has been studied from an approach based on the PSD curves exclusively.
Yoshikawa, Akira; Sato, Shuntaro; Tanaka, Tomonori; Hashisako, Mikiko; Kashima, Yukio; Tsuchiya, Tomoshi; Yamasaki, Naoya; Nagayasu, Takeshi; Yamamoto, Hiroshi; Fukuoka, Junya
2016-01-01
Pulmonary emphysema is the pathological prototype of chronic obstructive pulmonary disease and is also associated with other lung diseases. We considered that observation with different approaches may provide new insights for the pathogenesis of emphysema. We reviewed tissue blocks of the lungs of 25 cases with/without emphysema and applied a three-dimensional observation method to the blocks. Based on the three-dimensional characteristics of the alveolar structure, we considered one face of the alveolar polyhedron as a structural unit of alveoli and called it a framework unit (FU). We categorized FUs based on their morphological characteristics and counted their number to evaluate the destructive changes in alveoli. We also evaluated the number and the area of pores of Kohn in FUs. We performed linear regression analysis to estimate the effect of these data on pulmonary function tests. In multivariable regression analysis, a decrease in the number of FUs without an alveolar wall led to a significant decrease in the diffusing capacity of the lung for carbon monoxide (DLCO) and DLCO per unit alveolar volume, and an increase in the area of pores of Kohn had a significant effect on an increase in residual capacity. A breakdown in the lung framework and an increase in pores of Kohn are associated with a decrease in DLCO and DLCO per unit alveolar volume with/without emphysema.
NASA Astrophysics Data System (ADS)
Morsi, Rania E.; Mohamed, Rasha S.
2018-03-01
A series of ordered mesoporous silica such as MCM-41, SBA-3 and SBA-15, in addition to silica micro- (SM) and nano- (SN) mesoporous particles, were prepared. The preparation conditions were found to greatly influence the physical-surface properties including morphological structure, porosity, particle size, aggregate average size, surface area, pore size, pore volume and zeta potential of the prepared silica, while the chemical structure, predicted from FT-IR spectra, and the diffraction patterns, predicted from wide-angle X-ray diffraction spectra, were identical. Surface areas of approximately 1500, 1027, 600, 552 and 317 m2 g-1, pore volumes of 0.93, 0.56, 0.82, 0.72 and 0.5 cm3 g-1, radii of 2.48, 2.2, 5.66, 6.6 and 8.98 nm, average aggregate sizes of 56, 65.4, 220.9, 73, 61.1 and 261 nm and zeta potential values of -32.8, -46.1, -26.3, -31.4 and -25.9 mV were obtained for MCM-41, SBA-3, SBA-15, SN and SM, respectively. Methylene blue dye uptake capacity of the prepared silica types was investigated using the batch technique and, in addition, the most effective material was further studied by the column flow system. The kinetics and isotherms of the uptake process were studied. The morphological structure, surface area, pore radius and zeta potential values were the most correlated factors.
NASA Astrophysics Data System (ADS)
Hu, Ran; Wan, Jiamin; Kim, Yongman; Tokunaga, Tetsu K.
2017-08-01
How the wettability of pore surfaces affects supercritical (sc) CO2 capillary trapping in geologic carbon sequestration (GCS) is not well understood, and available evidence appears inconsistent. Using a high-pressure micromodel-microscopy system with image analysis, we studied the impact of wettability on scCO2 capillary trapping during short-term brine flooding (80 s, 8-667 pore volumes). Experiments on brine displacing scCO2 were conducted at 8.5 MPa and 45°C in water-wet (static contact angle θ = 20° ± 8°) and intermediate-wet (θ = 94° ± 13°) homogeneous micromodels under four different flow rates (capillary number Ca ranging from 9 × 10-6 to 8 × 10-4) with a total of eight conditions (four replicates for each). Brine invasion processes were recorded and statistical analysis was performed for over 2000 images of scCO2 saturations, and scCO2 cluster characteristics. The trapped scCO2 saturation under intermediate-wet conditions is 15% higher than under water-wet conditions under the slowest flow rate (Ca ˜ 9 × 10-6). Based on the visualization and scCO2 cluster analysis, we show that the scCO2 trapping process in our micromodels is governed by bypass trapping that is enhanced by the larger contact angle. Smaller contact angles enhance cooperative pore filling and widen brine fingers (or channels), leading to smaller volumes of scCO2 being bypassed. Increased flow rates suppress this wettability effect.
Othman, Rahimah; Vladisavljević, Goran T; Simone, Elena; Nagy, Zoltan K; Holdich, Richard G
2017-12-06
Microcrystals of piroxicam (PRX) monohydrate with a narrow size distribution were prepared from acetone/PRX solutions by antisolvent crystallization via metallic membranes with ordered pore arrays. Crystallization was achieved by controlled addition of the feed solution through the membrane pores into a well-stirred antisolvent. A complete transformation of an anhydrous form I into a monohydrate form of PRX was confirmed by Raman spectroscopy and differential scanning calorimetry. The size of the crystals was 7-34 μm and was controlled by the PRX concentration in the feed solution (15-25 g L -1 ), antisolvent/solvent volume ratio (5-30), and type of antisolvent (Milli-Q water or 0.1-0.5 wt % aqueous solutions of hydroxypropyl methyl cellulose (HPMC), poly(vinyl alcohol) or Pluronic P-123). The smallest crystals were obtained by injecting 25 g L -1 PRX solution through a stainless-steel membrane with a pore size of 10 μm into a 0.06 wt % HPMC solution stirred at 1500 rpm using an antisolvent/solvent ratio of 20. HPMC provided better steric stabilization of microcrystals against agglomeration than poly(vinyl alcohol) and Pluronic P-123, due to hydrogen bonding interactions with PRX and water. A continuous production of large PRX monohydrate microcrystals with a volume-weighted mean diameter above 75 μm was achieved in a continuous stirred membrane crystallizer. Rapid pouring of Milli-Q water into the feed solution resulted in a mixture of highly polydispersed prism-shaped and needle-shaped crystals.
Morsi, Rania E; Mohamed, Rasha S
2018-03-01
A series of ordered mesoporous silica such as MCM-41, SBA-3 and SBA-15, in addition to silica micro- (SM) and nano- (SN) mesoporous particles, were prepared. The preparation conditions were found to greatly influence the physical-surface properties including morphological structure, porosity, particle size, aggregate average size, surface area, pore size, pore volume and zeta potential of the prepared silica, while the chemical structure, predicted from FT-IR spectra, and the diffraction patterns, predicted from wide-angle X-ray diffraction spectra, were identical. Surface areas of approximately 1500, 1027, 600, 552 and 317 m 2 g -1 , pore volumes of 0.93, 0.56, 0.82, 0.72 and 0.5 cm 3 g -1 , radii of 2.48, 2.2, 5.66, 6.6 and 8.98 nm, average aggregate sizes of 56, 65.4, 220.9, 73, 61.1 and 261 nm and zeta potential values of -32.8, -46.1, -26.3, -31.4 and -25.9 mV were obtained for MCM-41, SBA-3, SBA-15, SN and SM, respectively. Methylene blue dye uptake capacity of the prepared silica types was investigated using the batch technique and, in addition, the most effective material was further studied by the column flow system. The kinetics and isotherms of the uptake process were studied. The morphological structure, surface area, pore radius and zeta potential values were the most correlated factors.
NASA Astrophysics Data System (ADS)
Jin, Y.; Konno, Y.; Kida, M.; Nagao, J.
2014-12-01
Hydrate saturation of gas-hydrate bearing sediment is a key of gas production from natural gas-hydrate reservoir. Developable natural gas-hydrates by conventional gas/oil production apparatus almost exist in unconsolidated sedimental layer. Generally, hydrate saturations of sedimental samples are directly estimated by volume of gas generated from dissociation of gas hydrates in pore spaces, porosity data and volume of the sediments. Furthermore, hydrate saturation can be also assessed using velocity of P-wave through sedimental samples. Nevertheless, hydrate saturation would be changed by morphological variations (grain-coating, cementing and pore-filling model) of gas hydrates in pore spaces. Jin et al.[1,2] recently observed the O-H stretching bands of H2O molecules of methane hydrate in porous media using an attenuated total reflection IR (ATR-IR) spectra. They observed in situ hydrate formation/dissociation process in sandy samples (Tohoku Keisya number 8, grain size of ca. 110 μm). In this presentation, we present IR spectroscopy approach to in situ evaluation of hydrate saturation of pressured gas-hydrate sediments. This work was supported by funding from the Research Consortium for Methane Hydrate Resources in Japan (MH21 Research Consortium) planned by the Ministry of Economy, Trade and Industry (METI), Japan. [1] Jin, Y.; Konno, Y.; Nagao, J. Energy Fules, 2012, 26, 2242-2247. [2] Jin, Y.; Oyama, H.; Nagao, J. Jpn. J. Appl. Phys. 2009, 48, No. 108001.
Holewinski, Adam; Sakwa-Novak, Miles A.; Jones, Christopher W.
2015-08-26
Composites of poly(ethylenimine) (PEI) and mesoporous silica are effective, reversible adsorbents for CO 2, both from flue gas and in direct air-capture applications. The morphology of the PEI within the silica can strongly impact the overall carbon capture efficiency and rate of saturation. Here, we directly probe the spatial distribution of the supported polymer through small-angle neutron scattering (SANS). Combined with textural characterization from physisorption analysis, the data indicate that PEI first forms a thin conformal coating on the pore walls, but all additional polymer aggregates into plug(s) that grow along the pore axis. This model is consistent with observedmore » trends in amine-efficiency (CO 2/N binding ratio) and pore size distributions, and points to a trade-off between achieving high chemical accessibility of the amine binding sites, which are inaccessible when they strongly interact with the silica, and high accessibility for mass transport, which can be hampered by diffusion through PEI plugs. In conclusion, we illustrate this design principle by demonstrating higher CO 2 capacity and uptake rate for PEI supported in a hydrophobically modified silica, which exhibits repulsive interactions with the PEI, freeing up binding sites.« less
Xue, Dong-Xu; Belmabkhout, Youssef; Shekhah, Osama; Jiang, Hao; Adil, Karim; Cairns, Amy J; Eddaoudi, Mohamed
2015-04-22
Reticular chemistry approach was successfully employed to deliberately construct new rare-earth (RE, i.e., Eu(3+), Tb(3+), and Y(3+)) fcu metal-organic frameworks (MOFs) with restricted window apertures. Controlled and selective access to the resultant contracted fcu-MOF pores permits the achievement of the requisite sorbate cutoff, ideal for selective adsorption kinetics based separation and/or molecular sieving of gases and vapors. Predetermined reaction conditions that permitted the formation in situ of the 12-connected RE hexanuclear molecular building block (MBB) and the establishment of the first RE-fcu-MOF platform, especially in the presence of 2-fluorobenzoic acid (2-FBA) as a modulator and a structure directing agent, were used to synthesize isostructural RE-1,4-NDC-fcu-MOFs based on a relatively bulkier 2-connected bridging ligand, namely 1,4-naphthalenedicarboxylate (1,4-NDC). The subsequent RE-1,4-NDC-fcu-MOF structural features, contracted windows/pores and high concentration of open metal sites combined with exceptional hydrothermal and chemical stabilities, yielded notable gas/solvent separation properties, driven mostly by adsorption kinetics as exemplified in this work for n-butane/methane, butanol/methanol, and butanol/water pair systems.
Stefanopoulos, Konstantinos L; Youngs, Tristan G A; Sakurovs, Richard; Ruppert, Leslie F; Bahadur, Jitendra; Melnichenko, Yuri B
2017-06-06
Shale is an increasingly viable source of natural gas and a potential candidate for geologic CO 2 sequestration. Understanding the gas adsorption behavior on shale is necessary for the design of optimal gas recovery and sequestration projects. In the present study neutron diffraction and small-angle neutron scattering measurements of adsorbed CO 2 in Marcellus Shale samples were conducted on the Near and InterMediate Range Order Diffractometer (NIMROD) at the ISIS Pulsed Neutron and Muon Source, STFC Rutherford Appleton Laboratory along an adsorption isotherm of 22 °C and pressures of 25 and 40 bar. Additional measurements were conducted at approximately 22 and 60 °C at the same pressures on the General-Purpose Small-Angle Neutron Scattering (GP-SANS) instrument at Oak Ridge National Laboratory. The structures investigated (pores) for CO 2 adsorption range in size from Å level to ∼50 nm. The results indicate that, using the conditions investigated densification or condensation effects occurred in all accessible pores. The data suggest that at 22 °C the CO 2 has liquid-like properties when confined in pores of around 1 nm radius at pressures as low as 25 bar. Many of the 2.5 nm pores, 70% of 2 nm pores, most of the <1 nm pores, and all pores <0.25 nm, are inaccessible or closed to CO 2 , suggesting that despite the vast numbers of micropores in shale, the micropores will be unavailable for storage for geologic CO 2 sequestration.
Sokolov, I; Kalaparthi, V; Volkov, D O; Palantavida, S; Mordvinova, N E; Lebedev, O I; Owens, J
2017-01-04
A large class of colloidal multi-micron mesoporous silica particles have well-defined cylindrical nanopores, nanochannels which self-assembled in the templated sol-gel process. These particles are of broad interest in photonics, for timed drug release, enzyme stabilization, separation and filtration technologies, catalysis, etc. Although the pore geometry and mechanism of pore formation of such particles has been widely investigated at the nanoscale, their pore geometry and its formation mechanism at a larger (extended) scale is still under debate. The extended geometry of nanochannels is paramount for all aforementioned applications because it defines accessibility of nanochannels, and subsequently, kinetics of interaction of the nanochannel content with the particle surrounding. Here we present both experimental and theoretical investigation of the extended geometry and its formation mechanism in colloidal multi-micron mesoporous silica particles. We demonstrate that disordered (and consequently, well accessible) nanochannels in the initially formed colloidal particles gradually align and form extended self-sealed channels. This knowledge allows to control the percentage of disordered versus self-sealed nanochannels, which defines accessibility of nanochannels in such particles. We further show that the observed aligning the channels is in agreement with theory; it is thermodynamically favored as it decreases the Gibbs free energy of the particles. Besides the practical use of the obtained results, developing a fundamental understanding of the mechanisms of morphogenesis of complex geometry of nanopores will open doors to efficient and controllable synthesis that will, in turn, further fuel the practical utilization of these particles.
Intercomparison of 3D pore-scale flow and solute transport simulation methods
Mehmani, Yashar; Schoenherr, Martin; Pasquali, Andrea; ...
2015-09-28
Multiple numerical approaches have been developed to simulate porous media fluid flow and solute transport at the pore scale. These include 1) methods that explicitly model the three-dimensional geometry of pore spaces and 2) methods that conceptualize the pore space as a topologically consistent set of stylized pore bodies and pore throats. In previous work we validated a model of the first type, using computational fluid dynamics (CFD) codes employing a standard finite volume method (FVM), against magnetic resonance velocimetry (MRV) measurements of pore-scale velocities. Here we expand that validation to include additional models of the first type based onmore » the lattice Boltzmann method (LBM) and smoothed particle hydrodynamics (SPH), as well as a model of the second type, a pore-network model (PNM). The PNM approach used in the current study was recently improved and demonstrated to accurately simulate solute transport in a two-dimensional experiment. While the PNM approach is computationally much less demanding than direct numerical simulation methods, the effect of conceptualizing complex three-dimensional pore geometries on solute transport in the manner of PNMs has not been fully determined. We apply all four approaches (FVM-based CFD, LBM, SPH and PNM) to simulate pore-scale velocity distributions and (for capable codes) nonreactive solute transport, and intercompare the model results. Comparisons are drawn both in terms of macroscopic variables (e.g., permeability, solute breakthrough curves) and microscopic variables (e.g., local velocities and concentrations). Generally good agreement was achieved among the various approaches, but some differences were observed depending on the model context. The intercomparison work was challenging because of variable capabilities of the codes, and inspired some code enhancements to allow consistent comparison of flow and transport simulations across the full suite of methods. This paper provides support for confidence in a variety of pore-scale modeling methods and motivates further development and application of pore-scale simulation methods.« less
Intercomparison of 3D pore-scale flow and solute transport simulation methods
DOE Office of Scientific and Technical Information (OSTI.GOV)
Yang, Xiaofan; Mehmani, Yashar; Perkins, William A.
2016-09-01
Multiple numerical approaches have been developed to simulate porous media fluid flow and solute transport at the pore scale. These include 1) methods that explicitly model the three-dimensional geometry of pore spaces and 2) methods that conceptualize the pore space as a topologically consistent set of stylized pore bodies and pore throats. In previous work we validated a model of the first type, using computational fluid dynamics (CFD) codes employing a standard finite volume method (FVM), against magnetic resonance velocimetry (MRV) measurements of pore-scale velocities. Here we expand that validation to include additional models of the first type based onmore » the lattice Boltzmann method (LBM) and smoothed particle hydrodynamics (SPH), as well as a model of the second type, a pore-network model (PNM). The PNM approach used in the current study was recently improved and demonstrated to accurately simulate solute transport in a two-dimensional experiment. While the PNM approach is computationally much less demanding than direct numerical simulation methods, the effect of conceptualizing complex three-dimensional pore geometries on solute transport in the manner of PNMs has not been fully determined. We apply all four approaches (FVM-based CFD, LBM, SPH and PNM) to simulate pore-scale velocity distributions and (for capable codes) nonreactive solute transport, and intercompare the model results. Comparisons are drawn both in terms of macroscopic variables (e.g., permeability, solute breakthrough curves) and microscopic variables (e.g., local velocities and concentrations). Generally good agreement was achieved among the various approaches, but some differences were observed depending on the model context. The intercomparison work was challenging because of variable capabilities of the codes, and inspired some code enhancements to allow consistent comparison of flow and transport simulations across the full suite of methods. This study provides support for confidence in a variety of pore-scale modeling methods and motivates further development and application of pore-scale simulation methods.« less
Rostad, C.E.; Sanford, W.E.
2009-01-01
Pore waters from the Chesapeake Bay impact structure cores recovered at Eyreville Farm, Northampton County, Virginia, were analyzed to characterize the dissolved organic carbon. After squeezing or centrifuging, a small volume of pore water, 100 ??L, was taken for analysis by electrospray ionization-mass spectrometry. Porewater samples were analyzed directly without filtration or fractionation, in positive and negative mode, for polar organic compounds. Spectra in both modes were dominated by low-molecular-weight ions. Negative mode had clusters of ions differing by -60 daltons, possibly due to increasing concentrations of inorganic salts. The numberaverage molecular weight and weight-average molecular weight values for the pore waters from the Chesapeake Bay impact structure are higher than those reported for other aquatic sources of natural dissolved organic carbon as determined by electrospray ionization-mass spectrometry. In order to address the question of whether drilling mud fluids may have contaminated the pore waters during sample collection, spectra from the pore waters were compared to spectra from drilling mud fluids. Ions indicative of drilling mud fluids were not found in spectra from the pore waters, indicating there was no detectable contamination, and highlighting the usefulness of this analytical technique for detecting potential contamination during sample collection. ?? 2009 The Geological Society of America.
NASA Astrophysics Data System (ADS)
Ramírez, Patricio; Apel, Pavel Yu; Cervera, Javier; Mafé, Salvador
2008-08-01
We present a complete theoretical study of the relationship between the structure (tip shape and dimensions) and function (selectivity and rectification) of asymmetric nanopores on the basis of previous experimental studies. The theoretical model uses a continuum approach based on the Nernst-Planck equations. According to our results, the nanopore transport properties, such as current-voltage (I-V) characteristics, conductance, rectification ratio, and selectivity, are dictated mainly by the shape of the pore tip (we have distinguished bullet-like, conical, trumpet-like, and hybrid shapes) and the concentration of pore surface charges. As a consequence, the nanopore performance in practical applications will depend not only on the base and tip openings but also on the pore shape. In particular, we show that the pore opening dimensions estimated from the pore conductance can be very different, depending on the pore shape assumed. The results obtained can also be of practical relevance for the design of nanopores, nanopipettes, and nanoelectrodes, where the electrical interactions between the charges attached to the nanostructure and the mobile charges confined in the reduced volume of the inside solution dictate the device performance in practical applications. Because single tracks are the elementary building blocks for nanoporous membranes, the understanding and control of their individual properties should also be crucial in protein separation, water desalination, and bio-molecule detection using arrays of identical nanopores.
Ramírez, Patricio; Apel, Pavel Yu; Cervera, Javier; Mafé, Salvador
2008-08-06
We present a complete theoretical study of the relationship between the structure (tip shape and dimensions) and function (selectivity and rectification) of asymmetric nanopores on the basis of previous experimental studies. The theoretical model uses a continuum approach based on the Nernst-Planck equations. According to our results, the nanopore transport properties, such as current-voltage (I-V) characteristics, conductance, rectification ratio, and selectivity, are dictated mainly by the shape of the pore tip (we have distinguished bullet-like, conical, trumpet-like, and hybrid shapes) and the concentration of pore surface charges. As a consequence, the nanopore performance in practical applications will depend not only on the base and tip openings but also on the pore shape. In particular, we show that the pore opening dimensions estimated from the pore conductance can be very different, depending on the pore shape assumed. The results obtained can also be of practical relevance for the design of nanopores, nanopipettes, and nanoelectrodes, where the electrical interactions between the charges attached to the nanostructure and the mobile charges confined in the reduced volume of the inside solution dictate the device performance in practical applications. Because single tracks are the elementary building blocks for nanoporous membranes, the understanding and control of their individual properties should also be crucial in protein separation, water desalination, and bio-molecule detection using arrays of identical nanopores.
Koebernick, Nicolai; Daly, Keith R; Keyes, Samuel D; George, Timothy S; Brown, Lawrie K; Raffan, Annette; Cooper, Laura J; Naveed, Muhammad; Bengough, Anthony G; Sinclair, Ian; Hallett, Paul D; Roose, Tiina
2017-10-01
In this paper, we provide direct evidence of the importance of root hairs on pore structure development at the root-soil interface during the early stage of crop establishment. This was achieved by use of high-resolution (c. 5 μm) synchrotron radiation computed tomography (SRCT) to visualise both the structure of root hairs and the soil pore structure in plant-soil microcosms. Two contrasting genotypes of barley (Hordeum vulgare), with and without root hairs, were grown for 8 d in microcosms packed with sandy loam soil at 1.2 g cm -3 dry bulk density. Root hairs were visualised within air-filled pore spaces, but not in the fine-textured soil regions. We found that the genotype with root hairs significantly altered the porosity and connectivity of the detectable pore space (> 5 μm) in the rhizosphere, as compared with the no-hair mutants. Both genotypes showed decreasing pore space between 0.8 and 0.1 mm from the root surface. Interestingly the root-hair-bearing genotype had a significantly greater soil pore volume-fraction at the root-soil interface. Effects of pore structure on diffusion and permeability were estimated to be functionally insignificant under saturated conditions when simulated using image-based modelling. © 2017 The Authors. New Phytologist © 2017 New Phytologist Trust.
Regulation of landslide motion by dilatancy and pore pressure feedback
Iverson, R.M.
2005-01-01
A new mathematical model clarifies how diverse styles and rates of landslide motion can result from regulation of Coulomb friction by dilation or contraction of water-saturated basal shear zones. Normalization of the model equations shows that feedback due to coupling between landslide motion, shear zone volume change, and pore pressure change depends on a single dimensionless parameter ??, which, in turn, depends on the dilatancy angle ?? and the intrinsic timescales for pore pressure generation and dissipation. If shear zone soil contracts during slope failure, then ?? 0, and negative feedback permits slow, steady landslide motion to occur while positive pore pressure is supplied by rain infiltration. Steady state slip velocities v0 obey v0 = -(K/??) p*e, where K is the hydraulic conductivity and p*e is the normalized (dimensionless) negative pore pressure generated by dilation. If rain infiltration and attendant pore pressure growth continue unabated, however, their influence ultimately overwhelms the stabilizing influence of negative p*e. Then, unbounded landslide acceleration occurs, accentuated by an instability that develops if ?? diminishes as landslide motion proceeds. Nonetheless, numerical solutions of the model equations show that slow, nearly steady motion of a clay-rich landslide may persist for many months as a result of negative pore pressure feedback that regulates basal Coulomb friction. Similarly stabilized motion is less likely to occur in sand-rich landslides that are characterized by weaker negative feedback.
Lapham, Laura L; Chanton, Jeffrey P; Martens, Christopher S; Higley, Paul D; Jannasch, Hans W; Woolsey, J Robert
2008-10-01
A specialized pore-fluid array (PFA) sampler was designed to collect and store pore fluids to monitor temporal changes of ions and gases in gas hydrate bearing sediments. We tested the hypothesis that pore-fluid chemistry records hydrate formation or decomposition events and reflects local seismic activity. The PFA is a seafloor probe that consists of an interchangeable instrument package that houses OsmoSamplers, long-term pore-fluid samplers, a specialized low-dead volume fluid coupler, and eight sample ports along a 10 m sediment probe shaft. The PFA was deployed at Mississippi Canyon 118, a Gulf of Mexico hydrate site. A 170 day record was acquired from the overlying water and 1.3 m below seafloor (mbsf). Fluids were measured for dissolved chloride, sulfate, and methane concentrations and dissolved inorganic carbon and methane stable carbon and deuterium isotope ratios. Chloride and sulfate did not change significantly over time, suggesting the absence of gas hydrate formation or decomposition events. Over the temporal record, methane concentrations averaged 4 mM at 1.3 mbsf, and methane was thermogenic in origin (delta13C-CH4 = -32.4 +/- 3.4 per thousand). The timing of an anomalous 14 mM methane spike coincided with a nearby earthquake (Mw = 5.8), consistent with the hypothesis that pore-fluid chemistry reflects seismic events.
Pore- and micro-structural characterization of a novel structural binder based on iron carbonation
DOE Office of Scientific and Technical Information (OSTI.GOV)
Das, Sumanta, E-mail: Sumanta.Das@asu.edu; Stone, David, E-mail: dajstone@gmail.com; Convey, Diana, E-mail: Diana.Convey@asu.edu
2014-12-15
The pore- and micro-structural features of a novel binding material based on the carbonation of waste metallic iron powder are reported in this paper. The binder contains metallic iron powder as the major ingredient, followed by additives containing silica and alumina to facilitate favorable reaction product formation. Compressive strengths sufficient for a majority of concrete applications are attained. The material pore structure is investigated primarily through mercury intrusion porosimetry whereas electron microscopy is used for microstructural characterization. Reduction in the overall porosity and the average pore size with an increase in carbonation duration from 1 day to 4 days ismore » noticed. The pore structure features are used in predictive models for gas and moisture transport (water vapor diffusivity and moisture permeability) through the porous medium which dictates its long-term durability when used in structural applications. Comparisons of the pore structure with those of a Portland cement paste are also provided. The morphology of the reaction products in the iron-based binder, and the distribution of constituent elements in the microstructure are also reported. - Highlights: • Carbonation of iron produces a dense microstructure. • Pore volume in iron carbonate lower, critical size higher than those in OPC pastes • Reaction product contains iron, carbon, silicon, aluminum and calcium. • Power-law for porosity-moisture permeability relationship was established.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhang, W.; Chang, Q.G.; Liu, W.D.
A series of follow-up investigations were performed to produce data for improving the four-indicator carbon selection method that we developed to identify high-potential activated carbons effective for removing specific organic water pollutants. The carbon's pore structure and surface chemistry are dependent on the raw material and the activation process. Coconut carbons have relatively more small pores than large pores; coal and apricot nutshell/walnut shell fruit carbons have the desirable pore structures for removing adsorbates of all sizes. Chemical activation, excessive activation, and/or thermal reactivation enlarge small pores, resulting in reduced phenol number and higher tannic acid number. Activated carbon's phenol,more » iodine, methylene blue, and tannic acid numbers are convenient indicators of its surface area and pore volume of pore diameters < 10, 10-15, 15-28, and > 28 angstrom, respectively. The phenol number of a carbon is also a good indicator of its surface acidity of oxygen-containing organic functional groups that affect the adsorptive capacity for aromatic and other small polar organics. The tannic acid number is an indicator of carbon's capacity for large, high-molecular-weight natural organic precursors of disinfection by-products in water treatment. The experimental results for removing nitrobenzene, methyl-tert-butyl ether, 4,4-bisphenol, humic acid, and the organic constituents of a biologically treated coking-plant effluent have demonstrated the effectiveness of this capacity-indicator-based method of carbon selection.« less
Side chain flexibility and the pore dimensions in the GABAA receptor
NASA Astrophysics Data System (ADS)
Rossokhin, Alexey V.; Zhorov, Boris S.
2016-07-01
Permeation of ions through open channels and their accessibility to pore-targeting drugs depend on the pore cross-sectional dimensions, which are known only for static X-ray and cryo-EM structures. Here, we have built homology models of the closed, open and desensitized α1β2γ2 GABAA receptor (GABAAR). The models are based, respectively, on the X-ray structure of α3 glycine receptor (α3 GlyR), cryo-EM structure of α1 GlyR and X-ray structure of β3 GABAAR. We employed Monte Carlo energy minimizations to explore how the pore lumen may increase due to repulsions of flexible side chains from a variable-diameter electroneutral atom (an expanding sphere) pulled through the pore. The expanding sphere computations predicted that the pore diameter averaged along the permeation pathway is larger by approximately 3 Å than that computed for the models with fixed sidechains. Our models predict three major pore constrictions located at the levels of -2', 9' and 20' residues. Residues around the -2' and 9' rings are known to form the desensitization and activation gates of GABAAR. Our computations predict that the 20' ring may also serve as GABAAR gate whose physiological role is unclear. The side chain flexibility of residues -2', 9' and 20' and hence the dimensions of the constrictions depend on the GABAAR functional state.
Highly sensitive detection using microring resonator and nanopores
NASA Astrophysics Data System (ADS)
Bougot-Robin, K.; Hoste, J. W.; Le Thomas, N.; Bienstman, P.; Edel, J. B.
2016-04-01
One of the most significant challenges facing physical and biological scientists is the accurate detection and identification of single molecules in free-solution environments. The ability to perform such sensitive and selective measurements opens new avenues for a large number of applications in biological, medical and chemical analysis, where small sample volumes and low analyte concentrations are the norm. Access to information at the single or few molecules scale is rendered possible by a fine combination of recent advances in technologies. We propose a novel detection method that combines highly sensitive label-free resonant sensing obtained with high-Q microcavities and position control in nanoscale pores (nanopores). In addition to be label-free and highly sensitive, our technique is immobilization free and does not rely on surface biochemistry to bind probes on a chip. This is a significant advantage, both in term of biology uncertainties and fewer biological preparation steps. Through combination of high-Q photonic structures with translocation through nanopore at the end of a pipette, or through a solid-state membrane, we believe significant advances can be achieved in the field of biosensing. Silicon microrings are highly advantageous in term of sensitivity, multiplexing, and microfabrication and are chosen for this study. In term of nanopores, we both consider nanopore at the end of a nanopipette, with the pore being approach from the pipette with nanoprecise mechanical control. Alternatively, solid state nanopores can be fabricated through a membrane, supporting the ring. Both configuration are discussed in this paper, in term of implementation and sensitivity.
Hu, Jingyi; Shang, Ran; Heijman, Bas; Rietveld, Luuk
2015-09-01
Spent granular activated carbons (sGACs) for drinking water treatments were reused via pulverizing as low-cost adsorbents for micro-pollutant adsorption from a secondary treated wastewater effluent. The changes of physicochemical characteristics of the spent carbons in relation to the fresh carbons were determined and were correlated to the molecular properties of the respective GAC influents (i.e. a surface water and a groundwater). Pore size distribution analysis showed that the carbon pore volume decreased over a wider size range due to preloading by surface water, which contains a broader molecular weight distribution of organic matter in contrast to the groundwater. However, there was still considerable capacity available on the pulverized sGACs for atrazine adsorption in demineralized water and secondary effluent, and this was particularly the case for the groundwater spent GAC. However, as compared to the fresh counterparts, the decreased surface area and the induced surface acidic groups on the pulverized sGACs contributed both to the lower uptake and the more impeded adsorption kinetic of atrazine in the demineralized water. Nonetheless, the pulverized sGACs, especially the one preloaded by surface water, was less susceptible to adsorption competition in the secondary effluent, due to its negatively charged surface which can repulse the accessibility of the co-present organic matter. This suggests the reusability of the drinking water spent GACs for micro-pollutant adsorption in the treated wastewater. Copyright © 2015 Elsevier Ltd. All rights reserved.
Transpiring purging access probe for particulate laden or hazardous environments
VanOsdol, John G
2013-12-03
An access probe for remote-sensing access through a viewing port, viewing volume, and access port into a vessel. The physical boundary around the viewing volume is partially formed by a porous sleeve lying between the viewing volume and a fluid conduit. In a first mode of operation, a fluid supplied to the fluid conduit encounters the porous sleeve and flows through the porous material to maintain the viewing volume free of ash or other matter. When additional fluid force is needed to clear the viewing volume, the pressure of the fluid flow is increased sufficiently to slidably translate the porous sleeve, greatly increasing the flow into the viewing volume. The porous sleeve is returned to position by an actuating spring. The access probe thereby provides for alternate modes of operation based on the pressure of an actuating fluid.
Lamina Cribrosa Microarchitecture in Monkey Early Experimental Glaucoma: Global Change
Reynaud, Juan; Lockwood, Howard; Gardiner, Stuart K.; Williams, Galen; Yang, Hongli; Burgoyne, Claude F.
2016-01-01
Purpose The purpose of this study was to characterize experimental glaucoma (EG) versus control eye differences in lamina cribrosa (LC), beam diameter (BD), pore diameter (PD), connective tissue volume fraction (CTVF), connective tissue volume (CTV), and LC volume (LV) in monkey early EG. Methods Optic nerve heads (ONHs) of 14 unilateral EG and 6 bilateral normal (BN) monkeys underwent three-dimensional reconstruction and LC beam segmentation. Each beam and pore voxel was assigned a diameter based on the largest sphere that contained it before transformation to a common cylinder with inner, middle, and outer layers. Full-thickness and layer averages for BD, PD, CTVF, CTV, and LV were calculated for each ONH. Beam diameter and PD distributions for each ONH were fit to a gamma distribution and summarized by scale and shape parameters. Experimental glaucoma and depth effects were assessed for each parameter by linear mixed-effects (LME) modeling. Animal-specific EG versus control eye differences that exceeded the maximum intereye difference among the six BN animals were considered significant. Results Overall EG eye mean PD was 12.8% larger (28.2 ± 5.6 vs. 25.0 ± 3.3 μm), CTV was 26.5% larger (100.06 ± 47.98 vs. 79.12 ± 28.35 × 106 μm3), and LV was 40% larger (229.29 ± 98.19 vs. 163.63 ± 39.87 × 106 μm3) than control eyes (P ≤ 0.05, LME). Experimental glaucoma effects were significantly different by layer for PD (P = 0.0097) and CTVF (P < 0.0001). Pore diameter expanded consistently across all PDs. Experimental glaucoma eye-specific parameter change was variable in magnitude and direction. Conclusions Pore diameter, CTV, and LV increase in monkey early EG; however, EG eye-specific change is variable and includes both increases and decreases in BD and CTVF. PMID:27362781
Hou, Xue-Dan; Li, Ning; Zong, Min-Hua
2013-05-01
Pretreatment of rice straw by using renewable cholinium lysine ionic liquid ([Ch][Lys] IL)-water mixtures and subsequent enzymatic hydrolysis of the residues were conducted in this work. There is a clear correlation between the delignification capacity of the pretreatment solvent and its basicity. After pretreatment, surface area and pore volume of rice straw increased significantly, which substantially improved polysaccharides accessibility to enzymes and thus enhanced polysaccharides digestion. By carefully controlling the pretreatment severity (IL content, temperature and duration), loss of readily extractable xylan could be minimized. The sugar yields of 81% for glucose and 48% for xylose were achieved in the enzymatic hydrolysis of rice straw after pretreatment with 20% [Ch][Lys]-water mixture at 90 °C for 1 h. This pretreatment process is highly promising for industrial application because of high sugar yields, low energy input, short pretreatment time, and being environmentally benign and highly tolerant to moisture. Copyright © 2013 Elsevier Ltd. All rights reserved.
Pathways of fluid transport and reabsorption across the peritoneal membrane.
Asghar, R B; Davies, S J
2008-05-01
The three-pore model of peritoneal fluid transport predicts that once the osmotic gradient has dissipated, fluid reabsorption will be due to a combination of small-pore reabsorption driven by the intravascular oncotic pressure, and an underlying disappearance of fluid from the cavity by lymphatic drainage. Our study measured fluid transport by these pathways in the presence and absence of an osmotic gradient. Paired hypertonic and standard glucose-dwell studies were performed using radio-iodinated serum albumin as an intraperitoneal volume marker and changes in intraperitoneal sodium mass to determine small-pore versus transcellular fluid transport. Disappearance of iodinated albumin was considered to indicate lymphatic drainage. Variability in transcellular ultrafiltration was largely explained by the rate of small-solute transport across the membrane. In the absence of an osmotic gradient, fluid reabsorption occurred via the small-pore pathway, the rate being proportional to the small-solute transport characteristics of the membrane. In most cases, fluid removal from the peritoneal cavity by this pathway was faster than by lymphatic drainage. Our study shows that the three-pore model describes the pathways of peritoneal fluid transport well. In the presence of high solute transport, poor transcellular ultrafiltration was due to loss of the osmotic gradient and an enhanced small-pore reabsorption rate after this gradient dissipated.
Roy, Sandipan; Panda, Debojyoti; Khutia, Niloy; Chowdhury, Amit Roy
2014-01-01
The present study investigates the mechanical response of representative volume elements of porous Ti-6Al-4V alloy, to arrive at a desired range of pore geometries that would optimize the reduction in stiffness necessary for biocompatibility with the stress concentration arising around the pore periphery, under physiological loading conditions with respect to orthopedic hip implants. A comparative study of the two is performed with the aid of a newly defined optimizing parameter called pore efficiency that takes into consideration both the stiffness quantity and the stress localization around pores. To perform a detailed analysis of the response of the porous structure over the entire spectrum of loading conditions that a hip implant is subjected to in vivo, the mechanical responses of 3D finite element models of cubic and rectangular parallelepiped geometries, with porosities varying over a range of 10% to 60%, are simulated under representative compressive, flexural as well as combined loading conditions. The results that are obtained are used to suggest a range of pore diameters that lower the effective stiffness and modulus of the implant to around 60% of the stiffness and modulus of dense solid implants while keeping the stress levels within permissible limits. PMID:25400663
NASA Astrophysics Data System (ADS)
Hikosaka, Ryouichi; Nagata, Fukue; Tomita, Masahiro; Kato, Katsuya
2016-10-01
Antibodies have received significant attention for use as antibody drugs, because they bind the objective protein (antigen) via antigen-antibody reactions. Recently, many reports have appeared on various monoclonal antibodies that recognize a single antigen. In this study, monoclonal antibodies are used as adsorbates on mesoporous silica (MPS) for affinity chromatography. MPS has high surface area and large pore volume; moreover, pore diameter, pore structure, and particle morphology are relatively easy to tune by adjusting the conditions of synthesis. The pore structure (two-dimensional (2D) hexagonal and three-dimensional cubic) and particle morphology (spherical and polyhedral) of MPS are optimized for use in a monoclonal antibody/MPS composite. When anti-IgG (one of the monoclonal antibodies) adsorbs on the MPS material and IgG (antigen) binds to anti-IgG/MPS composites, MCM-41p with a 2D-hexagonal pore structure and polyhedral particle morphology has the highest IgG binding efficiency. In addition, the antibody/MPS composites remain stable in chaotropic and low-pH solutions and can be cycled at least five times without decreasing IgG elution. In purification and removal tests, the use of the antibody/MPS composites allows only the objective protein from protein mixtures to be bound and eluted.
Normal Gravity Testing of a Microchannel Phase Separator for In Situ Resource Utilization
NASA Technical Reports Server (NTRS)
TeGrotenhuis, Ward E.; Stenkamp, Victoria S.; McQuillen, John (Technical Monitor)
2001-01-01
A microchannel separator, with 2.7 millimeters as the smallest dimension, was tested, and a pore throat structure captured and removed liquid from a gas-liquid stream. The microchannel device was tested over a of gas and liquid flow rates ranging from 0.0005 up to 0. 14 volume fraction of liquid. Four liquids were tested with air. The biggest factor affecting the throughput is the capacity of liquid flow through the pore throat, which is dictated by permeability, liquid viscosity, flow area, pore throat thickness, and pressure difference across the pore throat. Typically, complete separation of gas and liquid fractions was lost when the liquid flow rate reached about 40 to 60% of the pore throat capacity. However, this could occur over a range of 10 to 90% utilization of pore throat capacity. Breakthrough occurs in the microchannel phase separator at conditions similar to the annular to plug flow transition of two-phase microgravity pipe flow implying that operating in the proper flow regime is crucial. Analysis indicates that the Bond number did not affect performance, supporting the premise that hydrodynamic, interfacial, and capillary forces are more important than gravity. However, the relative importance of gravity is better discerned through testing under reduced gravity conditions.
Ahmad, Zaki Uddin; Chao, Bing; Konggidinata, Mas Iwan; Lian, Qiyu; Zappi, Mark E; Gang, Daniel Dianchen
2018-04-27
Numerous research works have been devoted in the adsorption area using experimental approaches. All these approaches are based on trial and error process and extremely time consuming. Molecular simulation technique is a new tool that can be used to design and predict the performance of an adsorbent. This research proposed a simulation technique that can greatly reduce the time in designing the adsorbent. In this study, a new Rhombic ordered mesoporous carbon (OMC) model is proposed and constructed with various pore sizes and oxygen contents using Materials Visualizer Module to optimize the structure of OMC for resorcinol adsorption. The specific surface area, pore volume, small angle X-ray diffraction pattern, and resorcinol adsorption capacity were calculated by Forcite and Sorption module in Materials Studio Package. The simulation results were validated experimentally through synthesizing OMC with different pore sizes and oxygen contents prepared via hard template method employing SBA-15 silica scaffold. Boric acid was used as the pore expanding reagent to synthesize OMC with different pore sizes (from 4.6 to 11.3 nm) and varying oxygen contents (from 11.9% to 17.8%). Based on the simulation and experimental validation, the optimal pore size was found to be 6 nm for maximum adsorption of resorcinol. Copyright © 2018 Elsevier B.V. All rights reserved.
Solventless visible light-curable coating: I. Critical formulation and processing parameters.
Bose, Sagarika; Bogner, Robin H
2010-06-30
Film coating is generally accomplished by spraying polymers dissolved in solvents onto a cascading bed of tablets. The limitations associated with the use of solvents (both aqueous and organic) can be overcome by the use of solventless coating technologies. In this proposed solventless photocurable film coating system, each layer of coating onto the pellets (non-pareil beads) was formed using liquid photocurable monomer, powdered pore-forming agents, photosensitizers and photoinitiators in a mini-coating pan and later cured by visible light. Yield, coating efficiency, variation in color, diameter and roundness were determined for each batch to evaluate process efficiency and coating quality. It was found that the ratio (S/L ratio) of the amount of solid (S) pore-forming agent to volume of liquid (L) monomer, particle size and type of the pore-forming agent, concentration of initiator, and total exposure (light intensity x exposure time) of light were critical formulation and processing parameters for the process. Using lactose as a pore-forming agent, an optimum ratio of pore-forming agent to photocurable polymer was 1.8-3.0 to achieve good process efficiency and uniformity. The ratio was sensitive to particle size and type of pore-forming agent. 2010 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Teama, Mostafa A.; Nabawy, Bassem S.
2016-09-01
Based on the available well log data of six wells chosen in the North Qarun oil field in the Western Desert of Egypt, the petrophysical evaluation for the Lower Cretaceous Kharita Formation was accomplished. The lithology of Kharita Formation was analyzed using the neutron porosity-density and the neutron porosity-gamma ray crossplots as well as the litho-saturation plot. The petrophysical parameters, include shale volume, effective porosity, water saturation and hydrocarbon pore volume, were determined and traced laterally in the studied field through the iso-parametric maps. The lithology crossplots of the studied wells show that the sandstone is the main lithology of the Kharita Formation intercalated with some calcareous shale. The cutoff values of shale volume, porosity and water saturation for the productive hydrocarbon pay zones are defined to be 40%, 10% and 50%, respectively, which were determined, based on the applied crossplots approach and their limits. The iso-parametric contour maps for the average reservoir parameters; such as net-pay thickness, average porosity, shale volume, water saturation and the hydrocarbon pore volume were illustrated. From the present study, it is found that the Kharita Formation in the North Qarun oil field has promising reservoir characteristics, particularly in the northwestern part of the study area, which is considered as a prospective area for oil accumulation.
A Bed-Deformation Experiment Beneath Engabreen, Norway
NASA Astrophysics Data System (ADS)
Iverson, N. R.; Hooyer, T. S.; Fischer, U. H.; Cohen, D.; Jackson, M.; Moore, P. L.; Lappegard, G.; Kohler, J.
2001-12-01
Although deformation of sediment beneath ice masses may contribute to their motion and may sometimes enable fast glacier flow, both the kinematics and mechanics of deformation are controversial. This controversy stems, in part, from subglacial measurements that are difficult to interpret. Measurements have been made either beneath ice margins or remotely through boreholes with interpretive limitations caused by uncertain instrument position and performance, uncertain sediment thickness and bed geometry, and unknown disturbance of the bed and stress state by drilling. We have used a different approach made possible by the Svartisen Subglacial Laboratory, which enables human access to the bed of Engabreen, Norway, beneath 230 m of temperate ice. A trough (2 m x 1.5 m x 0.4 m deep) was blasted in the rock bed and filled with sediment (75 percent sand and gravel, 20 percent silt, 5 percent clay). Instruments were placed in the sediment to record shear deformation (tiltmeters), dilation and contraction, total normal stress, and pore-water pressure. Pore pressure was manipulated by feeding water to the base of the sediment with a high-pressure pump, operated in a rock tunnel 4 m below the bed surface. After irregular deformation during closure of ice on the sediment, shear deformation and volume change stopped, and total normal stress became constant at 2.2 MPa. Subsequent pump tests, which lasted several hours, induced pore-water pressures greater than 70 percent of the total normal stress and resulted in shear deformation over most of the sediment thickness with attendant dilation. Ice separated from the sediment when effective normal stress was lowest, arresting shear deformation. Displacement profiles during pump tests were similar to those observed by Boulton and co-workers at Breidamerkurjökull, Iceland, with rates of shear strain increasing upward toward the glacier sole. Such deformation does not require viscous deformation resistance and is expected in a Coulomb material, a model for till advocated by B. Kamb.
Controlling Ionic Transport for Device Design in Synthetic Nanopores
NASA Astrophysics Data System (ADS)
Kalman, Eric Boyd
Polymer nanopores present a number of behaviors not seen in microscale systems, such as ion current rectification, ionic selectivity, size exclusion and potential dependent ion concentrations in and near the pore. The existence of these effects stems from the small size of nanopores with respect to the characteristic length scales of surface interactions at the interface between the nanopore surface and the solution within it. The large surface-to-volume ratio due to the nanoscale geometry of a nanopore, as well as similarity in scale between geometry and interaction demands the solution interact with the nanopore walls. As surfaces in solution almost always carry residual charge, these surface forces are primarily the electrostatic interactions between the charge groups on the pore surface and the ions in solution. These interactions may be used by the experimentalist to control ionic transport through synthetic nanopores, and use them as a template for the construction of devices. In this research, we present our work on creating a number of ionic analogs to seminal electronic devices, specifically diodes, and transistors, by controlling ionic transport through the electrostatic interactions between a single synthetic nanopore and ions. Control is achieved by "doping" the effective charge carrier concentration in specific regions of the nanopore through manipulation of the pore's surface charge. This manipulation occurs through two mechanisms: chemical modification of the surface charge and electrostatic manipulation of the local internal nanopore potential using a gate electrode. Additionally, the innate selectivity of the charged nanopores walls allows for the separation of charges in solution. This well-known effect, which spawns measureable quantities, the streaming potential and current, has been used to create nanoscale water desalination membranes. We attempt to create a device using membranes with large nanopore densities for the desalination of water which should theoretically outperform currently available devices, as through our previous work we have developed techniques allowing for transport manipulation not current accessible in traditional membrane motifs.
Dong, Yingbo; Lin, Hai; He, Yinhai
2017-03-01
The physicochemical properties of the 24 modified clinoptilolite samples and their ammonia-nitrogen removal rates were measured to investigate the correlation between them. The modified clinoptilolites obtained by acid modification, alkali modification, salt modification, and thermal modification were used to adsorb ammonia-nitrogen. The surface area, average pore width, macropore volume, mecropore volume, micropore volume, cation exchange capacity (CEC), zeta potential, silicon-aluminum ratios, and ammonia-nitrogen removal rate of the 24 modified clinoptilolite samples were measured. Subsequently, the linear regression analysis method was used to research the correlation between the physicochemical property of the different modified clinoptilolite samples and the ammonia-nitrogen removal rate. Results showed that the CEC was the major physicochemical property affecting the ammonia-nitrogen removal performance. According to the impacts from strong to weak, the order was CEC > silicon-aluminum ratios > mesopore volume > micropore volume > surface area. On the contrary, the macropore volume, average pore width, and zeta potential had a negligible effect on the ammonia-nitrogen removal rate. The relational model of physicochemical property and ammonia-nitrogen removal rate of the modified clinoptilolite was established, which was ammonia-nitrogen removal rate = 1.415[CEC] + 173.533 [macropore volume] + 0.683 [surface area] + 4.789[Si/Al] - 201.248. The correlation coefficient of this model was 0.982, which passed the validation of regression equation and regression coefficients. The results of the significance test showed a good fit to the correlation model.
Liu, Yiqun; Li, Chen; Liu, Cong; ...
2018-04-24
In situ contrast-matched neutron scattering was used to probe the electrolyte infiltration behavior of activated supercapacitor carbon electrodes using an aquoeus 1 M NaCl solution. It was found that only about 20% of the pore volume was infiltrated at chemical equilibrium. The partial infiltration can be attributed to the co-existence of hydrophilic and hydrophilic pores. As a result, the study suggests that for the achievement of optimal capacitance, supercapacitor electrodes should be evacuated before electrolyte infiltration.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Liu, Yiqun; Li, Chen; Liu, Cong
In situ contrast-matched neutron scattering was used to probe the electrolyte infiltration behavior of activated supercapacitor carbon electrodes using an aquoeus 1 M NaCl solution. It was found that only about 20% of the pore volume was infiltrated at chemical equilibrium. The partial infiltration can be attributed to the co-existence of hydrophilic and hydrophilic pores. As a result, the study suggests that for the achievement of optimal capacitance, supercapacitor electrodes should be evacuated before electrolyte infiltration.
Yaghi, Omar M.; Eddaoudi, Mohamed; Li, Hailian; Kim, Jaheon; Rosi, Nathaniel
2005-08-16
An isoreticular metal-organic framework (IRMOF) and method for systematically forming the same. The method comprises the steps of dissolving at least one source of metal cations and at least one organic linking compound in a solvent to form a solution; and crystallizing the solution under predetermined conditions to form a predetermined IRMOF. At least one of functionality, dimension, pore size and free volume of the IRMOF is substantially determined by the organic linking compound.
NASA Astrophysics Data System (ADS)
Chaynikov, S.; Porta, G.; Riva, M.; Guadagnini, A.
2012-04-01
We focus on a theoretical analysis of nonreactive solute transport in porous media through the volume averaging technique. Darcy-scale transport models based on continuum formulations typically include large scale dispersive processes which are embedded in a pore-scale advection diffusion equation through a Fickian analogy. This formulation has been extensively questioned in the literature due to its inability to depict observed solute breakthrough curves in diverse settings, ranging from the laboratory to the field scales. The heterogeneity of the pore-scale velocity field is one of the key sources of uncertainties giving rise to anomalous (non-Fickian) dispersion in macro-scale porous systems. Some of the models which are employed to interpret observed non-Fickian solute behavior make use of a continuum formulation of the porous system which assumes a two-region description and includes a bimodal velocity distribution. A first class of these models comprises the so-called ''mobile-immobile'' conceptualization, where convective and dispersive transport mechanisms are considered to dominate within a high velocity region (mobile zone), while convective effects are neglected in a low velocity region (immobile zone). The mass exchange between these two regions is assumed to be controlled by a diffusive process and is macroscopically described by a first-order kinetic. An extension of these ideas is the two equation ''mobile-mobile'' model, where both transport mechanisms are taken into account in each region and a first-order mass exchange between regions is employed. Here, we provide an analytical derivation of two region "mobile-mobile" meso-scale models through a rigorous upscaling of the pore-scale advection diffusion equation. Among the available upscaling methodologies, we employ the Volume Averaging technique. In this approach, the heterogeneous porous medium is supposed to be pseudo-periodic, and can be represented through a (spatially) periodic unit cell. Consistently with the two-region model working hypotheses, we subdivide the pore space into two volumes, which we select according to the features of the local micro-scale velocity field. Assuming separation of the scales, the mathematical development associated with the averaging method in the two volumes leads to a generalized two-equation model. The final (upscaled) formulation includes the standard first order mass exchange term together with additional terms, which we discuss. Our developments allow to identify the assumptions which are usually implicitly embedded in the usual adoption of a two region mobile-mobile model. All macro-scale properties introduced in this model can be determined explicitly from the pore-scale geometry and hydrodynamics through the solution of a set of closure equations. We pursue here an unsteady closure of the problem, leading to the occurrence of nonlocal (in time) terms in the upscaled system of equations. We provide the solution of the closure problems for a simple application documenting the time dependent and the asymptotic behavior of the system.
ERIC Educational Resources Information Center
de Jonge, J. F. M.; And Others
This report examines, country by country, the present state of student access to higher education institutions in the Member States of the European Community (EC), as well as the elements which affect access directly and the elements which can potentially have an effect on access. Volume 1 of the report gives an overview of the methods of data…
Maheshwari, Priya; Dutta, D; Muthulakshmi, T; Chakraborty, B; Raje, N; Pujari, P K
2017-02-08
The desorption mechanism of water from the hydrophilic mesopores of MCM-41 was studied using positron annihilation lifetime spectroscopy (PALS) and attenuated total reflection Fourier transform infrared spectroscopy supplemented with molecular dynamics (MD) simulation. PALS results indicated that water molecules do not undergo sequential evaporation in a simple layer-by-layer manner during desorption from MCM-41 mesopores. The results suggested that the water column inside the uniform cylindrical mesopore become stretched during desorption and induces cavitation (as seen in the case of ink-bottle type pores) inside it, keeping a dense water layer at the hydrophilic pore wall, as well as a water plug at both the open ends of the cylindrical pore, until the water was reduced to a certain volume fraction where the pore catastrophically empties. Before being emptied, the water molecules formed clusters inside the mesopores. The formation of molecular clusters below a certain level of hydration was corroborated by the MD simulation study. The results are discussed.
Pore-scale modeling of saturated permeabilities in random sphere packings.
Pan, C; Hilpert, M; Miller, C T
2001-12-01
We use two pore-scale approaches, lattice-Boltzmann (LB) and pore-network modeling, to simulate single-phase flow in simulated sphere packings that vary in porosity and sphere-size distribution. For both modeling approaches, we determine the size of the representative elementary volume with respect to the permeability. Permeabilities obtained by LB modeling agree well with Rumpf and Gupte's experiments in sphere packings for small Reynolds numbers. The LB simulations agree well with the empirical Ergun equation for intermediate but not for small Reynolds numbers. We suggest a modified form of Ergun's equation to describe both low and intermediate Reynolds number flows. The pore-network simulations agree well with predictions from the effective-medium approximation but underestimate the permeability due to the simplified representation of the porous media. Based on LB simulations in packings with log-normal sphere-size distributions, we suggest a permeability relation with respect to the porosity, as well as the mean and standard deviation of the sphere diameter.
Reactive Melt Infiltration of Silicon-Niobium Alloys in Microporous Carbons
NASA Technical Reports Server (NTRS)
Singh, M.; Behrendt, D. R.
1994-01-01
Studies of the reactive melt infiltration of silicon-niobium alloys in microporous carbon preforms prepared by the pyrolysis of a polymer precursor have been carried out using modeling, Differential Thermal Analysis (DTA), and melt infiltration. Mercury porosimetry results indicate a very narrow pore size distribution with virtually all the porosity within the carbon preforms open to infiltrants. The morphology and amount of the residual phases (niobium disilicide and silicon) in the infiltrated material can be tailored according to requirements by careful control of the properties (pore size and pore volume) of the porous carbon preforms and alloy composition. The average room temperature four-point flexural strength of a reaction-formed silicon carbide material (made by the infiltration of medium pore size carbon preform with Si - 5 at. % Nb alloy) is 290 +/- 40 MPa (42 +/- 6 ksi) and the fracture toughness is 3.7 +/- 0.3 MPa square root of m. The flexural strength decreases at high temperatures due to relaxation of residual thermal stresses and the presence of free silicon in the material.
Whey protein aerogel as blended with cellulose crystalline particles or loaded with fish oil.
Ahmadi, Maede; Madadlou, Ashkan; Saboury, Ali Akbar
2016-04-01
Whey protein hydrogels blended with nanocrystalline and microcrystalline cellulose particles (NCC and MCC, respectively) were prepared, followed by freeze-drying, to produce aerogels. NCC blending increased the Young's modulus, and elastic character, of the protein aerogel. Aerogels were microporous and mesoporous materials, as characterized by the pores sizing 1.2 nm and 12.2 nm, respectively. Blending with NCC decreased the count of both microporous and mesoporous-classified pores at the sub-100 nm pore size range investigated. In contrast, MCC blending augmented the specific surface area and pores volume of the aerogel. It also increased moisture sorption affinity of aerogel. The feasibility of conveying hydrophobic nutraceuticals by aerogels was evaluated through loading fish oil into the non-blended aerogel. Oil loading altered its microstructure, corresponding to a peak displacement in Fourier-transform infra-red spectra, which was ascribed to increased hydrophobic interactions. Surface coating of aerogel with zein decreased the oxidation susceptibility of the loaded oil during subsequent storage. Copyright © 2015 Elsevier Ltd. All rights reserved.
Adsorptive removal of naproxen and clofibric acid from water using metal-organic frameworks.
Hasan, Zubair; Jeon, Jaewoo; Jhung, Sung Hwa
2012-03-30
Adsorptive removal of naproxen and clofibric acid, two typical PPCPs (pharmaceuticals and personal care products), has been studied using metal-organic frameworks (MOFs) for the first time. The removal efficiency decreases in the order of MIL-101>MIL-100-Fe>activated carbon both in adsorption rate and adsorption capacity. The adsorption kinetics and capacity of PPCPs generally depend on the average pore size and surface area (or pore volume), respectively, of the adsorbents. The adsorption mechanism may be explained with a simple electrostatic interaction between PPCPs and the adsorbent. Finally, it can be suggested that MOFs having high porosity and large pore size can be potential adsorbents to remove harmful PPCPs in contaminated water. Copyright © 2012 Elsevier B.V. All rights reserved.
Freeze-drying of “pearl milk tea”: A general strategy for controllable synthesis of porous materials
Zhou, Yingke; Tian, Xiaohui; Wang, Pengcheng; Hu, Min; Du, Guodong
2016-01-01
Porous materials have been widely used in many fields, but the large-scale synthesis of materials with controlled pore sizes, pore volumes, and wall thicknesses remains a considerable challenge. Thus, the controllable synthesis of porous materials is of key general importance. Herein, we demonstrate the “pearl milk tea” freeze-drying method to form porous materials with controllable pore characteristics, which is realized by rapidly freezing the uniformly distributed template-containing precursor solution, followed by freeze-drying and suitable calcination. This general and convenient method has been successfully applied to synthesize various porous phosphate and oxide materials using different templates. The method is promising for the development of tunable porous materials for numerous applications of energy, environment, and catalysis, etc. PMID:27193866
Effects of catalyst pore structure and acid properties on the dehydration of glycerol.
Choi, Youngbo; Park, Hongseok; Yun, Yang Sik; Yi, Jongheop
2015-03-01
Hierarchical porous catalysts have recently attracted increasing interest because of the enhanced accessibility to active sites on such materials. In this context, previously reported hierarchically mesoporous ASN and ASPN materials are evaluated by applying them to the dehydration of glycerol, and demonstrate excellent catalytic performance. In addition, a comprehensive understanding of the effects of pore structures and the acid properties on the reaction through comparative studies with microporous HZSM-5 and mesoporous AlMCM-41 is provided. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Fluid Absorption and Release of Nonwovens and their Response to Compression
NASA Astrophysics Data System (ADS)
Bateny, Fatemeh
Fluid handling is a key property in one of the major nonwoven applications in absorbent product such as wipes, hygiene products, and baby diapers. These products are subjected to various levels of compression in real-use. The aim of this study was to investigate the liquid absorption and release properties of nonwovens to establish the absorption structure-property relationship at various compression levels. A comprehensive methodology, considering various flow directions, was employed to establish the relationship by decoupling the effect of structural parameters and material properties in two phases of this study respectively. In the first phase, the mechanism of absorption by pore structure was investigated through considering various fiber cross-sectional size and shape, as well as heterogeneous layered structures having a pore size reduction and expansion. In the second phase, the mechanism of absorption by fiber and consequent swelling was evaluated in view of fluid diffusion into the rayon fibers in samples having different percentages of PET fiber (non-absorbent) and rayon fiber (absorbent). The analysis of absorption and release properties through the entire dissertation was based on the pore characteristics of the nonwovens by measuring the average pore sizes, pore size distribution, and solidity. The investigation revealed that the absorption and release properties of nonwovens are governed by their pore characteristics. In homogeneous non-layered nonwoven fabrics, maximum absorption is mainly governed by the available pore volume. Absorbency rate is determined according to pore size and the maximum rate of absorption is achieved at a specific range of pore sizes. This indicates that an in-depth understanding of the absorption and release properties brings about valuable information for the absorbent product engineering.
NASA Astrophysics Data System (ADS)
Khan, Tasneem M. A.; Khan, Asiya; Sarawade, Pradip B.
2018-05-01
We report a method to synthesize low-density transparent mesoporous silica aerogel beads by ambient pressure drying (APD). The beads were prepared by acid-base sol-gel polymerization of sodium silicate in via the ball dropping method (BDM). To minimize shrinkage during drying, wet silica beads were initially prepared; their surfaces were then modified using trimethylchlorosilane (TMCS) via simultaneous solvent exchange and surface modification. The specific surface area and cumulative pore volume of the silica aerogel beads increased with an increase in the %V of TMCS. Silica aerogel beads with low packing bed density, high surface area, and large cumulative pore volume was obtained when TMCS was used. Properties of the final product were examined by BET, and TG-DT analyses. The hydrophobic silica aerogel beads were thermally stable up to 350°C. We discuss our results and compare our findings for modified versus unmodified silica beads.
Deformation Failure Characteristics of Coal Body and Mining Induced Stress Evolution Law
Wen, Zhijie; Wen, Jinhao; Shi, Yongkui; Jia, Chuanyang
2014-01-01
The results of the interaction between coal failure and mining pressure field evolution during mining are presented. Not only the mechanical model of stope and its relative structure division, but also the failure and behavior characteristic of coal body under different mining stages are built and demonstrated. Namely, the breaking arch and stress arch which influence the mining area are quantified calculated. A systematic method of stress field distribution is worked out. All this indicates that the pore distribution of coal body with different compressed volume has fractal character; it appears to be the linear relationship between propagation range of internal stress field and compressed volume of coal body and nonlinear relationship between the range of outburst coal mass and the number of pores which is influenced by mining pressure. The results provide theory reference for the research on the range of mining-induced stress and broken coal wall. PMID:24967438
Horowitz, A.J.; Lum, K.R.; Garbarino, J.R.; Hall, G.E.M.; Lemieux, C.; Demas, C.R.
1996-01-01
Field and laboratory experiments indicate that a number of factors associated with filtration other than just pore size (e.g., diameter, manufacturer, volume of sample processed, amount of suspended sediment in the sample) can produce significant variations in the 'dissolved' concentrations of such elements as Fe, Al, Cu, Zn, Pb, Co, and Ni. The bulk of these variations result from the inclusion/exclusion of colloidally associated trace elements in the filtrate, although dilution and sorption/desorption from filters also may be factors. Thus, dissolved trace element concentrations quantitated by analyzing filtrates generated by processing whole water through similar pore-sized filters may not be equal or comparable. As such, simple filtration of unspecified volumes of natural water through unspecified 0.45-??m membrane filters may no longer represent an acceptable operational definition for a number of dissolved chemical constituents.
NASA Technical Reports Server (NTRS)
Whiitson, Peggy A. (Inventor); Clift, Vaughan L. (Inventor)
1999-01-01
The present invention provides a method and apparatus for separating a blood sample having a volume of up to about 20 milliliters into cellular and acellular fractions. The apparatus includes a housing divided by a fibrous filter into a blood sample collection chamber having a volume of at least about 1 milliliter and a serum sample collection chamber. The fibrous filter has a pore size of less than about 3 microns, and is coated with a mixture including between about 1-40 wt/vol % mannitol and between about 0.1-15 wt/vol % of plasma fraction protein (or an animal or vegetable equivalent thereof). The coating causes the cellular fraction to be trapped by the small pores, leaving the cellular fraction intact on the fibrous filter while the acellular fraction passes through the filter for collection in unaltered form from the serum sample collection chamber.
Characterizing Adsorption Performance of Granular Activated Carbon with Permittivity.
Yang, Yang; Shi, Chao; Zhang, Yi; Ye, Jinghua; Zhu, Huacheng; Huang, Kama
2017-03-07
A number of studies have achieved the consensus that microwave thermal technology can regenerate the granular activated carbon (GAC) more efficiently and energy-conservatively than other technologies. In particular, in the microwave heating industry, permittivity is a crucial parameter. This paper developed two equivalent models to establish the relationship between effective complex permittivity and pore volume of the GAC. It is generally based on Maxwell-Garnett approximation (MGA) theory. With two different assumptions in the model, two quantificational expressions were derived, respectively. Permittivity measurements and Brunauer-Emmett-Teller (BET) testing had been introduced in the experiments. Results confirmed the two expressions, which were extremely similar. Theoretical and experimental graphs were matched. This paper set up a bridge which links effective complex permittivity and pore volume of the GAC. Furthermore, it provides a potential and convenient method for the rapid assisted characterization of the GAC in its adsorption performance.
Characterizing Adsorption Performance of Granular Activated Carbon with Permittivity
Yang, Yang; Shi, Chao; Zhang, Yi; Ye, Jinghua; Zhu, Huacheng; Huang, Kama
2017-01-01
A number of studies have achieved the consensus that microwave thermal technology can regenerate the granular activated carbon (GAC) more efficiently and energy-conservatively than other technologies. In particular, in the microwave heating industry, permittivity is a crucial parameter. This paper developed two equivalent models to establish the relationship between effective complex permittivity and pore volume of the GAC. It is generally based on Maxwell-Garnett approximation (MGA) theory. With two different assumptions in the model, two quantificational expressions were derived, respectively. Permittivity measurements and Brunauer–Emmett–Teller (BET) testing had been introduced in the experiments. Results confirmed the two expressions, which were extremely similar. Theoretical and experimental graphs were matched. This paper set up a bridge which links effective complex permittivity and pore volume of the GAC. Furthermore, it provides a potential and convenient method for the rapid assisted characterization of the GAC in its adsorption performance. PMID:28772628
Effect of heat treatment on CO2 adsorption of KOH-activated graphite nanofibers.
Meng, Long-Yue; Park, Soo-Jin
2010-12-15
In this work, graphite nanofibers (GNFs) were successfully expanded intercalating KOH followed by heat treatment in the temperature range of 700-1000 °C. The aim was to improve the CO(2) adsorption capacity of the GNFs by increasing the porosity of GNFs. The effects of heat treatment on the pore structures of GNFs were investigated by N(2) full isotherms, XRD, SEM, and TEM. The CO(2) adsorption capacity was measured by CO(2) isothermal adsorption at 25 °C and 1 atm. From the results, it was found that the activation temperature had a major influence on CO(2) adsorption capacity and textural properties of GNFs. The specific surface area, total pore volume, and mesopore volume of the GNFs increased after heat treatment. The CO(2) adsorption isotherms showed that G-900 exhibited the best CO(2) adsorption capacity with 59.2 mg/g. Copyright © 2010 Elsevier Inc. All rights reserved.
Ultrasound Algorithm Derivation for Soil Moisture Content Estimation
NASA Technical Reports Server (NTRS)
Belisle, W.R.; Metzl, R.; Choi, J.; Aggarwal, M. D.; Coleman, T.
1997-01-01
Soil moisture content can be estimated by evaluating the velocity at which sound waves travel through a known volume of solid material. This research involved the development of three soil algorithms relating the moisture content to the velocity at which sound waves moved through dry and moist media. Pressure and shear wave propagation equations were used in conjunction with soil property descriptions to derive algorithms appropriate for describing the effects of moisture content variation on the velocity of sound waves in soils with and without complete soil pore water volumes, An elementary algorithm was used to estimate soil moisture contents ranging from 0.08 g/g to 0.5 g/g from sound wave velocities ranging from 526 m/s to 664 m/s. Secondary algorithms were also used to estimate soil moisture content from sound wave velocities through soils with pores that were filled predominantly with air or water.
Capillary Pressure of a Liquid Between Uniform Spheres Arranged in a Square-Packed Layer
NASA Technical Reports Server (NTRS)
Alexader, J. Iwan D.; Slobozhanin, Lev A.; Collicott, Steven H.
2004-01-01
The capillary pressure in the pores defined by equidimensional close-packed spheres is analyzed numerically. In the absence of gravity the menisci shapes are constructed using Surface Evolver code. This permits calculation the free surface mean curvature and hence the capillary pressure. The dependences of capillary pressure on the liquid volume constructed here for a set of contact angles allow one to determine the evolution of basic capillary characteristics under quasi-static infiltration and drainage. The maximum pressure difference between liquid and gas required for a meniscus passing through a pore is calculated and compared with that for hexagonal packing and with approximate solution given by Mason and Morrow [l]. The lower and upper critical liquid volumes that determine the stability limits for the equilibrium capillary liquid in contact with square packed array of spheres are tabulated for a set of contact angles.
Aluminosilicate nanoparticles for catalytic hydrocarbon cracking.
Liu, Yu; Pinnavaia, Thomas J
2003-03-05
Aluminosilicate nanoparticles containing 9.0-20 nm mesopores were prepared through the use of protozeolitic nanoclusters as the inorganic precursor and starch as a porogen. The calcined, porogen-free composition containing 2 mol % aluminum exhibited the porosity, hydrothermal stability, and acidity needed for the cracking of very large hydrocarbons. In fact, the hydrothermal stability of the nanoparticles to pure steam at 800 degrees C, along with the cumene cracking activity, surpassed the analogous performance properties of ultrastable Y zeolite, the main catalyst component of commercial cracking catalysts. The remarkable hydrothermal stability and catalytic reactivity of the new nanoparticles are attributable to a unique combination of two factors, the presence of protozeolitic nanoclusters in the pore walls and the unprecedented pore wall thickness (7-15 nm). In addition, the excellent catalytic longevity of the nanoparticles is most likely facilitated by the small domain size of the nanoparticles that greatly improves access to the acid sites on the pore walls and minimizes the diffusion length of coke precursors out of the pores.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jerban, Saeed, E-mail: saeed.jerban@usherbrooke.ca
2016-08-15
The pore interconnection size of β-tricalcium phosphate scaffolds plays an essential role in the bone repair process. Although, the μCT technique is widely used in the biomaterial community, it is rarely used to measure the interconnection size because of the lack of algorithms. In addition, discrete nature of the μCT introduces large systematic errors due to the convex geometry of interconnections. We proposed, verified and validated a novel pore-level algorithm to accurately characterize the individual pores and interconnections. Specifically, pores and interconnections were isolated, labeled, and individually analyzed with high accuracy. The technique was verified thoroughly by visually inspecting andmore » verifying over 3474 properties of randomly selected pores. This extensive verification process has passed a one-percent accuracy criterion. Scanning errors inherent in the discretization, which lead to both dummy and significantly overestimated interconnections, have been examined using computer-based simulations and additional high-resolution scanning. Then accurate correction charts were developed and used to reduce the scanning errors. Only after the corrections, both the μCT and SEM-based results converged, and the novel algorithm was validated. Material scientists with access to all geometrical properties of individual pores and interconnections, using the novel algorithm, will have a more-detailed and accurate description of the substitute architecture and a potentially deeper understanding of the link between the geometric and biological interaction. - Highlights: •An algorithm is developed to analyze individually all pores and interconnections. •After pore isolating, the discretization errors in interconnections were corrected. •Dummy interconnections and overestimated sizes were due to thin material walls. •The isolating algorithm was verified through visual inspection (99% accurate). •After correcting for the systematic errors, algorithm was validated successfully.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Oldenburg, Curt; Pruess, Karsten; Birkholzer, Jens
The paper examines the pressure increase resulting from injection of CO2 into a 1D radial system with closed boundaries. The finding is that unacceptably high pressures are obtained when only 1% or less of the pore volume is occupied by injected CO2. These results are used to make the general conclusion that large-scale CCS is not feasible.