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At least 73 records · Page 4

Nanopore networks in colloidal silica assemblies characterized by XCT for confined fluid flow modeling

Fluid flow through nanopore structures has exhibited different behavior than that described by Darcy's law, derived from pore networks of micrometer scale. Here, pressure assemblies of colloidal silica spheres of specified diameters from 94 to 620 nanometers were prepared as model nano-porous media. The smaller silica spheres tended to form random packing, but some substantial ordering was found in the packing of the larger silica spheres. X-ray computed tomography (XCT), with a voxel resolution of 16 nm, was used to characterize the nanopore networks. The porosity of the Nano-XCT pore network (34%) was less than the total porosity of the assemblies as determined by X-ray attenuation (52%), possibly due to the limits of voxel resolution during segmentation. Fluid flow in the nanopore networks was simulated using the single-phase Lattice Boltzmann Method, and the simulated permeability was compared with the empirical and experimental values. Based on our characterization, although a well-ordered packing of silica spheres was not achieved, it was found that the nanopore networks in the colloidal silica assemblies had pore size distributions corresponding to the particle sizes. The simulated permeability was less than the experimental measurement for water flow, but the complex packing of silica spheres and surface chemistry issues need to be considered in future research.

02 PETROLEUM↗

XANES reflects coordination change and underlying surface disorder of zinc adsorbed to silica

In this work, zinc K -edge X-ray absorption near-edge structure (XANES) spectroscopy of Zn adsorbed to silica and Zn-bearing minerals, salts and solutions was conducted to explore how XANES spectra reflect coordination environment and disorder in the surface to which a metal ion is sorbed. Specifically, XANES spectra for five distinct Zn adsorption complexes (Zn ads ) on quartz and amorphous silica [SiO 2(am) ] are presented from the Zn–water–silica surface system: outer-sphere octahedral Zn ads on quartz, inner-sphere octahedral Zn ads on quartz, inner-sphere tetrahedral Zn ads on quartz, inner-sphere octahedral Zn ads on SiO 2(am) and inner-sphere tetrahedral Zn ads on SiO 2(am) . XANES spectral analysis of these complexes on quartz versus SiO 2(am) reveals that normalized peak absorbance and K -edge energy position generally decrease with increasing surface disorder and decreasing Zn–O coordination. On quartz, the absorption-edge energy of Zn ads ranges from 9663.0 to 9664.1 eV for samples dominated by tetrahedrally versus octahedrally coordinated species, respectively. On SiO 2(am) , the absorption-edge energy of Zn ads ranges from 9662.3 to 9663.4 eV for samples dominated by tetrahedrally versus octahedrally coordinated species, respectively. On both silica substrates, octahedral Zn ads presents a single K -edge peak feature, whereas tetrahedral Zn ads presents two absorbance features. The energy space between the two absorbance peak features of the XANES K -edge of tetrahedral Zn ads is 2.4 eV for Zn on quartz and 3.2 eV for Zn on SiO 2(am) . Linear combination fitting of samples with a mixture of Zn ads complex types demonstrates that the XANES spectra of octahedral and tetrahedral Zn ads on silica are distinct enough for quantitative identification. These results suggest caution when deciphering Zn speciation in natural samples via linear combination approaches using a single Zn ads standard to represent sorption on a particular mineral surface. Correlation between XANES spectral features and prior extended X-ray absorption fine structure (EXAFS) derived coordination environments for these Zn ads on silica samples provides insight into Zn speciation in natural systems with XANES compatible Zn concentrations too low for EXAFS analysis.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Hollow Silica Particles: A Novel Strategy for Cost Reduction

Thermal insulation materials are highly sought after for applications such as building envelopes, refrigerators, cryogenic fuel storage chambers, and water supply piping. However, current insulation materials either do not provide sufficient insulation or are costly. A new class of insulation materials, hollow silica particles, has attracted tremendous attention due to its potential to provide a very high degree of thermal insulation. However, current synthesis strategies provide hollow silica particles at very low yields and at high cost, thus, making the particles unsuitable for real-world applications. In the present work, a synthesis process that produces hollow silica particles at very high yields and at a lower cost is presented. The effect of an infrared heat absorber, carbon black, on the thermal conductivity of hollow silica particles is also investigated and it is inferred that a carbon black–hollow silica particle mixture can be a better insulating material than hollow silica particles alone.

36 MATERIALS SCIENCE↗

Interplay between Shelf Life and Printability of Silica-Filled Suspensions

Although fumed silica/siloxane suspensions are commonly employed in additive manufacturing technology, the interplay between shelf life, storage conditions, and printability has yet to be explored. In this work, direct ink writing (DIW) was used to print unique three-dimensional structures that required suspensions to retain shape and form while being printed onto a substrate. Suspensions containing varying concentrations of hydrophobic and hydrophilic silica were formulated and evaluated over a time span of thirty days. Storage conditions included low (8%) and high (50%) relative humidity and temperatures ranging from 4 °C to 25 °C. The shelf life of the suspensions was examined by comparing the print quality of pristine and aged samples via rheology, optical microscopy, and mechanical testing. Results showed a significant decrease in printability over time for suspensions containing hydrophilic fumed silica, whereas the printability of suspensions containing hydrophobic fumed silica remained largely unchanged after storage. The findings in this work established the following recommendations for extending the shelf life and printability of suspensions commonly used in DIW technology: (1) higher fumed silica concentrations, (2) low humidity and low temperature storage environments, and (3) the use of hydrophobic fumed silica instead of hydrophilic fumed silica.

36 MATERIALS SCIENCE↗

Effect of Silica and Mixing Time on Microstructures of Porous Polymer Composite by Emulsion Templating

Porous polymer composite with tailored porosity is applied in the myriads of areas such as energy storage, oil/water absorption, bioengineering, and advanced areas of material science. The emulsion templating technology is one of the most popular methods for synthesizing porous polymer composite. It involves solidifying a two-phase mixture of porogen and polymer, then removing porogen to create pores within the continuous emulsion phase by polymerization or curing. The surfactant plays a pivotal role in accomplishing a stable emulsion, a key factor in designing the internal porous structure. This study highlights the effect of silica filler and mixing time on pore morphology, i.e., shape, size, and distribution. on polydimethylsiloxane (PDMS) porous structure utilizing the water-in-oil emulsion templating method. Span® 80 is used as a surfactant to reduce the surface tension between water, silica, and PDMS and simultaneously create a strong foaming effect. Different weight concentrations of silica (1-10 wt%) were chosen while keeping the internal phase, i.e., water (50 wt%) constant. The designed porous structures were further characterized through scanning electron microscopy (SEM). Porous composite specimens fabricated with higher silica content and mixing time consistently exhibit smaller pore sizes than specimens fabricated with lower mixing time and silica content. A breakthrough of pore morphology is seen at silica content higher than 5wt% at 1 min mixing, however, pore morphology drastically changes when mixing time increases from 1 min to 6 min. Variation of finer mixing time beyond 1 min shows stepwise changes in pore morphology from a large single-phase porous structure to a bi-modal porous structure which eventually become a smaller single-mode porous structure. Thus, the emulsion templating technique, in combination with different filler content and mixing time, will effectively aid in designing engineered porous polymer composite with varying stiffness and pore morphology.

Porous polymer, Emulsion templating, Surfactant, P↗

Sol–Gel‐Based Advanced Porous Silica Materials for Biomedical Applications

Abstract Porous silica‐based materials have burgeoning applications ranging from fillers and additives, to adsorbents, catalysts, and recently therapeutic agents and vaccines in nanomedicine. The preponderance of these materials is made by sol–gel processing wherein soluble silica precursors are reacted to form amorphous networks composed of siloxane bonds. The facile sol–gel approach allows for an unlimited variety of binary tertiary and more complex chemical compositions including organic ligands and networks resulting in so‐called organic–inorganic hybrid materials. Here, a brief review of the recent progress in sol–gel‐derived silica materials prepared as particles, thin films, biosilica/silica bioreplicas (of molecules, cells and organisms), and their related preparation, properties, and bioapplications is provided. First, it highlights the recent achievements of mesoporous silica nanoparticles in biomedical applications, including therapeutic agent delivery, multimodal imaging and theranostics, and bone tissue engineering and repair. Second, the research in evaporation‐induced self‐assembly (EISA)‐based mesostructured silica thin films and cell‐directed EISA in bio/nano interfaces for various bioapplications, such as bioactive coatings, biosensing, and living cell immobilization, has been reviewed. Third, the pioneering work in biomimetic silicification/immobilization of biomolecules and bio‐organisms and silica bioreplication of complex bio‐organisms is summarized. Finally, it is concluded with personal perspectives on the directions of future work on this field.

Lei, Qi↗

Two‐Dimensional Superstructures of Silica Cages

Abstract Despite extensive studies on mesoporous silica since the early 1990s, the synthesis of two‐dimensional (2D) silica nanostructures remains challenging. Here, mesoporous silica is synthesized at an interface between two immiscible solvents under conditions leading to the formation of 2D superstructures of silica cages, the thinnest mesoporous silica films synthesized to date. Orientational correlations between cage units increase with increasing layer number controlled via pH, while swelling with oil and mixed surfactants increase micelle size dispersity, leading to complex clathrate type structures in multilayer superstructures. The results suggest that a three‐dimensional (3D) crystallographic registry within cage‐like superstructures emerges as a result of the concerted 3D co‐assembly of the organic and inorganic components. Mesoporous 2D superstructures can be fabricated over macroscopic film dimensions and stacked on top of each other. The realization of previously inaccessible mesoporous silica heterostructures with separation or catalytic properties unachievable via conventional bulk syntheses is envisioned.

Aubert, Tangi↗

Enabling thermal energy storage in structural cementitious composites with a novel phase change material microcapsule featuring an inorganic shell and a bio-inspired silica coating

Phase change material (PCM) microcapsules offer a promising approach for integrating PCM into building materials for efficient thermal energy storage. Here, this study presents the development of a novel PCM microcapsule specifically designed for incorporation into cementitious materials. The microcapsule consists of a low-cost PCM core derived from vegetable oil by-products and a durable inorganic shell made from cenosphere, a hollow fly ash generated from coal burning power plants. A novel process is developed to apply a silica coating to these cenosphere-based PCM microcapsules (CPCM), resulting in bioinspired-silica-coated CPCM microcapsules (BCPCM). This coating process draws inspiration from marine microorganism-based silica production and utilizes low-cost sodium silicate as a precursor, enabling eco-friendly and cost-effective manufacturing at ambient temperature and mild pH conditions. The morphology, chemical stability, and thermal properties of the BCPCM along with its thermo-mechanical performance in cementitious composites were comprehensively analyzed. Experimental results demonstrate successful silica deposition on BCPCM, leading to enhanced latent heat properties of the produced BCPCM. With the silica coating, BCPCM exhibits a 50 °C delay in thermal decomposition compared to CPCM, enhancing fire resistance and preventing premature PCM leakage of the microcapsule. The bioinspired silica coating effectively restores over 10% of the strength loss for each percent increase in CPCM incorporated into the mortar. The thermal performance experiments reveal that increasing the BCPCM content reduces temperature peaks and rates of temperature increase, indicating an improved capacity for thermal energy storage. This new PCM microcapsule provides a cost-effective solution to integrate thermal energy storage to cementitious material, as evidenced that over 30% of aggregates (in volume) can be replaced by the microcapsule without a drastic loss of strength.

25 ENERGY STORAGE↗

Accurate Force Field for Carbon Dioxide–Silica Interactions Based on Density Functional Theory

Fluid–silica interfaces are ubiquitous in chemistry, occurring in both natural geochemical environments and practical applications ranging from separations to catalysis. Simulations of these interfaces have been, and continue to be, a significant avenue for understanding their behavior. A constraining factor, however, is the availability of accurate force fields. Most simulations use traditional “mixing rules” to determine nonbonded dispersion interactions, an approach that has not been critically examined. Here, in this study, we present Lennard-Jones parameters for the interaction of carbon dioxide with silica interfaces that are optimized to reproduce density functional theory (DFT)-based binding energies. The modeling is based on the recently developed silica-DDEC force field, whose atomic charges are consistent with DFT calculations. Standard mixing rules are found to predict weaker CO 2 binding to silica than that obtained from DFT, an effect corrected by the optimized parameters given here. This behavior extends to other silica force fields (Clayff and Gulmen-Thompson), and the present Lennard-Jones parameters improve their performance as well. The effects of improved Lennard-Jones parameters on the structural and dynamical properties of condensed CO 2 in silica slit pores are also examined.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dispersion of surface-modified, aggregated, fumed silica in polymer nanocomposites

Surface modification of model silica to enhance compatibility in nanocomposites has been widely studied. In addition to model spherical silica, several authors have investigated the impact of surface conditions on compatibility in commercial aggregated carbon black and silica. Here, dispersion is investigated for a series of nanocomposites produced from commercially modified fumed silica mixed with styrene butadiene rubber, polystyrene, and polydimethylsiloxane. Surface modification includes variation in surface hydroxyl content, siloxane, and silane treatment. Qualitatively, hydroxyl groups on the silica surface are considered incompatible with non-polar polymers, while methyl groups are compatible with oleophilic polymers. X-ray scattering was used to analyze the filler aggregate structure before and after dispersion, and the second virial coefficient was used to quantify nanodispersion. The content of surface moieties was determined from Fourier-transform infrared spectroscopy. It is observed that modified silica can display mean field or specific interactions as reflected by the presence of a correlation peak in x-ray scattering. For systems with specific interactions, a critical ordering concentration is observed related to the free energy change for structuring. A van der Waals model was used to model the second virial coefficient as a function of accumulated strain, yielding the excluded volume and an energetic term. The excluded volume could be predicted from the structural information, and the bound polymer layer was directly related to the surface methyl content, whereas the energetic term was found to synergistically depend on both the methyl and hydroxyl surface content.

36 MATERIALS SCIENCE↗

Caution on Using Tetrahydrofuran for Processing Crystalline Silica Samples From Engineered Stone for XRD Analysis

Abstract We conducted laboratory experiments to investigate a suspected effect of tetrahydrofuran (THF) on quantifying crystalline silica in samples collected from working with engineered stone when THF is used to process samples prior to the X-ray diffraction (XRD) analysis. Two groups of samples from grinding either engineered stone or granite were simultaneously taken from a laboratory testing system, with one group of samples using THF for processing and another group using muffle furnace for ashing. For each stone type, we also tested four levels of respirable dust loading on the samples by varying the grinding time from 1 to 8 min. Statistical analysis of the experimental results on crystalline silica contents of the two groups of samples showed that the difference between the two methods was not significant (P ≥ 0.05) for the granite at all four levels of respirable dust loading and for the engineered stone at the two levels of respirable dust loading greater than 0.5 mg. However, the crystalline silica content from using THF processing was significantly lower (P = 0.001) than that from using muffle furnace ashing for engineered stone when the respirable dust loading levels were less than 0.5 mg. For the engineered stone dust samples with grinding times of 1 and 2 min, the average respirable dust loading was about 0.19 and 0.34 mg, respectively; while the crystalline silica content from using THF processing was 30.9 and 21.5% lower than that from using muffle furnace ashing, respectively. Since most full-shift samples from field assessments in this industry are expected to have respirable dust loading less than 0.5 mg, muffle furnace or radio frequency plasma ashing should be specified as the preferred sample processing method instead of the THF processing method for quantification of crystalline silica when engineered stone is expected to present to avoid artificially reduced silica content values, which are likely caused by the reactions between THF and the resins in engineered stone.

Public, Environmental & Occupational Health↗

Characterization of the adsorption of water vapor and chlorine on microcrystalline silica

The characterization of water adsorption on silica is necessary to an understanding of how hydrogen chloride interacts with silica. The adsorption as a function of outgas temperatures of silica and as a function of the isotherm temperature was studied. Characterization of the silica structure by infrared analysis, X-ray diffraction and differential scanning calorimetry, surface area determinations, characterization of the sample surface by electron spectroscopy for chemical analysis (ESCA), and determinations of the heat of immersion in water of silica were investigated. The silica with a scanning electron microscope was examined.

Skiles, J. A.↗

Development of an improved toughness hyperpure silica reflective heat shield

High purity three dimensionally woven silica-silica materials were evaluated for use as a tough reflective heat shield for planetary entry probes. A special weave design was selected to minimize light piping effects through the heat shield thickness. Various weave spacings were evaluated for densification efficiency with an 0.7 micron particle size high purity silica. Spectral hemispherical reflectance was measured from 0.2 to 2.5 microns at room temperature. Reflectance increases due to densification and purity of material were measured. Reflectance of 3D hyperpure silica was higher than 3D astroquartz silica for all wavelengths. Mechanical properties were measured in beam flexure and beam shear tests. Results indicated strengths lower than reported for slip cast fused silica. Low strengths were attributed to low densities achieved through vacuum impregnation.

Rusert, E. L.↗

Secular change in chert distribution: a reflection of evolving biological participation in the silica cycle

In the modern oceans, the removal of dissolved silica from sea water is principally a biological process carried out by diatoms, with lesser contributions from radiolaria, silicoflagellates, and sponges. Because such silica in sediments is often redistributed locally during diagenesis to from nodular or bedded chert, stratigraphic changes in the facies distribution of early diagenetic chert provide important insights into the development of biological participation in the silica cycle. The abundance of chert in upper Proterozoic peritidal carbonates suggests that at this time silica was removed from seawater principally by abiological processes operating in part of the margins of the oceans. With the evolution of demosponges near the beginning of the Cambrian Period, subtidal biogenetic cherts became increasingly common, and with the Ordovician rise of radiolaria to ecological and biogeochemical prominence, sedimented skeletons became a principal sink for oceanic silica. Cherts of Silurian to Cretaceous age share many features of facies distribution and petrography but they differ from Cenozoic siliceous deposits. These differences are interpreted to reflect the mid-Cretaceous radiation of diatoms and their subsequent rise to domination of the silica cycle. Biogeochemical cycles provide an important framework for the paleobiological interpretation of the organisms that participate in them.

Non-NASA Center↗

The Compressive Behavior of Isocyanate-crosslinked Silica Aerogel at High Strain Rates

Aerogels are low-density, highly nano-porous materials. Their engineering applications are limited due to their brittleness and hydrophilicity. Recently, a strong lightweight crosslinked silica aerogel has been developed by encapsulating the skeletal framework of amine-modified silica aerogels with polyureas derived by isocyanate. The mesoporous structure of the underlying silica framework is preserved through conformal polymer coating, and the thermal conductivity remains low. Characterization has been conducted on the thermal, physical properties and the mechanical properties under quasi-static loading conditions. In this paper, we present results on the dynamic compressive behavior of the crosslinked silica aerogel (CSA) using a split Hopkinson pressure bar (SHPB). A new tubing pulse shaper was employed to help reach the dynamic stress equilibrium and constant strain rate. The stress-strain relationship was determined at high strain rates within 114-4386/s. The effects of strain rate, density, specimen thickness and water absorption on the dynamic behavior of the CSA were investigated through a series of dynamic experiments. The Young's moduli (or 0.2% offset compressive yield strengths) at a strain rate approx.350/s were determined as 10.96/2.08, 159.5/6.75, 192.2/7.68, 304.6/11.46, 407.0/20.91 and 640.5/30.47 MPa for CSA with densities 0.205, 0.454, 0.492, 0.551,0.628 and 0.731 g/cu cm, respectively. The deformation and failure behaviors of a native silica aerogel with density (0.472 g/cu cm ), approximately the same as a typical CSA sample were observed with a high speed digital camera. Digital image correlation technique was used to determine the surface strains through a series of images acquired using high speed photography. The relative uniform axial deformation indicated that localized compaction did not occur at a compressive strain level of approx.17%, suggesting most likely failure mechanism at high strain rate to be different from that under quasi-static loading condition. The Poisson s ratio was determined to be 0.162 in nonlinear regime under high strain rates. CSA samples failed generally by splitting, but were much more ductile than native silica aerogels.

Luo, H.↗

Di-Isocyanate Crosslinked Aerogels with 1, 6-Bis (Trimethoxysilyl) Hexane Incorporated in Silica Backbone

Silica aerogels are desirable materials for many applications that take advantage of their light weight and low thermal conductivity. Addition of a conformal polymer coating which bonds with the amine decorated surface of the silica network improves the strength of the aerogels by as much as 200 times. Even with vast improvement in strength they still tend to undergo brittle failure due to the rigid silica backbone. We hope to increase the flexibility and elastic recovery of the silica based aerogel by altering the silica back-bone by incorporation of more flexible hexane links. To this end, we investigated the use of 1,6-bis(trimethoxysilyl)hexane (BTMSH), a polysilsesquioxane precursor3, as an additional co-reactant to prepare silica gels which were subsequently cross-linked with di-isocyanate. Previously, this approach of adding flexibility by BTMSH incorporation was demonstrated with styrene cross-linked aerogels. In our study, we varied silane concentration, mol % of silicon from BTMSH and di-isocyanate concentration by weight percent to attempt to optimize both the flexibility and the strength of the aerogels.

Vivod, Stephanie L.↗

Silica-Aerogel Composites Opacified with La(0.7)Sr(0.3)MnO3

As part of an effort to develop improved lightweight thermal-insulation tiles to withstand temperatures up to 1,000 C, silica aerogel/fused-quartz-fiber composite materials containing La0.7Sr0.3MnO3 particles as opacifiers have been investigated as potentially offering thermal conductivities lower than those of the otherwise equivalent silica-aerogel composite materials not containing La(0.7)Sr(0.3)MnO3 particles. The basic idea of incorporating opacifying particles into silica-aerogels composite to reduce infrared radiative contributions to thermal conductivities at high temperatures is not new: it has been reported in a number of previous NASA Tech Briefs articles. What is new here is the selection of La(0.7)Sr(0.3)MnO3 particles as candidate opacifiers that, in comparison with some prior opacifiers (carbon black and metal nanoparticles), are more thermally stable. The preparation of a composite material of the present type includes synthesis of the silica-aerogel component in a sol-gel process. The La(0.7)Sr(0.3)MnO3 particles, made previously in a separate process, are mixed into the sol, which is then cast onto fused-quartz-fiber batting. Then the aerogel-casting solution is poured into the mold, where it permeates the silica fiber felt. After the sol has gelled, the casting is aged and then subjected to supercritical drying to convert the gel to the final aerogel form. The separate process for making the La(0.7)Sr(0.3)MnO3 particles begins with the slow addition of corresponding proportions of La(CH3COOH)3, Mn(CH3COOH)3, and Sr(NO3)2 to a solution of H2O2 in H2O. The solution is then peptized by drop-wise addition of NH4OH to obtain a sol. Next, the sol is dried in an oven at a temperature of 120 C to obtain a glassy solid. The solid is calcined at 700 C to convert it to La(0.7)Sr(0.3)MnO3. Then La(0.7)Sr(0.3)MnO3 particles are made by ball-milling the calcined solid. The effectiveness of La(0.7)Sr(0.3)MnO3 particles as opacifiers and thermal-conductivity reducers depends on the statistical distribution of particle sizes as well as the relative proportions of La(0.7)Sr(0.3)MnO3 and aerogel. For experiments performed thus far, samples of aerogel/fiber composites were formulated to have, variously, silica target density of 0.07 or 0.14 g/cu cm and to contain 30 percent of La(0.7)Sr(0.3)MnO3 in average particle size of 0.3 or 3 microns. The thermal conductivities of the samples containing the 3 micron La(0.7)Sr(0.3)MnO3 particles were found to be lower than those of the samples containing the 0.3 micron La(0.7)Sr(0.3)MnO3 particles. The optimum particle size is believed to be between 1 and 5 microns.

Rhine, Wendell↗

Silica Dissolution and Precipitation in Galciated Volcanic Environments and Implications for Mars

The surface of Mars exhibits strong evidence for a widespread and long-lived cryosphere. Observations of the surface have identified phases produced by water-rock interactions, but the contribution of glaciers to the observed alteration mineralogy is unclear. To characterize the chemical alteration expected on an icy early Mars, we collected water and rock samples from terrestrial glaciated volcanics. We related geochemical measurements of meltwater to the mineralogy and chemistry of proglacial rock coatings. In these terrains, water is dominated by dissolved silica relative to other dissolved cations, particularly at mafic sites. Rock coatings associated with glacial striations on mafic boulders include a silica-rich component, indicating that silica precipitation is occurring in the subglacial environment. We propose that glacial alteration of volcanic bedrock is dominated by a combination of high rates of silica dissolution and precipitation of opaline silica. On Mars, cryosphere-driven chemical weathering could be the origin of observed silica-enriched phases.

Rutledge, A. M.↗