amorphous silica samples: Topics by Science.gov

Sample records for amorphous silica samples

Dissolution and analysis of amorphous silica in marine sediments.

USGS Publications Warehouse

Eggimann, D.W.; Manheim, F. T.; Betzer, P.R.

1980-01-01

The analytical estimation of amorphous silica in selected Atlantic and Antarctic Ocean sediments, the U.S.G.S. standard marine mud (MAG-1), A.A.P.G. clays, and samples from cultures of a marine diatom, Hemidiscus, has been examined. Our values for amorphous silica-rich circum-Antarctic sediments are equal to or greater than literature values, whereas our values for a set of amorphous silica-poor sediments from a transect of the N. Atlantic at 11oN, after appropriate correction for silica released from clays, are significantly lower than previous estimates from the same region. -from Authors
Linking Spectral Features with Composition, Crystallinity, and Roughness Properties of Silica and Implications for Candidate Hydrothermal Systems on Mars

NASA Astrophysics Data System (ADS)

Hamilton, V. E.; McDowell, M. L.; Berger, J. A.; Cady, S. L.; Knauth, L. P.

2011-12-01

We have collected visible to near infrared reflectance (VNIR, ~0.4 - 2.5 um), thermal infrared emissivity (TIR, ~5 - 45 um), SEM, XRD, surface roughness, and petrographic data for 18 silica samples. These rocks (e.g., replacement chert, geyserite, opal-A/-CT) represent a variety of geologic formation environments, including hydrothermal, and have XRD-determined crystallinities ranging from <1 to >10 according to the quartz crystallinity index. Our findings are relevant to the interpretation of orbital and in situ spectral observations of crystalline or amorphous silica on the Martian surface, some of which may have formed in hydrothermal systems. Almost all of our samples' VNIR spectra contain discernible bands. The most common features are related to hydration (H2O and/or OH) of silica (e.g., at ~1.4, 1.9, and 2.2 um). The visibility and strength of these bands is not always constant between spectra from different areas of a sample. Other features include those of carbonate, phyllosilicate, and iron oxide impurities. All of our amorphous silica samples have hydration features in the VNIR, but we note that the absorptions around ~2.2 um can be very weak in amorphous samples relative to features at other wavelengths and relative to ~2.2-um features observed in Martian data, suggesting that some amorphous silica on Mars could go undetected. Deposits containing significant anhydrous, crystalline silica (chert) may be assumed to lack features in the VNIR, but many of our cherts have spectral features and could be misidentified as materials dominated by what is a minor contaminant. Thermal infrared spectra of chert and opaline silica differ from each other as a result of the loss of long-range Si-O order in increasingly amorphous samples. Our samples display a clear trend in TIR band shapes where features attributable to crystalline quartz and amorphous silica are blended in samples with intermediate crystallinities. Most diagnostic TIR spectral features observable in laboratory data typically are recognizable in hyperspectral remote sensing data. These features are more difficult to distinguish (or are not included) at multispectral resolutions, but in nearly all uncontaminated samples, the positions of Si-O emissivity minima shift towards longer wavelengths with decreasing crystallinity. Contaminating phases with strong VNIR spectral features are observed in some of the TIR spectra but have a negligible effect in others, suggesting that TIR spectroscopy helps constrain the abundances of these phases. In addition to compositional and crystallinity information, our laboratory data demonstrate that TIR spectra can be used to deduce important information on silica phases' texture and orientation. If used in combination, VNIR and TIR spectroscopy can detect and characterize silica phases, allowing us to estimate conditions of silica formation, e.g., high- or low-temperature aqueous systems.
Amorphous Silica Micro Powder Additive Influence on Tensile Strength of One-Ply Particle Board

NASA Astrophysics Data System (ADS)

Pitukhin, A. V.; Kolesnikov, G. N.; Panov, N. G.; Vasilyev, S. B.

2018-03-01

The methods and results of experimental investigation on the additive influence of amorphous silica micro powder when mixed in the glue for one-ply particle board are presented in the article. Wooden particles of coniferous and hardwood species as well as glue solution based on carbamide-formaldehyde resin were used for boards manufacturing. The amorphous silica micro powder contained particles on the average 8 μm by the size and specific surface 120…400 m2/g was used in experiment. The samples were tested to determine their physical-mechanical properties. It was found that 1 % amorphous silica micro powder additive increases the breaking point of one-ply particle board under tensile stress by 143 %.
Thermal Infrared and Visible to Near-Infrared Spectral Analysis of Chert and Amorphous Silica

NASA Astrophysics Data System (ADS)

McDowell, M. L.; Hamilton, V. E.; Cady, S. L.; Knauth, P.

2009-03-01

We look in detail at the thermal infrared and visible to near-infrared spectra of various forms of chert and amorphous silica and compare the spectral variations between samples with variations in physical and chemical characteristics.
Pressure-induced silica quartz amorphization studied by iterative stochastic surface walking reaction sampling.

PubMed

Zhang, Xiao-Jie; Shang, Cheng; Liu, Zhi-Pan

2017-02-08

The crystal to amorphous transformation is a common phenomenon in Nature and has important impacts on material properties. Our current knowledge on such complex solid transformation processes is, however, limited because of their slow kinetics and the lack of long-range ordering in amorphous structures. To reveal the kinetics in the amorphization of solids, this work, by developing iterative reaction sampling based on the stochastic surface walking global optimization method, investigates the well-known crystal to amorphous transformation of silica (SiO 2 ) under external pressures, the mechanism of which has long been debated for its non-equilibrium, pressure-sensitive kinetics and complex product components. Here we report for the first time the global potential energy surface (PES) and the lowest energy pathways for α-quartz amorphization from first principles. We show that the pressurization at 15 GPa, the reaction condition, can lift the quartz phase energetically close to the amorphous zone, which thermodynamically initializes the amorphization. More importantly, the large flexibility of Si cation coordination (including four, five and six coordination) results in many kinetically competing routes to more stable dense forms, including the known MI, stishovite, newly-identified MII and TI phases. All these pathways have high barriers due to the local Si-O bond breaking and are mediated by amorphous structures with five-fold Si. This causes simultaneous crystal-to-crystal and crystal-to-amorphous transitions. The high barrier and the reconstructive nature of the phase transition are the key kinetics origin for silica amorphization under pressures.
Conversion of geothermal waste to commercial products including silica

DOEpatents

Premuzic, Eugene T.; Lin, Mow S.

2003-01-01

A process for the treatment of geothermal residue includes contacting the pigmented amorphous silica-containing component with a depigmenting reagent one or more times to depigment the silica and produce a mixture containing depigmented amorphous silica and depigmenting reagent containing pigment material; separating the depigmented amorphous silica and from the depigmenting reagent to yield depigmented amorphous silica. Before or after the depigmenting contacting, the geothermal residue or depigmented silica can be treated with a metal solubilizing agent to produce another mixture containing pigmented or unpigmented amorphous silica-containing component and a solubilized metal-containing component; separating these components from each other to produce an amorphous silica product substantially devoid of metals and at least partially devoid of pigment. The amorphous silica product can be neutralized and thereafter dried at a temperature from about 25.degree. C. to 300.degree. C. The morphology of the silica product can be varied through the process conditions including sequence contacting steps, pH of depigmenting reagent, neutralization and drying conditions to tailor the amorphous silica for commercial use in products including filler for paint, paper, rubber and polymers, and chromatographic material.
Synthesis of PANi-SiO2 Nanocomposite with In-Situ Polymerization Method: Nanoparticle Silica (NPS) Amorphous and Crystalline Phase

NASA Astrophysics Data System (ADS)

Munasir; Luvita, N. R. D.; Kusumawati, D. H.; Putri, N. P.; Triwikantoro; Supardi, Z. A. I.

2018-03-01

Silica which is synthesized from natural materials such as Bancar Tuban’s sand composited with Polyaniline (PANi), where the silica used are silica has an amorphous phase and cristobalite phase. In this research, the composite method used is in- situ polymerization, which is silica entered during the fabrication of PANi, then automatically silica will be substitute into the chain bonding of PANi. The aim of this research is to find out the results of a composite process using in-situ methods as well as differences in the morphology of PANi/a- SiO2 and PANi/c-SiO2. For the characterization of samples tested in the form of FTIR to determine the functional groups of the composite and SEM to determine the morphology of the sample. From the test results of FTIR are known composite possibility has occurred because there are several functional groups belonging to silica also functional groups belonging polyaniline, functional group that’s happened in wave numbers were almost identical between PANi/a-SiO2 and PANi/c-SiO2, but there are little differences were seen in the form of a graph generated from the peak and intensity that occurred charts for PANi/c-SiO2 has peak more pointed or sharp compared to PANi/a-SiO2 because that bond of crystal is strong, stiff and has a larger particle size than the amorphous composite. Then from the data of SEM seen clearly their morphological differences between PANi/a-SiO2 and PANi/c-SiO2 where polyaniline is composited with amorphous silica will have a fault that is not uniform or irregular different from PANi/c -SiO2 has a regular fault and this is corresponding with the nature of the typical structure of amorphous and crystalline.
Green synthesis of silica nanoparticles using sugarcane bagasse

NASA Astrophysics Data System (ADS)

Mohd, Nur Kamilah; Wee, Nik Nur Atiqah Nik; Azmi, Alyza A.

2017-09-01

Silica nanoparticles have been great attention as it being evaluated for used in abundant fields and applications. Due to this significance, this research was conducted to synthesis silica nanoparticles using local agricultural waste, sugarcane bagasse. We executed extraction and precipitation process as it involved low cost, less toxic and low energy process compared to other methods. The Infrared (IR) spectra showed the vibration peak of Si-O-Si, which clearly be the evidence for the silica characteristics in the sample. In this research, amorphous silica nanoparticles with spherical morphology with an average size of 30 nm, and specific surface area of 111 m2/g-1 have been successfully synthesized. The XRD patterns showed the amorphous nature of silica nanoparticles. As a comparison, the produced silica nanoparticles from sugarcane bagasse are compared with the respective nanoparticles synthesized using Stöber method.
Health hazards due to the inhalation of amorphous silica.

PubMed

Merget, R; Bauer, T; Küpper, H U; Philippou, S; Bauer, H D; Breitstadt, R; Bruening, T

2002-01-01

Occupational exposure to crystalline silica dust is associated with an increased risk for pulmonary diseases such as silicosis, tuberculosis, chronic bronchitis, chronic obstructive pulmonary disease (COPD) and lung cancer. This review summarizes the current knowledge about the health effects of amorphous (non-crystalline) forms of silica. The major problem in the assessment of health effects of amorphous silica is its contamination with crystalline silica. This applies particularly to well-documented pneumoconiosis among diatomaceous earth workers. Intentionally manufactured synthetic amorphous silicas are without contamination of crystalline silica. These synthetic forms may be classified as (1) wet process silica, (2) pyrogenic ("thermal" or "fumed") silica, and (3) chemically or physically modified silica. According to the different physicochemical properties, the major classes of synthetic amorphous silica are used in a variety of products, e.g. as fillers in the rubber industry, in tyre compounds, as free-flow and anti-caking agents in powder materials, and as liquid carriers, particularly in the manufacture of animal feed and agrochemicals; other uses are found in toothpaste additives, paints, silicon rubber, insulation material, liquid systems in coatings, adhesives, printing inks, plastisol car undercoats, and cosmetics. Animal inhalation studies with intentionally manufactured synthetic amorphous silica showed at least partially reversible inflammation, granuloma formation and emphysema, but no progressive fibrosis of the lungs. Epidemiological studies do not support the hypothesis that amorphous silicas have any relevant potential to induce fibrosis in workers with high occupational exposure to these substances, although one study disclosed four cases with silicosis among subjects exposed to apparently non-contaminated amorphous silica. Since the data have been limited, a risk of chronic bronchitis, COPD or emphysema cannot be excluded. There is no study that allows the classification of amorphous silica with regard to its carcinogenicity in humans. Further work is necessary in order to define the effects of amorphous silica on morbidity and mortality of workers with exposure to these substances.
Surface-enhanced Raman scattering of amorphous silica gel adsorbed on gold substrates for optical fiber sensors

NASA Astrophysics Data System (ADS)

Degioanni, S.; Jurdyc, A. M.; Cheap, A.; Champagnon, B.; Bessueille, F.; Coulm, J.; Bois, L.; Vouagner, D.

2015-10-01

Two kinds of gold substrates are used to produce surface-enhanced Raman scattering (SERS) of amorphous silica obtained via the sol-gel route using tetraethoxysilane Si(OC2H5)4 (TEOS) solution. The first substrate consists of a gold nanometric film elaborated on a glass slide by sputter deposition, controlling the desired gold thickness and sputtering current intensity. The second substrate consists of an array of micrometer-sized gold inverted pyramidal pits able to confine surface plasmon (SP) enhancing electric field, which results in a distribution of electromagnetic energy inside the cavities. These substrates are optically characterized to observe SPR with, respectively, extinction and reflectance spectrometries. Once coated with thin layers of amorphous silica (SiO2) gel, these samples show Raman amplification of amorphous SiO2 bands. This enhancement can occur in SERS sensors using amorphous SiO2 gel as shells, spacers, protective coatings, or waveguides, and represents particularly a potential interest in the field of Raman distributed sensors, which use the amorphous SiO2 core of optical fibers as a transducer to make temperature measurements.
Atomistic study of two-level systems in amorphous silica

NASA Astrophysics Data System (ADS)

Damart, T.; Rodney, D.

2018-01-01

Internal friction is analyzed in an atomic-scale model of amorphous silica. The potential energy landscape of more than 100 glasses is explored to identify a sample of about 700 two-level systems (TLSs). We discuss the properties of TLSs, particularly their energy asymmetry and barrier as well as their deformation potential, computed as longitudinal and transverse averages of the full deformation potential tensors. The discrete sampling is used to predict dissipation in the classical regime. Comparison with experimental data shows a better agreement with poorly relaxed thin films than well relaxed vitreous silica, as expected from the large quench rates used to produce numerical glasses. The TLSs are categorized in three types that are shown to affect dissipation in different temperature ranges. The sampling is also used to discuss critically the usual approximations employed in the literature to represent the statistical properties of TLSs.
Rapid Precipitation of Amorphous Silica in Experimental Systems with Nontronite (NAu-1) and Shewanella oneidensis MR-1

DTIC Science & Technology

2007-01-15

law, no person shall be subject to any penalty for failing to comply with a collection of information if it does not display a currently valid OMB...report, we focus on the rapid bio- life because much of our current understanding of early life mineralization of amorphous silica. comes from...matter. The Nanoplast-embedded sample was atomic emission spectroscopy (ICP). After pH analysis ultrathin-sectioned, and examined with JEOL3010 TEM with a
[Amorphous silica. Types, health effects of exposure, NDS].

PubMed

Woźniak, H; Wiecek, E

1995-01-01

Maximum allowable concentration (MAC) values for amorphous silica dust have not been identified in the Polish legal regulations up-to-date. In this work the authors review values of allowable (recommended) amorphous silica dust concentrations in other countries. Data on other types of amorphous silica (natural and synthetic) used in industry as well as data on health effects of exposure to these types of dust are presented. The work encompasses 42 entries in the references and one Table which includes the following proposed MAC values: Non-calcinate diatomaceous earth (diatomite) and synthetic silica: Total dust--10 mg/m3 Respirable dust--2 mg/m3 Calcinate diatomaceous earth (diatomite) and fused silica (vitreous silica): Total dust--2 mg/m3 Respirable dust--1 mg/m3.
The Phagocytosis and Toxicity of Amorphous Silica

PubMed Central

Costantini, Lindsey M.; Gilberti, Renée M.; Knecht, David A.

2011-01-01

Background Inhalation of crystalline silica is known to cause an inflammatory reaction and chronic exposure leads to lung fibrosis and can progress into the disease, silicosis. Cultured macrophages bind crystalline silica particles, phagocytose them, and rapidly undergo apoptotic and necrotic death. The mechanism by which particles are bound and internalized and the reason particles are toxic is unclear. Amorphous silica has been considered to be a less toxic form, but this view is controversial. We compared the uptake and toxicity of amorphous silica to crystalline silica. Methodology/Principal Findings Amorphous silica particles are phagocytosed by macrophage cells and a single internalized particle is capable of killing a cell. Fluorescent dextran is released from endo-lysosomes within two hours after silica treatment and Caspase-3 activation occurs within 4 hours. Interestingly, toxicity is specific to macrophage cell lines. Other cell types are resistant to silica particle toxicity even though they internalize the particles. The large and uniform size of the spherical, amorphous silica particles allowed us to monitor them during the uptake process. In mCherry-actin transfected macrophages, actin rings began to form 1-3 minutes after silica binding and the actin coat disassembled rapidly following particle internalization. Pre-loading cells with fluorescent dextran allowed us to visualize the fusion of phagosomes with endosomes during internalization. These markers provided two new ways to visualize and quantify particle internalization. At 37°C the rate of amorphous silica internalization was very rapid regardless of particle coating. However, at room temperature, opsonized silica is internalized much faster than non-opsonized silica. Conclusions/Significance Our results indicate that amorphous and crystalline silica are both phagocytosed and both toxic to mouse alveolar macrophage (MH-S) cells. The pathway leading to apoptosis appears to be similar in both cases. However, the result suggests a mechanistic difference between FcγRIIA receptor-mediated and non-opsonized silica particle phagocytosis. PMID:21311600
The phagocytosis and toxicity of amorphous silica.

PubMed

Costantini, Lindsey M; Gilberti, Renée M; Knecht, David A

2011-02-02

Inhalation of crystalline silica is known to cause an inflammatory reaction and chronic exposure leads to lung fibrosis and can progress into the disease, silicosis. Cultured macrophages bind crystalline silica particles, phagocytose them, and rapidly undergo apoptotic and necrotic death. The mechanism by which particles are bound and internalized and the reason particles are toxic is unclear. Amorphous silica has been considered to be a less toxic form, but this view is controversial. We compared the uptake and toxicity of amorphous silica to crystalline silica. Amorphous silica particles are phagocytosed by macrophage cells and a single internalized particle is capable of killing a cell. Fluorescent dextran is released from endo-lysosomes within two hours after silica treatment and Caspase-3 activation occurs within 4 hours. Interestingly, toxicity is specific to macrophage cell lines. Other cell types are resistant to silica particle toxicity even though they internalize the particles. The large and uniform size of the spherical, amorphous silica particles allowed us to monitor them during the uptake process. In mCherry-actin transfected macrophages, actin rings began to form 1-3 minutes after silica binding and the actin coat disassembled rapidly following particle internalization. Pre-loading cells with fluorescent dextran allowed us to visualize the fusion of phagosomes with endosomes during internalization. These markers provided two new ways to visualize and quantify particle internalization. At 37 °C the rate of amorphous silica internalization was very rapid regardless of particle coating. However, at room temperature, opsonized silica is internalized much faster than non-opsonized silica. Our results indicate that amorphous and crystalline silica are both phagocytosed and both toxic to mouse alveolar macrophage (MH-S) cells. The pathway leading to apoptosis appears to be similar in both cases. However, the result suggests a mechanistic difference between FcγRIIA receptor-mediated and non-opsonized silica particle phagocytosis.
Synthesis and characterization of amorphous mesoporous silica using TEMPO-functionalized amphiphilic templates

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

Vries, Wilke de; Doerenkamp, Carsten; Zeng, Zhaoyang

Inorganic–organic hybrid materials based on amorphous mesoporous silica containing organized nitroxide radicals within its mesopores have been prepared using the micellar self-assembly of TEOS solutions containing the nitroxide functionalized amphiphile (4-(N,N-dimethyl-N-hexadecylammonium)-2,2,6, 6-tetramethyl-piperidin-N-oxyl-iodide) (CAT-16). This template has been used both in its pure form and in various mixtures with cetyl trimethylammonium bromide (CTAB). The samples have been characterized by chemical analysis, N{sub 2} sorption studies, magnetic susceptibility measurements, and various spectroscopic methods. While electron paramagnetic resonance (EPR) spectra indicate that the strength of the intermolecular spin–spin interactions can be controlled via the CAT-16/CTAB ratio, nuclear magnetic resonance (NMR) data suggest thatmore » these interactions are too weak to facilitate cooperative magnetism. - Graphical abstract: The amphiphilic radical CAT-16 is used as a template for the synthesis of amorphous mesoporous silica. The resulting paramagnetic hybrid materials are characterized by BET, FTIR, NMR, EPR and magnetic susceptibility studies. - Highlights: • Amphiphilic CAT-16 as a template for mesoporous silica. • Comprehensive structural characterization by BET, FTIR; EPR and NMR. • Strength of radical-radical interactions tuable within CAT-16/CTAB mixtures.« less
Phase analysis of ZrO2-SiO2 systems synthesized through Ball milling mechanical activations

NASA Astrophysics Data System (ADS)

Nurlaila, Rizka; Musyarofah, Muwwaqor, Nibras Fuadi; Triwikantoro, Kuswoyo, Anton; Pratapa, Suminar

2017-01-01

Zircon powders have been produced from raw materials of amorphous zirconia and amorphous silica powders obtained from natural zircon sand of Kalimantan Tengah, Indonesia. Synthesis process was started with the extraction of zircon powder to produce sodium silicate solution and pure zircon powder. The amorphous zirconia and silica powders were prepared by alkali fusion and co-precipitation techniques. The powders were mixed using a planetary ball mill, followed by a calcination of various holding time of 3, 10, and 15 h. Phase characterization was done using X-Ray Diffraction (XRD) technique and analysis of the diffraction data was carried out using Rietica and MAUD software. The identified phases after the calcination were zircon, tetragonal zirconia, and cristobalite. The highest zircon content was obtained in the sample calcinated for15 hours - reaching 99.66 %wt. Crystallite size analysis revealed that the samples calcinated for 3, 10, and 15 h exhibited zircon crystal size of 176 (1) nm, 191 (1) nm and 233 (1) nm respectively.
Diffusion-driven D/H fractionation in silicates during hydration, dehydration and degassing

NASA Astrophysics Data System (ADS)

Roskosz, Mathieu; Laporte, Didier; Deloule, Etienne; Ingrin, Jannick; Remusat, Laurent; Depecker, Christophe; Leroux, Hugues

2017-04-01

Understanding how degassing occurs during accretion and differentiation is crucial to explain the water budget of planetary bodies. In this context, the hydrogen isotopic signature of water in mantle minerals and melts is particularly useful to trace reservoirs and their interactions. Nonetheless, little is known on the influence of mantle processes on the D/H signatures of silicates. In this study, we performed controlled hydration/dehydration experiments. We explore the possibility that diffusion-driven fractionation could affect the D/H signature of partially hydrated amorphous or molten silicates and nominally anhydrous minerals (NAMs). High purity synthetic fused silica samples were annealed at between 200 and 1000°C at 20 mbar water partial pressure for 1 to 30 days. Dehydration of initially hydrated silica was also performed at 1000°C for a few hours. A set of rhyolitic samples previously synthesized in order to study bubble nucleation during magma decompression was also analyzed. Finally a natural grossular monocrystal (Zillertaler Alps, Austria), partially dehydrated in air at 800°C for 10 hours was studied. Water content and speciation were measured both by Fourier-Transform Infra-Red and Raman spectroscopies. Isotopic analyses were performed with the IMS 1270 and 1280 ion microprobes. The silica samples, the rhyolitic glasses and the grossular monocrystal exhibit typical water concentration profiles. In all cases, water speciation does not change significantly along concentration profiles. Concerning D/H signatures, no isotopic variation is detectable across amorphous silica and rhyolitic glasses. The situation is however very different in the grossular monocrystal. A strong isotopic gradient appears correlated to the water concentration profile. Our data are interpreted in terms of diffusion mechanisms in both amorphous (and molten) silicates and NAMs. Hydration, dehydration and magma degassing are probably not able to promote large diffusion-driven fractionation of hydrogen in amorphous silicates. Conversely, the diffusion of water through the structure of NAMs affects the overall isotopic composition of dissolved water.
Grafting strategy to develop single site titanium on an amorphous silica surface.

PubMed

Capel-Sanchez, M C; Blanco-Brieva, G; Campos-Martin, J M; de Frutos, M P; Wen, W; Rodriguez, J A; Fierro, J L G

2009-06-16

Titanium/silica systems were prepared by grafting a titanium alkoxide (titanium isopropoxide and titanium (triethanolaminate) isopropoxide) precursor onto amorphous silica. The grafting process, which consisted of the hydrolysis of the Ti precursor by the hydroxyl groups on the silica surface, yielded samples containing Ti-loadings of 1-1.6 wt %. The as synthesized and calcined TiO(2)-SiO(2) samples were characterized by UV-vis, FTIR, XPS, and XANES spectroscopic techniques. These systems were tested in the liquid-phase epoxidation of oct-1-ene with hydrogen peroxide reaction. Spectroscopic data indicated that titanium anchoring takes place by reaction between the alkoxide precursor and surface OH groups of the silica substrate. The nature of surface titanium species generated by chemical grafting depends largely on the titanium precursor employed. Thus, the titanium isopropoxide precursor yields tetrahedrally coordinated polymeric titanium species, which give rise to a low-efficiency catalyst. However, if an atrane precursor (titanium (triethanolaminate) isopropoxide) is employed, isolated titanium species are obtained. The fact that these species remain isolated even after calcination is due to the protective effect of the triethanolaminate ligand that avoids titanium polymerization. These differences in the titanium environment have a pivotal role in the performance of these systems in the epoxidation of alkenes with hydrogen peroxide.
Grafting Strategy to Develop Single Site Titanium on an Amorphous Silica Surface

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

Capel-Sanchez, M.; Blanco-Brieva, G; Campos-Martin, J

2009-01-01

Titanium/silica systems were prepared by grafting a titanium alkoxide (titanium isopropoxide and titanium (triethanolaminate) isopropoxide) precursor onto amorphous silica. The grafting process, which consisted of the hydrolysis of the Ti precursor by the hydroxyl groups on the silica surface, yielded samples containing Ti-loadings of 1-1.6 wt %. The as synthesized and calcined TiO2-SiO2 samples were characterized by UV-vis, FTIR, XPS, and XANES spectroscopic techniques. These systems were tested in the liquid-phase epoxidation of oct-1-ene with hydrogen peroxide reaction. Spectroscopic data indicated that titanium anchoring takes place by reaction between the alkoxide precursor and surface OH groups of the silica substrate.more » The nature of surface titanium species generated by chemical grafting depends largely on the titanium precursor employed. Thus, the titanium isopropoxide precursor yields tetrahedrally coordinated polymeric titanium species, which give rise to a low-efficiency catalyst. However, if an atrane precursor (titanium (triethanolaminate) isopropoxide) is employed, isolated titanium species are obtained. The fact that these species remain isolated even after calcination is due to the protective effect of the triethanolaminate ligand that avoids titanium polymerization. These differences in the titanium environment have a pivotal role in the performance of these systems in the epoxidation of alkenes with hydrogen peroxide.« less

COHESION OF AMORPHOUS SILICA SPHERES: TOWARD A BETTER UNDERSTANDING OF THE COAGULATION GROWTH OF SILICATE DUST AGGREGATES

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

Kimura, Hiroshi; Wada, Koji; Senshu, Hiroki

2015-10-10

Adhesion forces between submicrometer-sized silicate grains play a crucial role in the formation of silicate dust agglomerates, rocky planetesimals, and terrestrial planets. The surface energy of silicate dust particles is the key to their adhesion and rolling forces in a theoretical model based on contact mechanics. Here we revisit the cohesion of amorphous silica spheres by compiling available data on the surface energy for hydrophilic amorphous silica in various circumstances. It turned out that the surface energy for hydrophilic amorphous silica in a vacuum is a factor of 10 higher than previously assumed. Therefore, the previous theoretical models underestimated themore » critical velocity for the sticking of amorphous silica spheres, as well as the rolling friction forces between them. With the most plausible value of the surface energy for amorphous silica spheres, theoretical models based on the contact mechanics are in harmony with laboratory experiments. Consequently, we conclude that silicate grains with a radius of 0.1 μm could grow to planetesimals via coagulation in a protoplanetary disk. We argue that the coagulation growth of silicate grains in a molecular cloud is advanced either by organic mantles rather than icy mantles or, if there are no mantles, by nanometer-sized grain radius.« less
Self-repairing properties of OPC clinker/natural zeolite blend in water and alkali carbonate environments at 270°C

DOE PAGES

Pyatina, Tatiana; Sugama, Toshifumi; Ronne, Arthur; ...

2018-01-01

The 10 d recoveries of the mechanical properties and crack sealing of an ordinary Portland cement (OPC) clinker/natural zeolite (ferrierite (Fer)) blend modified or unmodified with silica were tested at 270°C in water and alkali carbonate environments. The recoveries of the samples depended on their modification with silica and the curing environment, but were more than 100% after repeated damage under some test conditions. The mechanical properties and phase compositions of recovered samples were evaluated by compressive strength measurements and x-ray diffraction, differential thermogravimetric analyses, Fourier transform infrared analyses and scanning electron microscopy coupled with energy dispersive x-ray spectroscopy. Themore » sealing of 0·25 mm wide and ~2 mm deep cracks was visualised with a three-dimensional optical microscope. Fer decomposed under high-temperature alkaline conditions with the release of hydrolysates that, along with the hydrating clinker, participated in the formation of new phases contributing to strength recoveries. Here, these phases included crystalline magnesium and aluminium-containing silicates, calcium and carbonated calcium silicates and amorphous hydrates. Crack sealing was complete for the silica-modified samples and partial for unmodified ones cured in carbonate environments. The sealing was very poor for samples cured in water. Lastly, the main sealing phases included crystalline and amorphous silica, high-temperature-stable zeolites and talc mineral.« less
Self-repairing properties of OPC clinker/natural zeolite blend in water and alkali carbonate environments at 270°C

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

Pyatina, Tatiana; Sugama, Toshifumi; Ronne, Arthur

The 10 d recoveries of the mechanical properties and crack sealing of an ordinary Portland cement (OPC) clinker/natural zeolite (ferrierite (Fer)) blend modified or unmodified with silica were tested at 270°C in water and alkali carbonate environments. The recoveries of the samples depended on their modification with silica and the curing environment, but were more than 100% after repeated damage under some test conditions. The mechanical properties and phase compositions of recovered samples were evaluated by compressive strength measurements and x-ray diffraction, differential thermogravimetric analyses, Fourier transform infrared analyses and scanning electron microscopy coupled with energy dispersive x-ray spectroscopy. Themore » sealing of 0·25 mm wide and ~2 mm deep cracks was visualised with a three-dimensional optical microscope. Fer decomposed under high-temperature alkaline conditions with the release of hydrolysates that, along with the hydrating clinker, participated in the formation of new phases contributing to strength recoveries. Here, these phases included crystalline magnesium and aluminium-containing silicates, calcium and carbonated calcium silicates and amorphous hydrates. Crack sealing was complete for the silica-modified samples and partial for unmodified ones cured in carbonate environments. The sealing was very poor for samples cured in water. Lastly, the main sealing phases included crystalline and amorphous silica, high-temperature-stable zeolites and talc mineral.« less
Damage Accumulation in Silica Glass Nanofibers.

PubMed

Bonfanti, Silvia; Ferrero, Ezequiel E; Sellerio, Alessandro L; Guerra, Roberto; Zapperi, Stefano

2018-06-06

The origin of the brittle-to-ductile transition, experimentally observed in amorphous silica nanofibers as the sample size is reduced, is still debated. Here we investigate the issue by extensive molecular dynamics simulations at low and room temperatures for a broad range of sample sizes, with open and periodic boundary conditions. Our results show that small sample-size enhanced ductility is primarily due to diffuse damage accumulation, that for larger samples leads to brittle catastrophic failure. Surface effects such as boundary fluidization contribute to ductility at room temperature by promoting necking, but are not the main driver of the transition. Our results suggest that the experimentally observed size-induced ductility of silica nanofibers is a manifestation of finite-size criticality, as expected in general for quasi-brittle disordered networks.
Fracture-induced amorphization of polycrystalline SiO2 stishovite: a potential platform for toughening in ceramics

PubMed Central

Nishiyama, Norimasa; Wakai, Fumihiro; Ohfuji, Hiroaki; Tamenori, Yusuke; Murata, Hidenobu; Taniguchi, Takashi; Matsushita, Masafumi; Takahashi, Manabu; Kulik, Eleonora; Yoshida, Kimiko; Wada, Kouhei; Bednarcik, Jozef; Irifune, Tetsuo

2014-01-01

Silicon dioxide has eight stable crystalline phases at conditions of the Earth's rocky parts. Many metastable phases including amorphous phases have been known, which indicates the presence of large kinetic barriers. As a consequence, some crystalline silica phases transform to amorphous phases by bypassing the liquid via two different pathways. Here we show a new pathway, a fracture-induced amorphization of stishovite that is a high-pressure polymorph. The amorphization accompanies a huge volume expansion of ~100% and occurs in a thin layer whose thickness from the fracture surface is several tens of nanometers. Amorphous silica materials that look like strings or worms were observed on the fracture surfaces. The amount of amorphous silica near the fracture surfaces is positively correlated with indentation fracture toughness. This result indicates that the fracture-induced amorphization causes toughening of stishovite polycrystals. The fracture-induced solid-state amorphization may provide a potential platform for toughening in ceramics. PMID:25297473
Fracture-induced amorphization of polycrystalline SiO2 stishovite: a potential platform for toughening in ceramics.

PubMed

Nishiyama, Norimasa; Wakai, Fumihiro; Ohfuji, Hiroaki; Tamenori, Yusuke; Murata, Hidenobu; Taniguchi, Takashi; Matsushita, Masafumi; Takahashi, Manabu; Kulik, Eleonora; Yoshida, Kimiko; Wada, Kouhei; Bednarcik, Jozef; Irifune, Tetsuo

2014-10-09

Silicon dioxide has eight stable crystalline phases at conditions of the Earth's rocky parts. Many metastable phases including amorphous phases have been known, which indicates the presence of large kinetic barriers. As a consequence, some crystalline silica phases transform to amorphous phases by bypassing the liquid via two different pathways. Here we show a new pathway, a fracture-induced amorphization of stishovite that is a high-pressure polymorph. The amorphization accompanies a huge volume expansion of ~100% and occurs in a thin layer whose thickness from the fracture surface is several tens of nanometers. Amorphous silica materials that look like strings or worms were observed on the fracture surfaces. The amount of amorphous silica near the fracture surfaces is positively correlated with indentation fracture toughness. This result indicates that the fracture-induced amorphization causes toughening of stishovite polycrystals. The fracture-induced solid-state amorphization may provide a potential platform for toughening in ceramics.
Evaluation of silica nanoparticle toxicity after topical exposure for 90 days

PubMed Central

Ryu, Hwa Jung; Seong, Nak-won; So, Byoung Joon; Seo, Heung-sik; Kim, Jun-ho; Hong, Jeong-Sup; Park, Myeong-kyu; Kim, Min-Seok; Kim, Yu-Ri; Cho, Kyu-Bong; Seo, Mu Yeb; Kim, Meyoung-Kon; Maeng, Eun Ho; Son, Sang Wook

2014-01-01

Silica is a very common material that can be found in both crystalline and amorphous forms. Well-known toxicities of the lung can occur after exposure to the crystalline form of silica. However, the toxicities of the amorphous form of silica have not been thoroughly studied. The majority of in vivo studies of amorphous silica nanoparticles (NPs) were performed using an inhalation exposure method. Since silica NPs can be commonly administered through the skin, a study of dermal silica toxicity was necessary to determine any harmful effects from dermal exposures. The present study focused on the results of systemic toxicity after applying 20 nm colloidal silica NPs on rat skin for 90 days, in accordance with the Organization for Economic Cooperation and Development test guideline 411 with a good laboratory practice system. Unlike the inhalation route or gastrointestinal route, the contact of silica NPs through skin did not result in any toxicity or any change in internal organs up to a dose of 2,000 mg/kg in rats. PMID:25565831
Structural Coloration of a Colloidal Amorphous Array is Intensified by Carbon Nanolayers.

PubMed

Takeoka, Yukikazu; Iwata, Masanori; Seki, Takahiro; Nueangnoraj, Khanin; Nishihara, Hirotomo; Yoshioka, Shinya

2018-04-10

In this study, we introduce the possibility of applying a colloidal amorphous array composed of fine silica particles as a structural-color material to invisible information technology. The appearance of a thick filmlike colloidal amorphous array formed from fine silica particles is considerably influenced by incoherent light scattering across the entire visible region. Therefore, regardless of the diameter of the fine silica particles, the thick colloidal amorphous array exhibits a white color to the naked eye. When carbon is uniformly deposited in the colloidal amorphous array by a pressure-pulsed chemical vapor deposition method, incoherent light scattering in the colloidal amorphous array is suppressed. As a result, coherent light scattering due to the short-range order in the colloidal amorphous array becomes conspicuous and the array exhibits a vivid structural color. As structures, such as letters and pictures, can be drawn using this technology, the colloidal amorphous array as a structural-colored material may also be applicable for invisible information technology.
Effective utilizations of palm oil mill fly ash for synthetic amorphous silica and carbon zeolite composite synthesis

NASA Astrophysics Data System (ADS)

Utama, P. S.; Saputra, E.; Khairat

2018-04-01

Palm Oil Mill Fly Ash (POMFA) the solid waste of palm oil industry was used as a raw material for synthetic amorphous silica and carbon zeolite composite synthesis in order to minimize the wastes of palm oil industry. The alkaline extraction combine with the sol-gel precipitation and mechanical fragmentation was applied to produce synthetic amorphous silica. The byproduct, extracted POMFA was rich in carbon and silica content in a significant amount. The microwave heated hydrothermal process used to synthesize carbon zeolite composite from the byproduct. The obtained silica had chemical composition, specific surface area and the micrograph similar to commercial precipitated silica for rubber filler. The microwave heated hydrothermal process has a great potential for synthesizing carbon zeolite composite. The process only needs one-step and shorter time compare to conventional hydrothermal process.
Timescales and mechanisms of formation of amorphous silica coatings on fresh basalts at Kīlauea Volcano, Hawai'i

NASA Astrophysics Data System (ADS)

Chemtob, Steven M.; Rossman, George R.

2014-10-01

Young basalts from Kīlauea Volcano, Hawai'i, frequently feature opaque surface coatings, 1-80 μm thick, composed of amorphous silica and Fe-Ti oxides. These coatings are the product of interaction of the basaltic surface with volcanically-derived acidic fluids. Previous workers have identified these coatings in a variety of contexts on Hawai'i, but the timescales of coating development, coating growth rates, and factors controlling lateral coating heterogeneity were largely unconstrained. We sampled and analyzed young lava flows (of varying ages, from hours to ~ 40 years) along Kīlauea's southwest and east rift zones to characterize variation in silica coating properties across the landscape. Coating thickness varies as a function of flow age, flow surface type, and proximity to acid sources like local fissure vents and regional plumes emitted from Kīlauea Caldera and Pu'u Ō'ō. Silica coatings that form in immediate proximity to acid sources are more chemically pure than those forming in higher pH environments, which contain significant Al and Fe. Incipient siliceous alteration was observed on basalt surfaces as young as 8 days old, but periods of a year or more are required to develop contiguous coatings with obvious opaque coloration. Inferred coating growth rates vary with environmental conditions but were typically 1-5 μm/year. Coatings form preferentially on flow surfaces with glassy outer layers, such as spatter ramparts, volcanic bombs, and dense pahoehoe breakouts, due to glass strain weakening during cooling. Microtextural evidence suggests that the silica coatings form both by in situ dissolution-reprecipitation and by deposition of silica mobilized in solution. Thin films of water, acidified by contact with volcanic vapors, dissolved near-surface basalt, then precipitated amorphous silica in place, mobilizing more soluble cations. Additional silica was transported to and deposited on the surface by silica-bearing altering fluids derived from the basalt interior.
Synthesis and characterization of hematite pigment obtained from a steel waste industry.

PubMed

Prim, S R; Folgueras, M V; de Lima, M A; Hotza, D

2011-09-15

Pigments that meet environmental and technology requirements are the focus of the research in the ceramic sector. This study focuses on the synthesis of ceramic pigment by encapsulation of hematite in crystalline and amorphous silica matrix. Iron oxide from a metal sheet rolling process was used as chromophore. A different content of hematite and silica was homogenized by conventional and high energy milling. The powders obtained after calcinations between 1050 and 1200 °C for 2h were characterized by X-ray diffraction and SEM analysis. The pigments were applied to ceramic enamel and porcelain body. The effect of pigment was measured by comparing L*a*b* values of the heated samples. Results showed that the color developed is influenced by variables such as oxide content employed, conditions of milling and processing temperature. The results showed that the use of pigment developed does not interfere in microstructural characteristics of pigmented material. The best hue was obtained from samples with 15 wt% of chromophore, heated at 1200 °C in amorphous silica matrix. Copyright © 2011 Elsevier B.V. All rights reserved.
Phase transformations in 40-60-GPa shocked gneisses from the Haughton Crater (Canada): An Analytical Transmission Electron Microscopy (ATEM) study

NASA Technical Reports Server (NTRS)

Martinez, I.; Guyot, F.; Schaerer, U.

1992-01-01

In order to better understand phase transformations, chemical migration, and isotopic disequilibrium in highly shocked rocks, we have performed a microprobe and an ATEM study on gneisses shocked up to 60 GPa from the Haughton Crater. This study reveals the following chemical and structural characteristics: (1) SiO2 dominant areas are formed by a mixture of pure SiO2 polycrystalline quartz identified by electron diffraction pattern and chemical analysis and a silica-rich amorphous phase containing minor amounts of aluminium, potassium, and iron; (2) Areas with biotitelike composition are formed by less than 200-nm grains of iron-rich spinels embedded in a silica-rich amorphous phase that is very similar to the one described above; (3) Layers with feldsparlike composition are constituted by 100-200-nm-sized alumina-rich grains (the indexation of the crystalline structure is under progress) and the silica-rich amorphous phase; (4) Zones characterized by the unusual Al/Si ratio close to 1 are formed by spinel grains (200-nm-sized) embedded in the same silica-rich amorphous phase; and (5) The fracturated sillimanites contain domains with a lamellar structure, defined by the intercalation of 100-nm-wide lamellae of mullite crystals and of a silica-rich amorphous phase. These mullite crystals preserved the crystallographical orientation of the preshock sillimanite. All compositional domains, identified at the microprobe scale, can thus be explained by a mixture in different proportion between the following phases: (1) a silica-rich amorphous phase, with minor Al and K; (2) quartz crystals; (3) spinel crystals and alumina-rich crystals; (4) sillimanite; and (5) mullite. Such mixtures of amorphous phases and crystals in different proportions explain disturbed isotope systems in these rocks and chemical heterogeneities observed on the microprobe.
Design and basic properties of ternary gypsum-based mortars

NASA Astrophysics Data System (ADS)

Doleželová, M.; Vimmrová, A.

2017-10-01

Ternary mortars, prepared from gypsum, hydrated lime and three types of pozzolan were designed and tested. As a pozzolan admixture crushed ceramic, silica fume and granulated blast slag were used. The amount of pozzolans in the mixtures was determined according to molar weight of amorphous SiO2 in the material. The samples were stored under the water. The basic physical properties and mechanical properties were measured. The properties were compared with the properties of material without pozzolan. The best results in the water environment were achieved by the samples with silica fume.
Pozzolanic Characterization Of Waste Rice Husk Ash (RHA) From Muar, Malaysia

NASA Astrophysics Data System (ADS)

Hadipramana, J.; Riza, F. V.; Rahman, I. A.; Loon, L. Y.; Adnan, S. H.; Zaidi, A. M. A.

2016-11-01

Investigation of Rice Husk Ash (RHA) thoroughly under controlled burning is regular issue to obtain result to produce the amorphous silica that has high pozzolanic reactivity characteristic. This paper offered an observation about characteristic of ground and un-ground of un-controlled burning temperature RHA that were taken from rice millings in Muar, Johor Malaysia. Such tests as X-Ray Fluorescence (XRF), X-Ray Diffraction (XRD), Particle Size Analysis and Specific Area Surface, Fourier Transform Infrared Spectroscopy (FTIR), and Scanning Electron microscope (SEM) were conducted in this investigation to carry out the characteristic of RHA samples. The results show that the RHA was consist approximately 89.90% of silica and the RHA possessed the amorphous particle were dominant than its crystalline part. This proves that the RHA has a big potential as a pozzolanic material considering the silica content and porous structure. In addition, particle size analysis decides whether the pozzolanic reactivity can be increased by grinding process.
Inhibition of Recrystallization of Amorphous Lactose in Nanocomposites Formed by Spray-Drying.

PubMed

Hellrup, Joel; Alderborn, Göran; Mahlin, Denny

2015-11-01

This study aims at investigating the recrystallization of amorphous lactose in nanocomposites. In particular, the focus is on the influence of the nano- to micrometer length scale nanofiller arrangement on the amorphous to crystalline transition. Further, the relative significance of formulation composition and manufacturing process parameters for the properties of the nanocomposite was investigated. Nanocomposites of amorphous lactose and fumed silica were produced by co-spray-drying. Solid-state transformation of the lactose was studied at 43%, 84%, and 94% relative humidity using X-ray powder diffraction and microcalorimetry. Design of experiments was used to analyze spray-drying process parameters and nanocomposite composition as factors influencing the time to 50% recrystallization. The spray-drying process parameters showed no significant influence. However, the recrystallization of the lactose in the nanocomposites was affected by the composition (fraction silica). The recrystallization rate constant decreased as a function of silica content. The lowered recrystallization rate of the lactose in the nanocomposites could be explained by three mechanisms: (1) separation of the amorphous lactose into discrete compartments on a micrometer length scale (compartmentalization), (2) lowered molecular mobility caused by molecular interactions between the lactose molecules and the surface of the silica (rigidification), and/or (3) intraparticle confinement of the amorphous lactose. © 2015 Wiley Periodicals, Inc. and the American Pharmacists Association.
Ultra-Low Density Aerogel Mirror Substrates

DTIC Science & Technology

1993-04-01

Silica aerogel materials were fabricated by both the high temperature and low temperature methods at the Lawrence Livermore National Laboratory in...evaporation techniques were used to planarize the silica aerogel with SiO 2 prior to metalization. The PECVD was performed at the Cornell University...incident hv. Defect Physics Silica aerogel is an amorphous SiO, matrix of high porosity (or a low density disordered material). The amorphous r~ature of
Spheroidization of silica powders by radio frequency inductively coupled plasma with Ar-H2 and Ar-N2 as the sheath gases at atmospheric pressure

NASA Astrophysics Data System (ADS)

Li, Lin; Ni, Guo-hua; Guo, Qi-jia; Lin, Qi-fu; Zhao, Peng; Cheng, Jun-li

2017-09-01

Amorphous spherical silica powders were prepared by inductively coupled thermal plasma treatment at a radio frequency of 36.2 MHz. The effects of the added content of hydrogen and nitrogen into argon (serving as the sheath gas), as well as the carrier gas flow rate, on the spheroidization rate of silica powders, were investigated. The prepared silica powders before and after plasma treatment were examined by scanning electron microscopy, X-ray diffraction, and laser granulometric analysis. Results indicated that the average size of the silica particles increased, and the transformation of crystals into the amorphous state occurred after plasma treatment. Discharge image processing was employed to analyze the effect of the plasma temperature field on the spheroidization rate. The spheroidization rate of the silica powder increased with the increase of the hydrogen content in the sheath gas. On the other hand, the spheroidization rate of the silica power first increased and then decreased with the increase of the nitrogen content in the sheath gas. Moreover, the amorphous content increased with the increase of the spheroidization rate of the silica powder.
In situ observation of stishovite formation in shock-compressed fused silica

NASA Astrophysics Data System (ADS)

Tracy, Sally June; Turneaure, Stefan; Duffy, Thomas

2017-06-01

Silica, SiO2, has widespread applications ranging from optical components to refractory materials and is of geological importance as one of the major oxide components of the Earth's crust and mantle. The response of silica phases to dynamic loading has long been of interest for understanding the structural evolution of this fundamental oxide. Under shock compression both crystalline quartz and fused silica are characterized by the occurrence of a broad `mixed-phase region' (15-40 GPa) and a dense, high-pressure phase with much lower compressibility. Despite decades of study, the nature of this transformation and the identity of the high-pressure phase(s) remain poorly understood. In situ x-ray diffraction experiments on shock-compressed fused silica were conducted at the Dynamic Compression Sector of the Advanced Photon Source. The lattice-level structure was investigated through time-resolved x-ray diffraction measurements on samples reaching peak stress ranging from 12 to 47 GPa. Our results demonstrate that SiO2 adopts a dense amorphous structure in the `mixed-phase region' and abruptly transforms to stishovite above 34 GPa. These results provide clear evidence that high-pressure crystalline silicate phases can form from amorphous starting materials on the time-scale of laboratory shock experiments.
High-pressure infrared sepctra of alpha-quartz, coesite, stishovite and silica glass

NASA Technical Reports Server (NTRS)

Williams, Q.; Hemley, R. J.; Kruger, M. B.; Jeanloz, R.

1993-01-01

High-pressure infrared absorption spectra of alpha-quatz, coesite, stishovite, and SiO2 glass are consistent with the primary compression mechanism of the initially tetrahedrally bonded phases being the bending of the Si-O-Si angle at pressures less than 10-20 GPa. At higher pressures, up to 40 GPa, we observe a decline in the intensity of the infrared SiO4 asymmetric-stretching vibrations of all three phases, with an increase in the relative amplitude between 700 and 900/cm. This change in intensities is attributed to an increase in the average coordination number of silicon through extreme distortion of tetrahedra. At pressures above approximately 20 GPa, the low-pressure crystalline polymorphs gradually become amorphous, and the infrared spectra provide evidence for an increase in silicon coordination in these high-density amorphous phases. The pressure-amorphized samples prepared from quartz and coesite differ structurally both from each other and from silica glass that has been compressed, and the high pressure spectra indicate that these materials are considerably more disordered than stishovite under comparable pressure conditions. Average mode Grueneisen parameters calculated for quartz, stishovite and fused silica from both infrared and Raman spectra are compatible with the corresponding thermodynamic value of the Grueneisen parameter, however, that of coesite is significantly discrepant.
Raman Scattering Studies on Ag Nanocluster Composites Formed by Ion Implantation into Silica

NASA Astrophysics Data System (ADS)

Ren, Feng; Jiang, Chang Zhong; Fu, De Jun; Fu, Qiang

2005-12-01

Highly-pure amorphous silica slides were implanted by 200 keV Ag ions with doses ranged from 1× 1016 to 2× 1017 ions/cm2. Optical absorption spectra show that Ag nanoclusters with various sizes have been formed. Enhancement of surface enhanced Raman scattering signal by a factor up to about 103 was obtained by changing the Ag particle size. The silica was damaged by the implanted Ag ions, and the large compression stress on the silica leads to the shift of Raman peaks. New bands at 1368 and 1586 cm-1, which are attributed to the vibration of Ag-O bond and O2 molecules in silica, are observed in the samples with doses higher than 1× 1017 ions/cm2.

Physical processes of quartz amorphization due to friction

NASA Astrophysics Data System (ADS)

Nakamura, Y.; Muto, J.; Nagahama, H.; Miura, T.; Arakawa, I.; Shimizu, I.

2011-12-01

Solid state amorphization of minerals occurs in indentations, in shock experiments, and in high pressure metamorphic quartz rock. A production of amorphous material is also reported in experimentally created silicate gouges (Yund et al., 1990), and in San Andreas Fault core samples (Janssen et al., 2010). Rotary-shear friction experiments of quartz rocks imply dynamic weakening at seismic rates (Di Toro et al., 2004). These experiments have suggested that weakening is caused by formation and thixotropic behavior of a silica gel layer which comprises of very fine particles of hydrated amorphous silica on fault gouges (Goldsby & Tullis, 2002; Hayashi & Tsutsumi, 2010). Therefore, physical processes of amorphization are important to better understand weakening of quartz bearing rocks. In this study, we conducted a pin-on-disk friction experiment to investigate details of quartz amorphization (Muto et al, 2007). Disks were made of single crystals of synthetic and Brazilian quartz. The normal load F and sliding velocity V were ranged from 0.01 N to 1 N and from 0.01 m/s to 2.6 m/s, respectively. The friction was conducted using quartz and diamond pins (curvature radii of 0.2 ~ 3 mm) to large displacements (> 1000 m) under controlled atmosphere. We analyzed experiment samples by Raman spectroscopy and FT-IR. Raman spectroscopy (excitation wavelength 532.1 nm) provides lattice vibration modes, and was used to investigate the degree of amorphization of samples. Raman spectra of friction tracks on the disk show clear bands at wavenumbers of 126, 204, 356, 394, and 464 cm-1, characteristic of intact α-quartz. Remarkably, in experiments using diamond pins (F = 0.8 N, normal stress σr calculated by contact area = 293 ~ 440 MPa, V = 0.12 ~ 0.23 m/s), the bands at 204 and 464 cm-1 gradually broaden to reveal shoulders on the higher-wavenumber sides of these peaks. Especially, two distinguished peaks at 490 and 515 cm-1 and a weak broad peak at 606 cm-1 appear sporadically on the track after the slip distance of 43 m. The bands at 490 and 606 cm-1 can be assigned to the symmetric stretching of four-membered Si-O ring (D1 band) and planar three-membered Si-O ring (D2 band) in amorphous silica, respectively. The peak at 515 cm-1 corresponds to the strongest coesite A1 mode arising from four-membered Si-O ring structure. On the other hand, the bands at 464 cm-1 broaden to reveal a shoulder adjacent to the main peak in experiments using quartz pins (F = 1 N, σr = 1 MPa, V = 0.01 ~ 2.6 m/s) after a large displacement (>1000m). These results indicate that quartz change intermediate range structure of SiO2 network during friction, and four or three-membered Si-O rings gradually increase in six-membered quartz. The results of FT-IR analyses on friction tracks showed a broad peak at 3000 -3600 cm-1 which indicates the -OH symmetric stretching band of molecular H2O. It shows that hydration of quartz on friction tracks occur due to friction. The results of Raman spectroscopy and FT-IR imply that Si-O-Si bridging of strained rings preferentially react with water to form hydrated amorphous silica layer on friction surfaces, which is likely to occur weakening.
Si-29 NMR spectroscopy of naturally-shocked quartz from Meteor Crater, Arizona: Correlation to Kieffer's classification scheme

NASA Technical Reports Server (NTRS)

Boslough, M. B.; Cygan, R. T.; Kirkpatrick, R. J.

1993-01-01

We have applied solid state Si-29 nuclear magnetic resonance (NMR) spectroscopy to five naturally-shocked Coconino Sandstone samples from Meteor Crater, Arizona, with the goal of examining possible correlations between NMR spectral characteristics and shock level. This work follows our observation of a strong correlation between the width of a Si-29 resonance and peak shock pressure for experimentally shocked quartz powders. The peak width increase is due to the shock-induced formation of amorphous silica, which increases as a function of shock pressure over the range that we studied (7.5 to 22 GPa). The Coconino Sandstone spectra are in excellent agreement with the classification scheme of Kieffer in terms of presence and approximate abundances of quartz, coesite, stishovite, and glass. We also observe a new resonance in two moderately shocked samples that we have tentatively identified with silicon in tetrahedra with one hydroxyl group in a densified form of amorphous silica.
Amorphous Phases on the Surface of Mars

NASA Technical Reports Server (NTRS)

Rampe, E. B.; Morris, R. V.; Ruff, S. W.; Horgan, B.; Dehouck, E.; Achilles, C. N.; Ming, D. W.; Bish, D. L.; Chipera, S. J.

2014-01-01

Both primary (volcanic/impact glasses) and secondary (opal/silica, allophane, hisingerite, npOx, S-bearing) amorphous phases appear to be major components of martian surface materials based on orbital and in-situ measurements. A key observation is that whereas regional/global scale amorphous components include altered glass and npOx, local scale amorphous phases include hydrated silica/opal. This suggests widespread alteration at low water-to-rock ratios, perhaps due to snow/ice melt with variable pH, and localized alteration at high water-to-rock ratios. Orbital and in-situ measurements of the regional/global amorphous component on Mars suggests that it is made up of at least three phases: npOx, amorphous silicate (likely altered glass), and an amorphous S-bearing phase. Fundamental questions regarding the composition and the formation of the regional/global amorphous component(s) still remain: Do the phases form locally or have they been homogenized through aeolian activity and derived from the global dust? Is the parent glass volcanic, impact, or both? Are the phases separate or intimately mixed (e.g., as in palagonite)? When did the amorphous phases form? To address the question of source (local and/or global), we need to look for variations in the different phases within the amorphous component through continued modeling of the chemical composition of the amorphous phases in samples from Gale using CheMin and APXS data. If we find variations (e.g., a lack of or enrichment in amorphous silicate in some samples), this may imply a local source for some phases. Furthermore, the chemical composition of the weathering products may give insight into the formation mechanisms of the parent glass (e.g., impact glasses contain higher Al and lower Si [30], so we might expect allophane as a weathering product of impact glass). To address the question of whether these phases are separate or intimately mixed, we need to do laboratory studies of naturally altered samples made up of mixed phases (e.g., palagonite) and synthetic single phases to determine their short-range order structures and calculate their XRD patterns to use in models of CheMin data. Finally, to address the timing of the alteration, we need to study rocks on the martian surface of different ages that may contain glass (volcanic or impact) with MSL and future rovers to better understand how glass alters on the martian surface, if that alteration mechanism is universal, and if alteration spans across long periods of time or if there is a time past which unaltered glass remains.
Effect of radiation-induced amorphization on smectite dissolution.

PubMed

Fourdrin, C; Allard, T; Monnet, I; Menguy, N; Benedetti, M; Calas, G

2010-04-01

Effects of radiation-induced amorphization of smectite were investigated using artificial irradiation. Beams of 925 MeV Xenon ions with radiation dose reaching 73 MGy were used to simulate the effects generated by alpha recoil nuclei or fission products in the context of high level nuclear waste repository. Amorphization was controlled by X-ray diffraction, transmission electron microscopy, and Fourier transform infrared spectroscopy. An important coalescence of the smectite sheets was observed which lead to a loss of interparticle porosity. The amorphization is revealed by a loss of long-range structure and accompanied by dehydroxylation. The dissolution rate far-from-equilibrium shows that the amount of silica in solution is two times larger in the amorphous sample than in the reference clay, a value which may be enhanced by orders of magnitude when considering the relative surface area of the samples. Irradiation-induced amorphization thus facilitates dissolution of the clay-derived material. This has to be taken into account for the safety assessment of high level nuclear waste repository, particularly in a scenario of leakage of the waste package which would deliver alpha emitters able to amorphize smectite after a limited period of time.
Amorphous silica maturation in chemically weathered clastic sediments

NASA Astrophysics Data System (ADS)

Liesegang, Moritz; Milke, Ralf; Berthold, Christoph

2018-03-01

A detailed understanding of silica postdepositional transformation mechanisms is fundamental for its use as a palaeobiologic and palaeoenvironmental archive. Amorphous silica (opal-A) is an important biomineral, an alteration product of silicate rocks on the surface of Earth and Mars, and a precursor material for stable silica phases. During diagenesis, amorphous silica gradually and gradationally transforms to opal-CT, opal-C, and eventually quartz. Here we demonstrate the early-stage maturation of several million year old opal-A from deeply weathered Early Cretaceous and Ordovician sedimentary rocks of the Great Artesian Basin (central Australia). X-ray diffraction, scanning electron microscopy, and electron probe microanalyses show that the mineralogical maturation of the nanosphere material is decoupled from its chemical properties and begins significantly earlier than micromorphology suggests. Non-destructive and locally highly resolved X-ray microdiffraction (μ-XRD2) reveals an almost linear positive correlation between the main peak position (3.97 to 4.06 Å) and a new asymmetry parameter, AP. Heating experiments and calculated diffractograms indicate that nucleation and growth of tridymite-rich nanodomains induce systematic peak shifts and symmetry variations in diffraction patterns of morphologically juvenile opal-A. Our results show that the asymmetry parameter traces the early-stage maturation of amorphous silica, and that the mineralogical opal-A/CT stage extends to smaller d-spacings and larger FWHM values than previously suggested.
Role of Substrate on Quartz Cementation in Quartz Aggregates

NASA Astrophysics Data System (ADS)

Farver, J. R.; Winslow, D.; Onasch, C.

2010-12-01

Quartz cementation in quartz aggregates has been experimentally investigated. The starting material was disaggregated detrital quartz grains from the well-sorted, mature St. Peter Sandstone. The ‘as-is’ grains have patches of iron oxide coatings and some have euhedral overgrowths that contain iron oxide dust rims. In addition a set of experiments was run using grains that were cleaned by soaking in sodium hydrosulfite and sodium bisulfate solutions to remove exposed iron oxide coatings. Experimental charges consisted of amorphous silica powder (≈30 mg) to provide a source of silica for the quartz cement, AlCl3 powder (≈3 mg) to provide a tracer for Cathodoluminescence (CL) identification of cement formed during the experiment, 25 wt% NaCl brine solution (≈25 mg) to increase the silica solubility and to better mimic oil field brines, and the natural quartz grains (100-130 mg). The charges were weld-sealed in Au capsules and run in cold-seal pressure vessels at 250°C to 450°C at 150 MPa confining pressure for up to 8 weeks. After the experiments, the samples were vacuum impregnated with a low viscosity epoxy containing a blue dye. After curing, the sample charge was sawn in half along its long axis and one half was polished (to 1 micron diamond paste) for analysis. The nature and amount of quartz cement in the samples were determined by a combination of CL, light microscopy, and scanning electron microscopy. Photomosaics of the samples were created and the amount of cement, porosity, and average grain sizes were determined by point-counting. The cement formed during the experiment was easily recognized from the quartz grains (and previous overgrowths) by the difference in luminescence. The results indicate the amorphous silica powder provides a ready source for silica for quartz cementation due to its greater solubility than the quartz. The cementation rates are rapid (>14% cement formed in 2 weeks at 450°C and >7% in 8 weeks at 250°C). Compared to experiments using crushed fragments of synthetic quartz (Pepple, 2007), the amount of cement in these natural samples was greater. Cementation followed a common pattern in all samples. Microfractures, which formed during pressurization of the charges, healed very rapidly followed by overgrowths on the quartz grains. Cementation began closest to the amorphous silica, then progressed away. There was no measurable difference in the amount of quartz cement formed in samples of the as-is and cleaned St. Peter Sandstone indicating that iron played no role in the rate of cementation. Although the amount of cement formed increased with increasing temperature and duration of the experiments, the rate of cementation decreased dramatically in longer duration (8 weeks) experiments suggesting a change in the precipitation mechanism/rate. This apparent change in precipitation rate may reflect a decrease in available surfaces for nucleation and/or a decrease in growth rate as euhedral faces develop as proposed by Lander et al (2008).
Cutaneous exposure scenarios for engineered nanoparticles used in semiconductor fabrication: a preliminary investigation of workplace surface contamination.

PubMed

Shepard, Michele; Brenner, Sara

2014-01-01

Numerous studies are ongoing in the fields of nanotoxicology and exposure science; however, gaps remain in identifying and evaluating potential exposures from skin contact with engineered nanoparticles in occupational settings. The aim of this study was to identify potential cutaneous exposure scenarios at a workplace using engineered nanoparticles (alumina, ceria, amorphous silica) and evaluate the presence of these materials on workplace surfaces. Process review, workplace observations, and preliminary surface sampling were conducted using microvacuum and wipe sample collection methods and transmission electron microscopy with elemental analysis. Exposure scenarios were identified with potential for incidental contact. Nanoparticles of silica or silica and/or alumina agglomerates (or aggregates) were identified in surface samples from work areas where engineered nanoparticles were used or handled. Additional data are needed to evaluate occupational exposures from skin contact with engineered nanoparticles; precautionary measures should be used to minimize potential cutaneous exposures in the workplace.
Non-Reductive Strategies for U Sequestration: Natural Analogues and Practical Application

NASA Astrophysics Data System (ADS)

Maher, K.; Bethke, C. M.; Massey, M. S.

2011-12-01

A number of strategies have been proposed for the in situ remediation of U contaminated zones, including bioreduction, permeable reactive barriers, and incorporation into secondary phases such as phosphates. An alternative approach is to sequester U within amorphous Si phases such as opaline silica. We have investigated the isotopic and major element composition and structure of naturally occurring U-rich opaline silica in semi-arid soil environments across the western United States. These phases constitute a large natural reservoir of sequestered U. By combining these observations with geochemical considerations, we propose a remedial strategy for sequestering U in amorphous silica. The U-rich opal occurs as laminations, veins, and coatings on clasts in soils developed on a range of parent materials. U-rich opal deposits are also found as speleothems in caves, as silica-rich spring deposits, and as cavity fillings and hydrothermal veins in volcanic tuffs. Measurements of U, Th and Pb isotopes reveal the age of the opaline silica, demonstrating the long-term stability of U sequestration in open chemical environments. The isotopic data also suggest that opaline silica will retain the majority of the initial U over millions of years. U in naturally occurring opal generally ranges between 200 to 1000 ppm. In contrast, co-existing calcite contains less than 100 ppb U. From pore water chemistry, the distribution coefficient for U incorporation into opaline silica is approximately 20, whereas the coefficient for calcite is typically between 0.2 and 1. X-ray absorption spectroscopy investigations confirm that hexavalent U is incorporated in amorphous silica as the UO22+ ion. Coexisting Fe-oxides provide a further sink for sequestering UO22+ from the pore water. However, preliminary calculations suggest that incorporation of U into amorphous silica may be a dominant mechanism for isolating UO22+from groundwater over long time scales. Nature's mechanism for sequestering UO22+ from the environment might be profitably incorporated into groundwater remediation strategies. We consider a remedial strategy in which Na2SiO3 is amended into the subsurface. The silicate flood reacts with the surface acidity in the sediments to lower pH and precipitate amorphous silica. Hexavalent uranium is partitioned strongly into the silica, as well as complexed with the sediment surfaces.
Predicting catalyst-support interactions between metal nanoparticles and amorphous silica supports

NASA Astrophysics Data System (ADS)

Ewing, Christopher S.; Veser, Götz; McCarthy, Joseph J.; Lambrecht, Daniel S.; Johnson, J. Karl

2016-10-01

Metal-support interactions significantly affect the stability and activity of supported catalytic nanoparticles (NPs), yet there is no simple and reliable method for estimating NP-support interactions, especially for amorphous supports. We present an approach for rapid prediction of catalyst-support interactions between Pt NPs and amorphous silica supports for NPs of various sizes and shapes. We use density functional theory calculations of 13 atom Pt clusters on model amorphous silica supports to determine linear correlations relating catalyst properties to NP-support interactions. We show that these correlations can be combined with fast discrete element method simulations to predict adhesion energy and NP net charge for NPs of larger sizes and different shapes. Furthermore, we demonstrate that this approach can be successfully transferred to Pd, Au, Ni, and Fe NPs. This approach can be used to quickly screen stability and net charge transfer and leads to a better fundamental understanding of catalyst-support interactions.
Crystallization of biogenic hydrous amorphous silica

NASA Astrophysics Data System (ADS)

Kyono, A.; Yokooji, M.; Chiba, T.; Tamura, T.; Tuji, A.

2017-12-01

Diatom, Nitzschia cf. frustulum, collected from Lake Yogo, Siga prefecture, Japan was cultured in laboratory. Organic components of the diatom cell were removed by washing with acetone and sodium hypochlorite. The remaining frustules were studied by SEM-EDX, FTIR spectroscopy, and synchrotron X-ray diffraction. The results showed that the spindle-shaped morphology of diatom frustule was composed of hydrous amorphous silica. Pressure induced phase transformation of the diatom frustule was investigated by in situ Raman spectroscopic analysis. With exposure to 0.3 GPa at 100 oC, Raman band corresponding to quartz occurred at ν = 465 cm-1. In addition, Raman bands known as a characteristic Raman pattern of moganite was also observed at 501 cm-1. From the integral ratio of Raman bands, the moganite content in the probed area was estimated to be approximately 50 wt%. With the pressure and temperature effect, the initial morphology of diatom frustule was completely lost and totally changed to a characteristic spherical particle with a diameter of about 2 mm. With keeping the compression of 5.7 GPa at 100 oC, a Raman band assignable to coesite appeared at 538 cm-1. That is, with the compression and heating, the hydrous amorphous silica can be readily crystallized into quartz, moganite, and coesite. The first-principles calculations revealed that a disiloxane molecule stabilized in a trans configuration is twisted 60o and changed into the cis configuration with a close approach of water molecule. It is therefore a reasonable assumption that during crystallization of hydrous amorphous silica, the Si-O-Si bridging unit with the cis configuration would survive as a structural defect and then crystallized into moganite by keeping the geometry. This hypothesis is adaptable to the phase transformation from hydrous amorphous silica to coesite as well, because coesite has the four-membered rings and easily formed from the hydrous amorphous silica under high pressure and high temperature conditions.
A SIGNIFICANT AMOUNT OF CRYSTALLINE SILICA IN RETURNED COMETARY SAMPLES: BRIDGING THE GAP BETWEEN ASTROPHYSICAL AND METEORITICAL OBSERVATIONS

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

Roskosz, Mathieu; Leroux, Hugues

2015-03-01

Crystalline silica (SiO{sub 2}) is recurrently identified at the percent level in the infrared spectra of protoplanetary disks. By contrast, reports of crystalline silica in primitive meteorites are very unusual. This dichotomy illustrates the typical gap existing between astrophysical observations and meteoritical records of the first solids formed around young stars. The cometary samples returned by the Stardust mission in 2006 offer an opportunity to have a closer look at a silicate dust that experienced a very limited reprocessing since the accretion of the dust. Here, we provide the first extended study of silica materials in a large range ofmore » Stardust samples. We show that cristobalite is the dominant form. It was detected in 5 out of 25 samples. Crystalline silica is thus a common minor phase in Stardust samples. Furthermore, olivine is generally associated with this cristobalite, which put constraints on possible formation mechanisms. A low-temperature subsolidus solid–solid transformation of an amorphous precursor is most likely. This crystallization route favors the formation of olivine (at the expense of pyroxenes), and crystalline silica is the natural byproduct of this transformation. Conversely, direct condensation and partial melting are not expected to produce the observed mineral assemblages. Silica is preserved in cometary materials because they were less affected by thermal and aqueous alterations than their chondritic counterparts. The common occurrence of crystalline silica therefore makes the cometary material an important bridge between the IR-based mineralogy of distant protoplanetary disks and the mineralogy of the early solar system.« less
Silicic volcanism on Mars evidenced by tridymite in high-SiO2 sedimentary rock at Gale crater

NASA Astrophysics Data System (ADS)

Morris, Richard V.; Vaniman, David T.; Blake, David F.; Gellert, Ralf; Chipera, Steve J.; Rampe, Elizabeth B.; Ming, Douglas W.; Morrison, Shaunna M.; Downs, Robert T.; Treiman, Allan H.; Yen, Albert S.; Grotzinger, John P.; Achilles, Cherie N.; Bristow, Thomas F.; Crisp, Joy A.; Des Marais, David J.; Farmer, Jack D.; Fendrich, Kim V.; Frydenvang, Jens; Graff, Trevor G.; Morookian, John-Michael; Stolper, Edward M.; Schwenzer, Susanne P.

2016-06-01

Tridymite, a low-pressure, high-temperature (>870 °C) SiO2 polymorph, was detected in a drill sample of laminated mudstone (Buckskin) at Marias Pass in Gale crater, Mars, by the Chemistry and Mineralogy X-ray diffraction instrument onboard the Mars Science Laboratory rover Curiosity. The tridymitic mudstone has ˜40 wt.% crystalline and ˜60 wt.% X-ray amorphous material and a bulk composition with ˜74 wt.% SiO2 (Alpha Particle X-Ray Spectrometer analysis). Plagioclase (˜17 wt.% of bulk sample), tridymite (˜14 wt.%), sanidine (˜3 wt.%), cation-deficient magnetite (˜3 wt.%), cristobalite (˜2 wt.%), and anhydrite (˜1 wt.%) are the mudstone crystalline minerals. Amorphous material is silica-rich (˜39 wt.% opal-A and/or high-SiO2 glass and opal-CT), volatile-bearing (16 wt.% mixed cation sulfates, phosphates, and chlorides-perchlorates-chlorates), and has minor TiO2 and Fe2O3T oxides (˜5 wt.%). Rietveld refinement yielded a monoclinic structural model for a well-crystalline tridymite, consistent with high formation temperatures. Terrestrial tridymite is commonly associated with silicic volcanism, and detritus from such volcanism in a “Lake Gale” catchment environment can account for Buckskin's tridymite, cristobalite, feldspar, and any residual high-SiO2 glass. These cogenetic detrital phases are possibly sourced from the Gale crater wall/rim/central peak. Opaline silica could form during diagenesis from high-SiO2 glass, as amorphous precipitated silica, or as a residue of acidic leaching in the sediment source region or at Marias Pass. The amorphous mixed-cation salts and oxides and possibly the crystalline magnetite (otherwise detrital) are primary precipitates and/or their diagenesis products derived from multiple infiltrations of aqueous solutions having variable compositions, temperatures, and acidities. Anhydrite is post lithification fracture/vein fill.
Silicic volcanism on Mars evidenced by tridymite in high-SiO2 sedimentary rock at Gale crater

PubMed Central

Morris, Richard V.; Vaniman, David T.; Blake, David F.; Gellert, Ralf; Chipera, Steve J.; Rampe, Elizabeth B.; Ming, Douglas W.; Morrison, Shaunna M.; Downs, Robert T.; Treiman, Allan H.; Yen, Albert S.; Grotzinger, John P.; Achilles, Cherie N.; Bristow, Thomas F.; Crisp, Joy A.; Des Marais, David J.; Farmer, Jack D.; Fendrich, Kim V.; Graff, Trevor G.; Morookian, John-Michael; Stolper, Edward M.; Schwenzer, Susanne P.

2016-01-01

Tridymite, a low-pressure, high-temperature (>870 °C) SiO2 polymorph, was detected in a drill sample of laminated mudstone (Buckskin) at Marias Pass in Gale crater, Mars, by the Chemistry and Mineralogy X-ray diffraction instrument onboard the Mars Science Laboratory rover Curiosity. The tridymitic mudstone has ∼40 wt.% crystalline and ∼60 wt.% X-ray amorphous material and a bulk composition with ∼74 wt.% SiO2 (Alpha Particle X-Ray Spectrometer analysis). Plagioclase (∼17 wt.% of bulk sample), tridymite (∼14 wt.%), sanidine (∼3 wt.%), cation-deficient magnetite (∼3 wt.%), cristobalite (∼2 wt.%), and anhydrite (∼1 wt.%) are the mudstone crystalline minerals. Amorphous material is silica-rich (∼39 wt.% opal-A and/or high-SiO2 glass and opal-CT), volatile-bearing (16 wt.% mixed cation sulfates, phosphates, and chlorides−perchlorates−chlorates), and has minor TiO2 and Fe2O3T oxides (∼5 wt.%). Rietveld refinement yielded a monoclinic structural model for a well-crystalline tridymite, consistent with high formation temperatures. Terrestrial tridymite is commonly associated with silicic volcanism, and detritus from such volcanism in a “Lake Gale” catchment environment can account for Buckskin’s tridymite, cristobalite, feldspar, and any residual high-SiO2 glass. These cogenetic detrital phases are possibly sourced from the Gale crater wall/rim/central peak. Opaline silica could form during diagenesis from high-SiO2 glass, as amorphous precipitated silica, or as a residue of acidic leaching in the sediment source region or at Marias Pass. The amorphous mixed-cation salts and oxides and possibly the crystalline magnetite (otherwise detrital) are primary precipitates and/or their diagenesis products derived from multiple infiltrations of aqueous solutions having variable compositions, temperatures, and acidities. Anhydrite is post lithification fracture/vein fill. PMID:27298370
Dielectric breakdown in silica-amorphous polymer nanocomposite films: the role of the polymer matrix.

PubMed

Grabowski, Christopher A; Fillery, Scott P; Westing, Nicholas M; Chi, Changzai; Meth, Jeffrey S; Durstock, Michael F; Vaia, Richard A

2013-06-26

The ultimate energy storage performance of an electrostatic capacitor is determined by the dielectric characteristics of the material separating its conductive electrodes. Polymers are commonly employed due to their processability and high breakdown strength; however, demands for higher energy storage have encouraged investigations of ceramic-polymer composites. Maintaining dielectric strength, and thus minimizing flaw size and heterogeneities, has focused development toward nanocomposite (NC) films; but results lack consistency, potentially due to variations in polymer purity, nanoparticle surface treatments, nanoparticle size, and film morphology. To experimentally establish the dominant factors in broad structure-performance relationships, we compare the dielectric properties for four high-purity amorphous polymer films (polymethyl methacrylate, polystyrene, polyimide, and poly-4-vinylpyridine) incorporating uniformly dispersed silica colloids (up to 45% v/v). Factors known to contribute to premature breakdown-field exclusion and agglomeration-have been mitigated in this experiment to focus on what impact the polymer and polymer-nanoparticle interactions have on breakdown. Our findings indicate that adding colloidal silica to higher breakdown strength amorphous polymers (polymethyl methacrylate and polyimide) causes a reduction in dielectric strength as compared to the neat polymer. Alternatively, low breakdown strength amorphous polymers (poly-4-vinylpyridine and especially polystyrene) with comparable silica dispersion show similar or even improved breakdown strength for 7.5-15% v/v silica. At ∼15% v/v or greater silica content, all the polymer NC films exhibit breakdown at similar electric fields, implying that at these loadings failure becomes independent of polymer matrix and is dominated by silica.
Porous, S-bearing silica in metal-sulfide nodules and in the interchondrule clastic matrix in two EH3 chondrites

NASA Astrophysics Data System (ADS)

Lehner, S. W.; Németh, P.; Petaev, M. I.; Buseck, P. R.

2017-11-01

Two new occurrences of porous, S-bearing, amorphous silica are described within metal-sulfide nodules (MSN) and as interchondrule patches in EH3 chondrites SAH 97072 and ALH 84170. This porous amorphous material, which was first reported from sulfide-bearing chondrules, consists of sinewy SiO2-rich areas containing S with minor Na or Ca as well as Fe, Mg, and Al. Some pores contain minerals including pyrite, pyrrhotite, and anhydrite. Most pores appear vacant or contain unidentified material that is unstable under analytical conditions. Niningerite, olivine, enstatite, albite, and kumdykolite occur enclosed within porous silica patches. Porous silica is commonly interfingered with cristobalite suggesting its amorphous structure resulted from high-temperature quenching. We interpret the S-bearing porous silica to be a product of silicate sulfidation, and the Na, Ca, Fe, Mg, and Al detectable within this material are chemical residues of sulfidized silicates and metal. The occurrence of porous silica in the cores of MSN, which are considered to be pre-accretionary objects, suggests the sulfidizing conditions occurred prior to final parent-body solidification. Ubiquitous S-bearing porous silica among sulfide-bearing chondrules, MSN, and in the interchondrule clastic matrix, suggests that similar sulfidizing conditions affected all the constituents of these EH3 chondrites.
Interface-coupled dissolution-precipitation processes allow a photonic crystal to replace an ionic crystal along lattice planes

NASA Astrophysics Data System (ADS)

Liesegang, Moritz; Milke, Ralf

2015-04-01

Nanocolloidal amorphous silica (SiO2×nH2O) is a major component of environmental aqueous solutions and surface coatings on rocks or mineral grains. Detailed knowledge of amorphous silica formation is indispensable for a better understanding of silicate rock alteration and diagenetic processes. We analyzed a wide range of samples from the Australian precious opal fields in South Australia and Queensland using petrographic microscopy, XRPD, SEM, and EPMA to characterize opaline silica, the mineral assemblage, and the host rock. Over the past 90 Ma the Lower Cretaceous lithologies of central Australia have undergone a weathering regime ranging from sub-tropical to arid, in which pH fluctuated from alkaline to acidic. The prolonged chemical alteration of sedimentary rocks derived from andesitic volcaniclastics and organic matter liberated large volumes of silica into solution, eventually leading to precipitation of nanocolloidal amorphous silica and formation of opal-A. A regular arrangement of close-packed uniform (monodisperse) spheres permits diffraction of white light and gives rise to the famous play-of-color. The opals in this study consist of silica spheres with an average diameter of 100-320 nm and often show a prominent core-shell structure. Two groups are separated by their relative standard deviation (RSD): monodisperse spheres (RSD<6%) and polydisperse spheres (RDS>10%). Monodisperse and polydisperse spheres are separated by their Na/K ratio, restricting the appearance of monodisperse spheres to values <1.2 and polydisperse spheres to values >3.0. We suggest that the Na/K ratio represents significant differences in the overall solution characteristics. The associated minerals (e.g., alunite, gypsum, kaolinite, K feldspar) indicate large variations of fluid composition and pH. Probably, uniform spheres grew at acidic pH, with repulsive forces large enough to arrange them in an ordered array prior to the evaporation of interstitial fluids. The investigation of fossil shells replaced by opal-A reveals clues for the understanding of structural and chemical reorganization mechanisms behind silica pseudomorphism. Fundamental knowledge about the highly selective replacement process is absent so far, impeding an adequate interpretation of the observations. The replacement of calcitic shells by amorphous silica spheres (~300 nm in size) is a unique example for the transformation of an ionic to a photonic crystal accompanied by a large size contrast of ions and spheres, respectively, but preserving lattice planes. The observed replication of polysynthetic twinning and cleavage planes of calcite by opal-A spheres indicates that silicification occurs via dissolution of shell material and immediate precipitation of amorphous silica. This follows the interface-coupled dissolution-precipitation mechanism model (Putnis and Putnis, 2007), but requires some modification to allow for open space necessary to form spheres in the 100s-nm size range with a core-shell structure. While sphere growth by a gravitational ordering process is implausible, we assume that the ordered array of monodisperse spheres forms via layer-by-layer deposition. References: Putnis A. and Putnis C.V. (2007), J. Solid State Chem., 180, 1783-1786
Processing pathway dependence of amorphous silica nanoparticle toxicity - colloidal versus pyrolytic

PubMed Central

Zhang, Haiyuan; Dunphy, Darren R.; Jiang, Xingmao; Meng, Huan; Sun, Bingbing; Tarn, Derrick; Xue, Min; Wang, Xiang; Lin, Sijie; Ji, Zhaoxia; Li, Ruibin; Garcia, Fred L.; Yang, Jing; Kirk, Martin L.; Xia, Tian; Zink, Jeffrey I; Nel, Andre; Brinker, C. Jeffrey

2012-01-01

We have developed structure/toxicity relationships for amorphous silica nanoparticles (NPs) synthesized through low temperature, colloidal (e.g. Stöber silica) or high temperature pyrolysis (e.g. fumed silica) routes. Through combined spectroscopic and physical analyses, we have determined the state of aggregation, hydroxyl concentration, relative proportion of strained and unstrained siloxane rings, and potential to generate hydroxyl radicals for Stöber and fumed silica NPs with comparable primary particle sizes (16-nm in diameter). Based on erythrocyte hemolytic assays and assessment of the viability and ATP levels in epithelial and macrophage cells, we discovered for fumed silica an important toxicity relationship to post-synthesis thermal annealing or environmental exposure, whereas colloidal silicas were essentially non-toxic under identical treatment conditions. Specifically, we find for fumed silica a positive correlation of toxicity with hydroxyl concentration and its potential to generate reactive oxygen species (ROS) and cause red blood cell hemolysis. We propose fumed silica toxicity stems from its intrinsic population of strained three-membered rings (3MRs) along with its chain-like aggregation and hydroxyl content. Hydrogen-bonding and electrostatic interactions of the silanol surfaces of fumed silica aggregates with the extracellular plasma membrane cause membrane perturbations sensed by the Nalp3 inflammasome, whose subsequent activation leads to secretion of the cytokine IL-1β. Hydroxyl radicals generated by the strained 3MRs in fumed silica but largely absent in colloidal silicas may contribute to the inflammasome activation. Formation of colloidal silica into aggregates mimicking those of fumed silica had no effect on cell viability or hemolysis. This study emphasizes that not all amorphous silica is created equal and that the unusual toxicity of fumed silica compared to colloidal silica derives from its framework and surface chemistry along with its fused chain-like morphology established by high temperature synthesis (>1300°C) and rapid thermal quenching. PMID:22924492
Adsorption onto Mesoporous Silica Using Supercritical Fluid Technology Improves Dissolution Rate of Carbamazepine-a Poorly Soluble Compound.

PubMed

Gandhi, Aditya V; Thipsay, Priyanka; Kirthivasan, Bharat; Squillante, Emilio

2017-11-01

The purpose of this research was to design and characterize an immediate-release formulation of carbamazepine (CBZ), a poorly soluble anti-epileptic drug, using a porous silica carrier. Carbon dioxide in its supercritical state (2000 psi, 30-35°C) was used as an anti-solvent to precipitate CBZ onto two particle size variants of silica. Adsorption isotherms were used as a pre-formulation strategy to select optimum ratios of silica and CBZ. The obtained drug-silica formulations were characterized by dissolution studies, differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), and scanning electron microscopy (SEM). This formulation strategy resulted in a 2.4-fold improvement in dissolution rate when compared to pure drug after 30 min of dissolution testing. PXRD and DSC confirmed the amorphous nature of CBZ in the formulations as well as the differences in polymorphic forms of commercial and supercritical fluid-processed CBZ. Additionally, solid-state NMR spectroscopy showed that the spin-lattice relaxation time for bulk drug (without silica) was ∼7.5 times greater than that for silica-confined CBZ, implying that when CBZ was adsorbed onto mesoporous silica, it is structurally disordered and had higher structural mobility, a characteristic of amorphous solids. The mesoporous silica matrix prevented CBZ crystal growth by imposing spatial constraint on CBZ nuclei and hence resulted in faster dissolution compared to bulk solid drug. Adsorption onto mesoporous silica using supercritical fluid technology may be used as a novel formulation strategy for amorphization of poorly soluble compounds, in turn improving their dissolution rate.
The composition of secondary amorphous phases under different environmental conditions

NASA Astrophysics Data System (ADS)

Smith, R.; Rampe, E. B.; Horgan, B. H. N.; Dehouck, E.; Morris, R. V.

2017-12-01

X-ray diffraction (XRD) patterns measured by the CheMin instrument on the Mars Science Laboratory Curiosity rover demonstrate that amorphous phases are major components ( 15-60 wt%) of all rock and soil samples in Gale Crater. The nature of these phases is not well understood and could be any combination of primary (e.g., glass) and secondary (e.g., silica, ferrihydrite) phases. Secondary amorphous phases are frequently found as weathering products in soils on Earth, but these materials remain poorly characterized. Here we study a diverse suite of terrestrial samples including: sediments from recently de-glaciated volcanoes (Oregon), modern volcanic soils (Hawaii), and volcanic paleosols (Oregon) in order to determine how formation environment, climate, and diagenesis affect the abundance and composition of amorphous phases. We combine bulk XRD mineralogy with bulk chemical compositions (XRF) to calculate the abundance and bulk composition of the amorphous materials in our samples. We then utilize scanning transmission electron microscopy (STEM) and energy dispersive x-ray spectroscopy (EDS) to study the composition of individual amorphous phases at the micrometer scale. XRD analyses of 8 samples thus far indicate that the abundance of amorphous phases are: modern soils (20-80 %) > paleosols (15-40 %) > glacial samples (15-30 %). Initial calculations suggest that the amorphous components consist primarily of SiO2, Al2O3, TiO2, FeO and Fe2O3, with minor amounts of other oxides (e.g., MgO, CaO, Na2O). Compared to their respective crystalline counterparts, calculations indicate bulk amorphous components enriched in SiO2 for the glacial sample, and depleted in SiO2 for the modern soil and paleosol samples. STEM analyses reveal that the amorphous components consist of a number of different phases. Of the two samples analyzed using STEM thus far, the secondary amorphous phases have compositions with varying ratios of SiO2, Al2O3, TiO2, and Fe-oxides, consistent with mass balance calculation results, but inconsistent with well-known amorphous phase compositions (e.g., allophane, ferrihydrite). These results show that a number of secondary amorphous phases can form within a single soil environment. Continued analysis can help determine whether compositional trends can be linked to environmental factors.
A new parameter-free soft-core potential for silica and its application to simulation of silica anomalies

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

Izvekov, Sergei, E-mail: sergiy.izvyekov.civ@mail.mil; Rice, Betsy M.

2015-12-28

A core-softening of the effective interaction between oxygen atoms in water and silica systems and its role in developing anomalous thermodynamic, transport, and structural properties have been extensively debated. For silica, the progress with addressing these issues has been hampered by a lack of effective interaction models with explicit core-softening. In this work, we present an extension of a two-body soft-core interatomic force field for silica recently reported by us [S. Izvekov and B. M. Rice, J. Chem. Phys. 136(13), 134508 (2012)] to include three-body forces. Similar to two-body interaction terms, the three-body terms are derived using parameter-free force-matching ofmore » the interactions from ab initio MD simulations of liquid silica. The derived shape of the O–Si–O three-body potential term affirms the existence of repulsion softening between oxygen atoms at short separations. The new model shows a good performance in simulating liquid, amorphous, and crystalline silica. By comparing the soft-core model and a similar model with the soft-core suppressed, we demonstrate that the topology reorganization within the local tetrahedral network and the O–O core-softening are two competitive mechanisms responsible for anomalous thermodynamic and kinetic behaviors observed in liquid and amorphous silica. The studied anomalies include the temperature of density maximum locus and anomalous diffusivity in liquid silica, and irreversible densification of amorphous silica. We show that the O–O core-softened interaction enhances the observed anomalies primarily through two mechanisms: facilitating the defect driven structural rearrangements of the silica tetrahedral network and modifying the tetrahedral ordering induced interactions toward multiple characteristic scales, the feature which underlies the thermodynamic anomalies.« less

Size distributions of coastal ocean suspended particulate inorganic matter: Amorphous silica and clay minerals and their dynamics

NASA Astrophysics Data System (ADS)

Zhang, Xiaodong; Stavn, Robert H.; Falster, Alexander U.; Rick, Johannes J.; Gray, Deric; Gould, Richard W.

2017-04-01

Particulate inorganic matter (PIM) is a key component in estuarine and coastal systems and plays a critical role in trace metal cycling. Better understanding of coastal dynamics and biogeochemistry requires improved quantification of PIM in terms of its concentration, size distribution, and mineral species composition. The angular pattern of light scattering contains detailed information about the size and composition of particles. These volume scattering functions (VSFs) were measured in Mobile Bay, Alabama, USA, a dynamic, PIM dominated coastal environment. From measured VSFs, we determined through inversion the particle size distributions (PSDs) of major components of PIM, amorphous silica and clay minerals. An innovation here is the extension of our reported PSDs significantly into the submicron range. The PSDs of autochthonous amorphous silica exhibit two unique features: a peak centered at about 0.8 μm between 0.2 and 4 μm and a very broad shoulder essentially extending from 4 μm to >100 μm. With an active and steady particle source from blooming diatoms, the shapes of amorphous silica PSDs for sizes <10 μm varied little across the study area, but showed more particles of sizes >10 μm inside the bay, likely due to wind-induced resuspension of larger frustules that have settled. Compared to autochthonous amorphous silica, the allochthonous clay minerals are denser and exhibit relatively narrower PSDs with peaks located between 1 and 4 μm. Preferential settling of larger mineral particles as well as the smaller but denser illite component further narrowed the size distributions of clay minerals as they were being transported outside the bay. The derived PSDs also indicated a very dynamic situation in Mobile Bay when a cold weather front passed through during the experiment. With northerly winds of speeds up to 15 m s-1, both amorphous silica and clay minerals showed a dramatic increase in concentration and broadening in size distribution outside the exit of the barrier islands, indicative of wind-induced resuspension and subsequent advection of particles out of Mobile Bay. While collectively recognized as the PIM, amorphous silica and clay minerals, as shown in this study, possess very different size distributions. Considering how differences in PSDs and the associated particle areas will effect differences in sorption/desorption properties of these components, the results also demonstrate the potential of applying VSF-inversion in studying biogeochemistry in the estuarine-coastal ocean system.
Chemical interactions of aluminum with aqueous silica at 25 degrees Celsius

USGS Publications Warehouse

Hem, John David; Roberson, C.E.; Lind, Carol J.; Polxer, W.L.

1973-01-01

Solutions containing from 10 -5 to 10 -2 moles per liter of aluminum and dissolved silica in various ratios were aged at pH levels between 4 and 10 at 25?C. A colloidal amorphous product having the composition of halloysite was produced in most solutions. It had a consistent and reversible equilibrium solubility equivalent to a standard free energy of formation of -8974 ? 1.0 kcal per mole for the formula A12Si2O5(OH)4. Some aging times were longer than 4 years, but most solutions gave consistent solubilities after only a few months of aging. Where silica concentrations were below about 10 -4 molar, microcrystalline gibbsite was formed below pH 6.0 and crystalline bayerite above pH 7.0, but only after much longer aging than was required for crystallization in silica-free solutions. Electron micrographs and diffraction patterns of the synthesized material indicate some crystallinity in the aluminosilicate, but no X-ray diffraction patterns could be obtained even in the material aged 4 years. Solubility relationships for solutions containing fluoride as well as silica and aluminum are explainable by using cryolite stabilities determined in previous work. Aluminum contents of 51 samples of water analyzed for other purposes are in reasonable agreement with the assumption of equilibrium with amorphous clay mineral species similar to the material synthesized in this work. Solubility calculations are summarized graphically for solutions of ionic strength of 0.01 and 0.10.
Production and Application of Olivine Nano-Silica in Concrete

NASA Astrophysics Data System (ADS)

Mardiana, Oesman; Haryadi

2017-05-01

The aim of this research was to produce nano silica by synthesis of nano silica through extraction and dissolution of ground olivine rock, and applied the nano silica in the design concrete mix. The producing process of amorphous silica used sulfuric acid as the dissolution reagent. The separation of ground olivine rock occurred when the rock was heated in a batch reactor containing sulfuric acid. The results showed that the optimum mole ratio of olivine- acid was 1: 8 wherein the weight ratio of the highest nano silica generated. The heating temperature and acid concentration influenced the mass of silica produced, that was at temperature of 90 °C and 3 M acid giving the highest yield of 44.90%. Characterization using Fourier Transform Infrared (FTIR ) concluded that amorphous silica at a wavenumber of 1089 cm-1 indicated the presence of siloxane, Si-O-Si, stretching bond. Characterization using Scanning Electron Microscope - Energy Dispersive Spectroscopy (SEM-EDS) showed the surface and the size of the silica particles. The average size of silica particles was between 1-10 μm due to the rapid aggregation of the growing particles of nano silica into microparticles, caused of the pH control was not fully achieved.
Cutaneous exposure scenarios for engineered nanoparticles used in semiconductor fabrication: a preliminary investigation of workplace surface contamination

PubMed Central

Shepard, Michele; Brenner, Sara

2014-01-01

Background: Numerous studies are ongoing in the fields of nanotoxicology and exposure science; however, gaps remain in identifying and evaluating potential exposures from skin contact with engineered nanoparticles in occupational settings. Objectives: The aim of this study was to identify potential cutaneous exposure scenarios at a workplace using engineered nanoparticles (alumina, ceria, amorphous silica) and evaluate the presence of these materials on workplace surfaces. Methods: Process review, workplace observations, and preliminary surface sampling were conducted using microvacuum and wipe sample collection methods and transmission electron microscopy with elemental analysis. Results: Exposure scenarios were identified with potential for incidental contact. Nanoparticles of silica or silica and/or alumina agglomerates (or aggregates) were identified in surface samples from work areas where engineered nanoparticles were used or handled. Conclusions: Additional data are needed to evaluate occupational exposures from skin contact with engineered nanoparticles; precautionary measures should be used to minimize potential cutaneous exposures in the workplace. PMID:25000112
Evolution of Morphology and Crystallinity of Silica Minerals Under Hydrothermal Conditions

NASA Astrophysics Data System (ADS)

Isobe, H.

2011-12-01

Silica minerals are quite common mineral species in surface environment of the terrestrial planets. They are good indicator of terrestrial processes including hydrothermal alteration, diagenesis and soil formation. Hydrothermal quartz, metastable low temperature cristobalite and amorphous silica show characteristic morphology and crystallinity depending on their formation processes and kinetics under wide range of temperature, pressure, acidity and thermal history. In this study, silica minerals produced by acidic hydrothermal alteration related to volcanic activities and hydrothermal crystallization experiments from diatom sediment are examined with crystallographic analysis and morphologic observations. Low temperature form of cistobalite is a metastable phase and a common alteration product occured in highly acidic hydrothermal environment around fumaroles in geothermal / volcanic areas. XRD analysis revealed that the alteration degree of whole rock is represented by abundance of cristobalite. Detailed powder XRD analysis show that the primary diffraction peak of cristobalite composed with two or three phases with different d-spacing and FWHM by peak profile fitting analysis. Shorter d-spacing and narrower FWHM cristobalite crystallize from precursor materials with less-crystallized, longer d-spacing and wider FWHM cristobalite. Textures of hydrothermal cristobalite in altered rock shows remnant of porphylitic texture of the host rock, pyroxene-amphibole andesite. Diatom has amorphous silica shell and makes diatomite sediment. Diatomite found in less diagenetic Quarternary formation keeps amorphous silica diatom shells. Hydrothermal alteration experiments of amorphous silica diatomite sediment are carried out from 300 °C to 550 °C. Mineral composition of run products shows crystallization of cristobalite and quartz progress depending on temperature and run durations. Initial crystallization product, cristobalite grains occur as characteristic lepispheres and granules with various surface structures. At the very initial stage of cristobalite crystallization within 2 days run duration, cristobalite shows lepispheres a few micron meters in diameter with irregular, submicron scale ridges and grooves on the surface. With the run duration up to 7 days, lepispheres change to granules with smooth surface remaining a few micron meters in diameter. Crystallinity of cristobalite lepispheres and granules corresponds to opal-CT. Euhedral quartz crystals grow with dissolution of cristobalite grains. Growth rate of cristobalite and quartz is controlled by crystallization kinetics with induction period strongly depending on temperature. Induction period of cristobalite crystallization from amorphous silica may exceed several million years at temperature below 100 °C. Crystallinity, morphology and growth rate of silica minerals occurred in various terrestrial and planetary processes are controlled by temperature and acidity of hydrothermal fluid and nucleation and growth kinetics of silica minerals.
Synchrotron WAXS and XANES studies of silica (SiO2) powders synthesized from Indonesian natural sands

NASA Astrophysics Data System (ADS)

Muchlis, Khairanissa; Aini Fauziyah, Nur; Soontaranon, Siriwat; Limpirat, Wanwisa; Pratapa, Suminar

2017-01-01

In this study, we have investigated polymorphic silica (SiO2) powders using, Wide Angle X-ray Scattering (WAXS) and X-Ray Absorption Near Edge Spectroscopy (XANES), laboratory X-Ray Diffraction (XRD) instruments. The WAXS and XANES spectra were collected using synchrotron radiation at Synchrotron Light Research Institute (SLRI), Nakhon Ratchasima, Thailand. The silica powders were obtained by processing silica sand from Tanah Laut, South Kalimantan, Indonesia. Purification process of silica sand was done by magnetic separation and immersion with HCl. The purification step was needed to reduce impurity or undesirable non Si elements. Three polymorphs of silica were produced, i.e. amorphous phase (A), quartz (B), and cristobalite (C). WAXS profile for each phase was presented in terms of intensity vs. 2θ prior to analyses. Both XRD (λCuKα=1.54056 Å) and WAXS (λ=1.09 Å) patttern show that (1) A sample contains no crystallites, (2) B sample is monophasic, contains only quartz, and (3) C sample contains cristobalite and trydimite. XRD quantitative analysis using Rietica gave 98,8 wt% cristobalite, while the associated WAXS data provided 98.7 wt% cristobalite. Si K-edge XANES spectra were measured at energy range 1840 to 1920 eV. Qualitatively, the pre-edge and edge features for all phases are similar, but their main peaks in the post-edge region are different.
Laser-driven formation of a high-pressure phase in amorphous silica.

PubMed

Salleo, Alberto; Taylor, Seth T; Martin, Michael C; Panero, Wendy R; Jeanloz, Raymond; Sands, Timothy; Génin, François Y

2003-12-01

Because of its simple composition, vast availability in pure form and ease of processing, vitreous silica is often used as a model to study the physics of amorphous solids. Research in amorphous silica is also motivated by its ubiquity in modern technology, a prominent example being as bulk material in transmissive and diffractive optics for high-power laser applications such as inertial confinement fusion (ICF). In these applications, stability under high-fluence laser irradiation is a key requirement, with optical breakdown occurring when the fluence of the beam is higher than the laser-induced damage threshold (LIDT) of the material. The optical strength of polished fused silica transmissive optics is limited by their surface LIDT. Surface optical breakdown is accompanied by densification, formation of point defects, cratering, material ejection, melting and cracking. Through a combination of electron diffraction and infrared reflectance measurements we show here that synthetic vitreous silica transforms partially into a defective form of the high-pressure stishovite phase under high-intensity (GW cm(-2)) laser irradiation. This phase transformation offers one suitable mechanism by which laser-induced damage grows catastrophically once initiated, thereby dramatically shortening the service lifetime of optics used for high-power photonics.
Atomically designed precursors in optical fiber amplifiers: The thermal stability of the heterobimetallic ErAl3(OPri)12 in a solution-coated silica soot

NASA Astrophysics Data System (ADS)

Engholm, M.; Lashgari, K.; Edvardsson, S.; Westin, G.; Norin, L.

2005-06-01

The thermal stability of the bimetallic alkoxide ErAl3(OPri)12 doped in an unsintered silica (soot) has been investigated. Samples have been heated to different temperatures (up to 1500°C and analyzed by using ultraviolet-visible-near infrared absorption spectroscopy, infrared spectroscopy, scanning electron microscopy, energy dispersive spectroscopy, thermal gravimetric analysis, and powder x-ray diffraction. It is seen that the doped samples heated up to 1000°C show broad glasslike absorption spectra, indicating an amorphous structure, while the high-temperature sample shows an ordered crystallinelike structure with sharp characteristic absorption peaks. X-ray diffraction measurements indicate the formation of an ordered structure at temperatures of 1500°C, revealing a crystal phase of silica and phases of erbium and aluminosilicate. A comparison is also made with a sample doped with aqueous ErCl3 and Al(NO3)3. It is concluded that the local structure of the ErAl3 precursor is not preserved at temperatures above 1000°C. Alternative doping procedures are discussed.
Morphological and textural characterization of functionalized particulate silica xerogels

NASA Astrophysics Data System (ADS)

de Miranda, Lazaro A.; Mohallem, Nelcy D. S.; de Magalhães, Welington F.

2006-03-01

The functionalization of xerogels for use in chromatography and catalysis was carried out by solubilization of amorphous silica using a soxhlet extractor. Xerogels were prepared by sol-gel method using tetraethoxysilane, TEOS, ethanol, and water in a 1/3/10 molar ratio with HCl and HF as catalysts. The samples were prepared in monolithic form and dried at 70 °C and 550 °C for 1 h each. After functionalization, changes in textural and morphological characteristics of xerogels were investigated by means of nitrogen gas adsorption, positron annihilation lifetime spectroscopy (PALS), and scanning electron microscopy (SEM). As the analysis methods are based on different physical principles, the results are complementary, leading to a good knowledge of the texture of the samples studied.
Renewable Decyl-alcohol Templated Synthesis of Si-Cu Core-Shell Nanocomposite

NASA Astrophysics Data System (ADS)

Salim, M. A.; >H Misran, S. Z.; Shah, N. N. H.; Razak, N. A. A.; >A Manap,
2013-06-01

Monodispersed silica spheres with particles size of ca. 450 nm were successfully synthesized using a modified Stöber method. The synthesized monodispersed silica spheres were successfully coated with copper using modified sol-gel method employing nonsurfactant surface modifiers and catalyst. A renewable palm oil based decyl-alcohol (C10) as nonsurfactant surface modifiers and catalyst were used to modify the silica surfaces prior to coating with copper. The X-ray diffraction patterns of Si-Cu core-shell exhibited a broad peak corresponding to amorphous silica networks and monoclinic CuO phase. It was found that samples modified in the presence of 1 ml catalyst exhibited homogeneous deposition. The surface area of core materials (SiO2) was at ca. 7.04 m2/g and Si-Cu core-shell was at ca. 8.21 m2/g. The band gap of samples prepared with and without catalyst was calculated to be ca. 2.45 eV and ca. 3.90 eV respectively based on the UV-vis absorption spectrum of the product.
Predicting the switchable screw sense in fluorene-based polymers.

PubMed

Pietropaolo, Adriana; Wang, Yue; Nakano, Tamaki

2015-02-23

A chirality-switching free-energy landscape was reconstructed on a 43-mer of poly(9,9-dioctylfluoren-2,7-diyl) (PDOF). The simulations were conducted on amorphous silica surface as well as in the vacuum phase for a single chain or for a group of sixteen chains. The achiral-to-chiral transition occurs only on amorphous silica (activation free-energy 35 kcal mol(-1) ), where the enantiomeric (homochiral) basins are detected. This was supported by the experiments where effective chirality induction to PDOF using circularly polarized light (CPL) was attained only for a film deposited on a quartz glass and not for a solution or a suspension. These results indicate that interactions of PDOF with amorphous silica play a crucial role in chirality switching. Importance of chain assembling was also indicated. Theoretical ECD spectra of the enantiomeric basins containing a 51 helix reproduce the experimental spectra. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Nano-scale observations of interface between lichen and basaltic rock: Pseudomorphic growth of amorphous silica on augite

NASA Astrophysics Data System (ADS)

Tamura, T.; Kyono, A.; Kebukawa, Y.; Takagi, S.

2017-12-01

Recently, lichens as the earliest colonizers of terrestrial habitats are recognized to accelerate the mineral degradation at the interface between lichens and surface rocks. Much interest has been therefore devoted in recent years to the weathering induced by the lichen colonization. Here, we report nano-scale observations of the interface between lichens and basaltic rock by TEM and STXM techniques. Some samples of basaltic rocks totally covered by lichens were collected from the 1986 lava flows on the northwest part of Izu-Oshima volcano, Japan. To prepare specimens for the nano-scale observation, we utilized the focused ion beam (FIB) system. The microstructure and local chemistry of the specimens were thoroughly investigated by TEM equipped with energy-dispersive X-ray spectroscopy (EDX). Chemical components and chemical heterogeneity at the interface were observed by scanning transmission X-ray microscopy (STXM) at Advanced Light Source branch line 5.3.2.2. The collected rocks were classified into the augite-pigeonite-bronzite basalt including 6 to 8% plagioclase phenocrysts. The lichens adhering to the rocks were mainly Stereocaulon vesuvianum, fruticose lichen, which are widespread over the study area. The metabolites of the Stereocaulon vesuvianum exhibited a mean pH of 4.5 and dominance by acids. The STEM-EDX observations revealed that the interface between augite and the lichen was completely covered with amorphous silica multilayer with a thickness of less than 1 µm. Ca L-edge XANES spectra of the augite showed that the energy profile of the absorption edge at 349 eV was varied with the depth from the surface, indicating that the M2 site coordination accommodating Ca2+ undergoes significant change in shape as a function of distance from the surface. This behavior results from the fact that the M2 site is more distorted and more flexible in the C2/c clinopyroxene phase. Taking into consideration that the S. vesuvianum can produce acidic organic compounds during metabolism, the amorphous silica multilayers observed at the interface were produced by mineral dissolution induced by the lichen, and formed as a pseudomorphic replacement of augite by amorphous silica.
Occurrences of dendritic gold at the McLaughlin Mine hot-spring gold deposit

NASA Astrophysics Data System (ADS)

Sherlock, R. L.; Lehrman, N. J.

1995-06-01

Two styles of gold dendrites are variably developed at the McLaughlin Mine. The most abundant occurrence is hosted by amber-coloured hydrocarbon-rich opal. Silica likely precipitated from a boiling hydrothermal fluid and complexed with immiscible hydrocarbons forming an amorphous hydrocarbon-silica phase. This phase likely scavenged particulate gold by electrostatic attraction to the hydrocarbon-silica phase. The dendritic nature of the gold is secondary and is the result of dewatering of the amorphous hydrocarbon-silica phase and crystallization of gold into syneresis fractures. The second style of dendritic gold is hosted within vein swarms that focused large volumes of fluid flow. The dendrites occur along with hydrocarbon-rich silica at the upper contact of the vein margins which isolated the dendrites allowing sufficient time for them to grow. In a manner similar to the amber-coloured opal, the dendrites may have formed by scavenging particulate gold by electrostatic attraction to the hydrocarbon-silica phase.
In situ X-Ray Diffraction of Shock-Compressed Fused Silica

NASA Astrophysics Data System (ADS)

Tracy, Sally June; Turneaure, Stefan J.; Duffy, Thomas S.

2018-03-01

Because of its widespread applications in materials science and geophysics, SiO2 has been extensively examined under shock compression. Both quartz and fused silica transform through a so-called "mixed-phase region" to a dense, low compressibility high-pressure phase. For decades, the nature of this phase has been a subject of debate. Proposed structures include crystalline stishovite, another high-pressure crystalline phase, or a dense amorphous phase. Here we use plate-impact experiments and pulsed synchrotron x-ray diffraction to examine the structure of fused silica shock compressed to 63 GPa. In contrast to recent laser-driven compression experiments, we find that fused silica adopts a dense amorphous structure at 34 GPa and below. When compressed above 34 GPa, fused silica transforms to untextured polycrystalline stishovite. Our results can explain previously ambiguous features of the shock-compression behavior of fused silica and are consistent with recent molecular dynamics simulations. Stishovite grain sizes are estimated to be ˜5 - 30 nm for compression over a few hundred nanosecond time scale.
Photoinduced electro-optics measurements of biosilica transformation to cristobalite

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

Fuchs, Ido; Aluma, Yaniv; Ilan, Micha

2015-03-15

In this paper we studied the photoinduced electro optics effects in the thermal transformation process of biosilica to cristobalite, at a relatively low temperature and ambient pressure. This process was characterized by a variety of standards techniques with emphasis on linear electro optic effect measurements. Overall we demonstrated that photoinduced electro optics measurements are very sensitive to the transformation from amorphous structure of silica in the natural sponge samples to laminar string morphology of cristobalite. With this technique we could probe the change in the samples chirality from achiral bio silica to chiral cristobalite structure. Furthermore it is shown thatmore » natural biosilica have photoinduced linear electro optics respond indicating the chiral natural of biosilica. - Graphical abstract: The phase transformation of biosilica from marine sponges to Cristobalite under thermal treatment was investigated using photoinduced electro optics measurements. The figure shows the changes of the electro-optic coefficient of cristobalite and biosilica. - Highlights: • We examine phase transformation of biosilica. • We report transition from amorphous biosilica to crystalline Cristobalite. • Biosilica transformation to Cristobalite at temperature of 850 °C. • Biosilica transformation is studied with photoinduced measurements. • We examine changes in the photoinduced linear electro optics properties.« less
Bio-Based Approaches to Inorganic Material Synthesis (Preprint)

DTIC Science & Technology

2007-03-01

involves the fungus and plant pathogen Fusarium oxysporum acting on amorphous silica in rice husks to transform it into crystalline silica...nanoparticles after 24 hrs at room temperature [3]. Specific cationic proteins from F. oxysporum were found to be associated with the crystalline silica 2 after
Recovery of Stishovite-Structure at Ambient Conditions out of Shock-Generated Amorphous Silica

NASA Astrophysics Data System (ADS)

Luo, S. N.; Tschauner, O.; Asimow, P. D.; Ahrens, T. J.

2006-12-01

We show that bulk amorphous silica recovered from shock wave experiments on quartz to 56 GPa is not a true glass but rather keeps a large degree of long range structural information that can be recovered by static cold recompression to 13 GPa. At this pressure shock-retrieved silica assumes the structure of crystalline stishovite. This amorphous-crystal transition is characterized by long coherence length, resulting in formation of large crystallites. Therefore, the shock-recovered amorphous material studied here is a slightly disordered six-fold coordinated silica phase but not a glass, which possesses only medium range order [1]. It is therefore most likely that stishovite or a structurally closely related solid phase represent the state this material had assumed during shock, while post-shock heating to 500 -1000 K [2-4] induces the observed slight disorder. This probable memory-effect allows for physically more precise characterization of diaplectic silica `glass' and may be extended to other diaplectic `glasses' [1] O.Tschauner, S.N. Luo, P.D.Asimow, T.J. Ahrens, Am. Min. in print (2006) [2] J. Wackerle, Journal of Applied Physics, 33, 922 - 937 (1962) [3] M.B. Boslough, Journal of Geophysical Research, 93, 6477 - 9484 (1988) [4] S.N. Luo, T.J. Ahrens, P.D. Asimow, Journal of Geophysical Research, 108, 2421- 2434 (2003) Supported under the NNSA Cooperative Agreement DE-FC88-01NV14049 and under NASA PGG Grant NNG04G107G and Contribution # 9144, Division of Geological and Planetary Sciences, California Institute of Technology.
Size- and structure-dependent toxicity of silica particulates

NASA Astrophysics Data System (ADS)

Hanada, Sanshiro; Miyaoi, Kenichi; Hoshino, Akiyoshi; Inasawa, Susumu; Yamaguchi, Yukio; Yamamoto, Kenji

2011-03-01

Nano- and micro-particulates firmly attach with the surface of various biological systems. In some chronic pulmonary disease such as asbestosis and silicosis, causative particulates will induce chronic inflammatory disorder, followed by poor prognosis diseases. However, nano- and micro-scale specific toxicity of silica particulates is not well examined enough to recognize the risk of nano- and micro-particulates from the clinical aspect. To clarify the effect of the size and structure of silica particulates on the cellular damage and the biological response, we assessed the cytotoxicity of the various kinds of silica particles including amorphous and crystalline silica, in mouse alveolar macrophage culture, focusing on the fibrotic and inflammatory response. Our study showed that the cytotoxicity, which depends on the particle size and surface area, is correlated with their inflammatory response. By contrast, production of TGF-β, which is one of the fibrotic agents in lung, by addition of crystal silica was much higher than that of amorphous silica. We conclude that fibrosis and inflammation are induced at different phases and that the size- and structure-differences of silica particulates affect the both biological responses, caused by surface activity, radical species, and so on.
Surface modification of zinc oxide nanoparticles with amorphous silica alters their fate in the circulation.

PubMed

Konduru, Nagarjun V; Murdaugh, Kimberly M; Swami, Archana; Jimenez, Renato J; Donaghey, Thomas C; Demokritou, Philip; Brain, Joseph D; Molina, Ramon M

2016-08-01

Nanoparticle (NP) pharmacokinetics and biological effects are influenced by many factors, especially surface physicochemical properties. We assessed the effects of an amorphous silica coating on the fate of zinc after intravenous (IV) injection of neutron activated uncoated (65)ZnO or silica-coated (65)ZnO NPs in male Wistar Han rats. Groups of IV-injected rats were sequentially euthanized, and 18 tissues were collected and analyzed for (65)Zn radioactivity. The protein coronas on each ZnO NP after incubation in rat plasma were analyzed by SDS-PAGE gel electrophoresis and mass spectrometry of selected gel bands. Plasma clearance for both NPs was biphasic with rapid initial and slower terminal clearance rates. Half-lives of plasma clearance of silica-coated (65)ZnO were shorter (initial - <1 min; terminal - 2.5 min) than uncoated (65)ZnO (initial - 1.9 min; terminal - 38 min). Interestingly, the silica-coated (65)ZnO group had higher (65)Zn associated with red blood cells and higher initial uptake in the liver. The (65)Zn concentrations in all the other tissues were significantly lower in the silica-coated than uncoated groups. We also found that the protein corona formed on silica-coated ZnO NPs had higher amounts of plasma proteins, particularly albumin, transferrin, A1 inhibitor 3, α-2-hs-glycoprotein, apoprotein E and α-1 antitrypsin. Surface modification with amorphous silica alters the protein corona, agglomerate size, and zeta potential of ZnO NPs, which in turn influences ZnO biokinetic behavior in the circulation. This emphasizes the critical role of the protein corona in the biokinetics, toxicology and nanomedical applications of NPs.
W-containing oxide layers obtained on aluminum and titanium by PEO as catalysts in thiophene oxidation

NASA Astrophysics Data System (ADS)

Rudnev, V. S.; Lukiyanchuk, I. V.; Vasilyeva, M. S.; Morozova, V. P.; Zelikman, V. M.; Tarkhanova, I. G.

2017-11-01

W-containing oxide layers fabricated on titanium and aluminum alloys by Plasma electrolytic oxidation (PEO) have been tested in the reaction of the peroxide oxidation of thiophene. Samples with two types of coatings have been investigated. Coatings I contained tungsten oxide in the matrix and on the surface of amorphous silica-titania or silica-alumina layers, while coatings II comprised crystalline WO3 and/or Al2(WO4)3. Aluminum-supported catalyst containing a smallest amount of transition metals in the form of tungsten oxides and manganese oxides in low oxidation levels showed high activity and stability.

Calcium aluminates hydration in presence of amorphous SiO{sub 2} at temperatures below 90 deg. C

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

Rivas Mercury, J.M.; Turrillas, X.; Aza, A.H. de

2006-10-15

The hydration behaviour of Ca{sub 3}Al{sub 2}O{sub 6}, Ca{sub 12}Al{sub 14}O{sub 33} and CaAl{sub 2}O{sub 4} with added amorphous silica at 40, 65 and 90 deg. C has been studied for periods ranging from 1 to 31 days. In hydrated samples crystalline phases like katoite (Ca{sub 3}Al{sub 2}(SiO{sub 4}){sub 3-} {sub x} (OH){sub 4} {sub x} ) and gibbsite, Al(OH){sub 3}, were identified, likewise amorphous phases like Al(OH) {sub x} , calcium silicate hydrates, C-S-H, and calcium aluminosilicate hydrates, C-S-A-H, were identified. The stoichiometry of Ca{sub 3}Al{sub 2}(SiO{sub 4}){sub 3-} {sub x} (OH){sub 4} {sub x} (0{<=}3-x{<=}0.334), which was themore » main crystalline product, was established by Rietveld refinement of X-ray and neutron diffraction data and by transmission electron microscopy. - Graphical abstract: Katoite, Ca{sub 3}Al{sub 2}(SiO{sub 4}){sub 3-} {sub x} (OH){sub 4} {sub x} (0{<=}3-x{<=}0.334), was identified besides gibbsite, Al(OH){sub 3}, as a crystalline stable hydration products in Ca{sub 3}Al{sub 2}O{sub 6}, Ca{sub 12}Al{sub 14}O{sub 33} and CaAl{sub 2}O{sub 4} hydrated with added amorphous silica between 40 and 90 deg. C.« less
Removal of dissolved and colloidal silica

DOEpatents

Midkiff, William S.

2002-01-01

Small amorphous silica particles are used to provide a relatively large surface area upon which silica will preferentially adsorb, thereby preventing or substantially reducing scaling caused by deposition of silica on evaporative cooling tower components, especially heat exchange surfaces. The silica spheres are contacted by the cooling tower water in a sidestream reactor, then separated using gravity separation, microfiltration, vacuum filtration, or other suitable separation technology. Cooling tower modifications for implementing the invention process have been designed.
NMR Relaxometry to Characterize the Drug Structural Phase in a Porous Construct.

PubMed

Thrane, Linn W; Berglund, Emily A; Wilking, James N; Vodak, David; Seymour, Joseph D

2018-06-14

Nuclear magnetic resonance (NMR) frequency spectra and T 2 relaxation time measurements, using a high-power radio frequency probe, are shown to characterize the presence of an amorphous drug in a porous silica construct. The results indicate the ability of non-solid-state NMR methods to characterize crystalline and amorphous solid structural phases in drugs. Two-dimensional T 1 - T 2 magnetic relaxation time correlation experiments are shown to monitor the impact of relative humidity on the drug in a porous silica tablet.
A lucrative chemical processing of bamboo leaf biomass to synthesize biocompatible amorphous silica nanoparticles of biomedical importance

NASA Astrophysics Data System (ADS)

Rangaraj, Suriyaprabha; Venkatachalam, Rajendran

2017-06-01

Synthesis of silica nanoparticles from natural resources/waste via cost effective route is presently one of the anticipating strategies for extensive applications. This study reports the low-cost indigenous production of silica nanoparticles from the leftover of bamboo (leaf biomass) through thermal combustion and alkaline extraction, and examination of physico-chemical properties and yield percentage using comprehensive characterization tools. The outcome of primed silica powder exhibits amorphous particles (average size: 25 nm) with high surface area (428 m2 g-1) and spherical morphology. Despite the yield percentage of silica nanoparticles from bamboo leave ash is 50.2%, which is less than rice husk ask resources (62.1%), the bamboo waste is only an inexpensive resource yielding high purity (99%). Synthesis of silica nanoparticles from natural resources/waste with the help of lucrative route is at present times one of the anticipating strategies for extensive applications. In vitro study on animal cell lines (MG-63) shows non-toxic nature of silica nanoparticles up to 125 µg mL-1. Hence, this study highlights the feasibility for the mass production of silica nanoparticles from bamboo leave waste rather using chemical precursor of silica for drug delivery and other medical applications.
Amorphization of quartz by friction: Implication to silica-gel lubrication of fault surfaces

NASA Astrophysics Data System (ADS)

Nakamura, Yu; Muto, Jun; Nagahama, Hiroyuki; Shimizu, Ichiko; Miura, Takashi; Arakawa, Ichiro

2012-11-01

To understand physico-chemical processes at real contacts (asperities) on fault surfaces, we conducted pin-on-disk friction experiments at room temperature, using single crystalline quartz disks and quartz pins. Velocity weakening from friction coefficient μ ˜ 0.6 to 0.4 was observed under apparent normal stresses of 8-19 (18 > 19), when the slip rate was increased from 0.003 to 2.6 m/s. Frictional surfaces revealed ductile deformation of wear materials. The Raman spectra of frictional tracks showed blue shifts and broadening of quartz main bands, and appearance of new peaks at 490-520 and 610 cm-1. All these features are indicative of pressure- and strain-induced amorphization of quartz. The mapping analyses of Fourier transform infrared (FT-IR) spectroscopy at room dry conditions suggest selective hydration of wear materials. It is possible that the strained Si-O-Si bridges in amorphous silica preferentially react with water to form silica-gel. In natural fault systems, amorphous materials would be produced at real fault contacts and accumulate over the fault surfaces with displacements. Subsequent hydration would lead to significant reduction of fault strength during slip.
Molecular dynamics study of interfacial thermal transport between silicene and substrates.

PubMed

Zhang, Jingchao; Hong, Yang; Tong, Zhen; Xiao, Zhihuai; Bao, Hua; Yue, Yanan

2015-10-07

In this work, the interfacial thermal transport across silicene and various substrates, i.e., crystalline silicon (c-Si), amorphous silicon (a-Si), crystalline silica (c-SiO2) and amorphous silica (a-SiO2) are explored by classical molecular dynamics (MD) simulations. A transient pulsed heating technique is applied in this work to characterize the interfacial thermal resistance in all hybrid systems. It is reported that the interfacial thermal resistances between silicene and all substrates decrease nearly 40% with temperature from 100 K to 400 K, which is due to the enhanced phonon couplings from the anharmonicity effect. Analysis of phonon power spectra of all systems is performed to interpret simulation results. Contradictory to the traditional thought that amorphous structures tend to have poor thermal transport capabilities due to the disordered atomic configurations, it is calculated that amorphous silicon and silica substrates facilitate the interfacial thermal transport compared with their crystalline structures. Besides, the coupling effect from substrates can improve the interface thermal transport up to 43.5% for coupling strengths χ from 1.0 to 2.0. Our results provide fundamental knowledge and rational guidelines for the design and development of the next-generation silicene-based nanoelectronics and thermal interface materials.
Vapor Pressure and Evaporation Coefficient of Silicon Monoxide over a Mixture of Silicon and Silica

NASA Technical Reports Server (NTRS)

Ferguson, Frank T.; Nuth, Joseph A., III

2012-01-01

The evaporation coefficient and equilibrium vapor pressure of silicon monoxide over a mixture of silicon and vitreous silica have been studied over the temperature range (1433 to 1608) K. The evaporation coefficient for this temperature range was (0.007 plus or minus 0.002) and is approximately an order of magnitude lower than the evaporation coefficient over amorphous silicon monoxide powder and in general agreement with previous measurements of this quantity. The enthalpy of reaction at 298.15 K for this reaction was calculated via second and third law analyses as (355 plus or minus 25) kJ per mol and (363.6 plus or minus 4.1) kJ per mol respectively. In comparison with previous work with the evaporation of amorphous silicon monoxide powder as well as other experimental measurements of the vapor pressure of silicon monoxide gas over mixtures of silicon and silica, these systems all tend to give similar equilibrium vapor pressures when the evaporation coefficient is correctly taken into account. This provides further evidence that amorphous silicon monoxide is an intimate mixture of small domains of silicon and silica and not strictly a true compound.
Laboratory Simulated Acid-Sulfate Weathering of Basaltic Materials: Implications for Formation of Sulfates at Meridiani Planum and Gusev Crater, Mars

NASA Technical Reports Server (NTRS)

Golden, D. C.; Ming, Douglas W.; Morris, Richard V.; Mertzman, A.

2006-01-01

Acid-sulfate weathering of basaltic materials is a candidate formation process for the sulfate-rich outcrops and rocks at the MER rover Opportunity and Spirit landing sites. To determine the style of acid-sulfate weathering on Mars, we weathered basaltic materials (olivine-rich glassy basaltic sand and plagioclase feldspar-rich basaltic tephra) in the laboratory under different oxidative, acid-sulfate conditions and characterized the alteration products. We investigated alteration by (1) sulfuric-acid vapor (acid fog), (2) three-step hydrothermal leaching treatment approximating an open system and (3) single-step hydrothermal batch treatment approximating a "closed system." In acid fog experiments, Al, Fe, and Ca sulfates and amorphous silica formed from plagioclase-rich tephra, and Mg and Ca sulfates and amorphous silica formed from the olivine-rich sands. In three-step leaching experiments, only amorphous Si formed from the plagioclase-rich basaltic tephra, and jarosite, Mg and Ca sulfates and amorphous silica formed from olivine-rich basaltic sand. Amorphous silica formed under single-step experiments for both starting materials. Based upon our experiments, jarosite formation in Meridiani outcrop is potential evidence for an open system acid-sulfate weathering regime. Waters rich in sulfuric acid percolated through basaltic sediment, dissolving basaltic phases (e.g., olivine) and forming jarosite, other sulfates, and iron oxides. Aqueous alteration of outcrops and rocks on the West Spur of the Columbia Hills may have occurred when vapors rich in SO2 from volcanic sources reacted with basaltic materials. Soluble ions from the host rock (e.g., olivine) reacted with S to form Ca-, Mg-, and other sulfates along with iron oxides and oxyhydroxides.
Low cost routes to high purity silicon and derivatives thereof

DOEpatents

Laine, Richard M; Krug, David James; Marchal, Julien Claudius; Mccolm, Andrew Stewart

2013-07-02

The present invention is directed to a method for providing an agricultural waste product having amorphous silica, carbon, and impurities; extracting from the agricultural waste product an amount of the impurities; changing the ratio of carbon to silica; and reducing the silica to a high purity silicon (e.g., to photovoltaic silicon).
In vitro efficacies of oils, silicas and plant preparations against the poultry red mite Dermanyssus gallinae.

PubMed

Maurer, Veronika; Perler, Erika; Heckendorn, Felix

2009-06-01

The aim of this study was to test the effectiveness of physically acting substances (oils and silicas) and plant preparations for the control of the poultry red mite Dermanyssus gallinae (De Geer 1778). Reproduction and survival of fed D. gallinae females were evaluated in vitro for a total of 168 h using the "area under the survival curve" (AUC) to compare survival of the mites between treatments. Four oils (two plant oils, one petroleum spray oil and diesel), one soap, three silicas (one synthetic amorphous silica, one diatomaceous earth (DE) and one DE with 2% pyrethrum extract) and seven plant preparations (derived from Chrysanthemum cineariaefolium, Allium sativum, Tanacetum vulgare, Yucca schidigera, Quillaja saponaria, Dryopteris filix-mas, and Thuja occidentalis) were tested at various concentrations. All the oils, diesel and soap significantly reduced D. gallinae survival. All silicas tested inhibited reproduction. DE significantly reduced mite survival, but amorphous silica was less effective in vitro. Except for pure A. sativum juice and the highest concentration of C. cineariaefolium extract, the plant preparations tested resulted in statistically insignificant control of D. gallinae.
Microstructural evolution of ion-irradiated sol–gel-derived thin films

DOE PAGES

Shojaee, S. A.; Qi, Y.; Wang, Y. Q.; ...

2017-07-17

In this paper, the effects of ion irradiation on the microstructural evolution of sol–gel-derived silica-based thin films were examined by combining the results from Fourier transform infrared, Raman, and X-ray photoelectron spectroscopy, Rutherford backscattering spectrometry, and elastic recoil detection. Variations in the chemical composition, density, and structure of the constituent phases and interfaces were studied, and the results were used to propose a microstructural model for the irradiated films. It was discovered that the microstructure of the films after ion irradiation and decomposition of the starting organic materials consisted of isolated hydrogenated amorphous carbon clusters within an amorphous and carbon-incorporatedmore » silica network. A decrease in the bond angle of Si–O–Si bonds in amorphous silica network along with an increase in the concentration of carbon-rich SiO x C y tetrahedra were the major structural changes caused by ion irradiation. Finally, in addition, hydrogen release from free carbon clusters was observed with increasing ion energy and fluence.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)

Shojaee, S. A.; Qi, Y.; Wang, Y. Q.

In this paper, the effects of ion irradiation on the microstructural evolution of sol–gel-derived silica-based thin films were examined by combining the results from Fourier transform infrared, Raman, and X-ray photoelectron spectroscopy, Rutherford backscattering spectrometry, and elastic recoil detection. Variations in the chemical composition, density, and structure of the constituent phases and interfaces were studied, and the results were used to propose a microstructural model for the irradiated films. It was discovered that the microstructure of the films after ion irradiation and decomposition of the starting organic materials consisted of isolated hydrogenated amorphous carbon clusters within an amorphous and carbon-incorporatedmore » silica network. A decrease in the bond angle of Si–O–Si bonds in amorphous silica network along with an increase in the concentration of carbon-rich SiO x C y tetrahedra were the major structural changes caused by ion irradiation. Finally, in addition, hydrogen release from free carbon clusters was observed with increasing ion energy and fluence.« less
In vitro characterisation of a sol-gel derived in situ silica-coated silicate and carbonate co-doped hydroxyapatite nanopowder for bone grafting.

PubMed

Latifi, Seyed Mohsen; Fathi, Mohammadhossein; Sharifnabi, Ali; Varshosaz, Jaleh

2017-06-01

Design and synthesis of materials with better properties and performance are essential requirements in the field of biomaterials science that would directly improve patient quality of life. For this purpose, in situ silica-coated silicate and carbonate co-doped hydroxyapatite (Sc/S.C.HA) nanopowder was synthesized via the sol-gel method. Characterisation of the prepared nanopowder was carried out by XRD, FTIR, TEM, SEM, EDX, ICP, zeta potential, acid dissolution test, and cell culture test. The substitution of the silicate and carbonate ions into hydroxyapatite structure was confirmed by FTIR analysis. XRD analysis showed that silica is an amorphous phase, which played a role in covering the surface of the S.C.HA nanoparticles as confirmed by acid dissolution test. Low thickness and low integrity of the amorphous silica surface layer facilitated ions release from S.C.HA nanoparticles into physiological saline solution. Zeta potential of the prepared nanopowder suspended in physiological saline solution was -27.3±0.2mV at pH7.4. This negatively charged surface, due to the presence of amorphous silica layer upon the S.C.HA nanoparticles, not only had an accelerating effect on in vitro biomineralization of apatite, but also had a positive effect on cell attachment. Copyright © 2017 Elsevier B.V. All rights reserved.
Face-specific Replacement of Calcite by Amorphous Silica Nanoparticles

NASA Astrophysics Data System (ADS)

Liesegang, M.; Milke, R.; Neusser, G.; Mizaikoff, B.

2016-12-01

Amorphous silica, composed of nanoscale spheres, is an important biomineral, alteration product of silicate rocks on the Earth's surface, and precursor material for stable silicate minerals. Despite constant progress in silica sphere synthesis, fundamental knowledge of natural silica particle interaction and ordering processes leading to colloidal crystals is absent so far. To understand the formation pathways of silica spheres in a geologic environment, we investigated silicified Cretaceous mollusk shell pseudomorphs from Coober Pedy (South Australia) using focused ion beam (FIB)-SEM tomography, petrographic microscopy, µ-XRD, and EMPA. The shells consist of replaced calcite crystals (<2 mm) composed of ordered arrays of uniform, close-packed silica spheres 300 ± 10 nm in size. Concentric layered spheres composed of 40 nm-sized subparticles provide evidence that, at least in the final stage, particle aggregation was the major sphere growth mechanism. Silica sphere arrays in periodically changing orientations perfectly replicate polysynthetic twinning planes of calcite. FIB-SEM tomography shows that cubic closed-packed sphere arrangements preserve the twin lamellae, while the twin plane consists of a submicrometer layer of randomly ordered spheres and vacancies. To transfer crystallographic information from parent to product, the advancement of synchronized dissolution and precipitation fronts along lattice planes is essential. We assume that the volume-preserving replacement process proceeds via a face-specific dissolution-precipitation mechanism with intermediate subparticle aggregation and subsequent layer-by-layer deposition of spheres along a planar surface. Porosity created during the replacement reaction allows permanent fluid access to the propagating reaction interface. Fluid pH and ionic strength remain constant throughout the replacement process, permitting continuous silica nanoparticle formation and diffusion-limited colloid aggregation. Our study provides a natural example of the transformation of an atomic crystal to an amorphous, mesoscale ordered material; thus, links the research fields of natural colloidal crystal formation, carbonate-silica replacement, and crystallization by oriented particle aggregation (CPA).
Monitoring the recrystallisation of amorphous xylitol using Raman spectroscopy and wide-angle X-ray scattering.

PubMed

Palomäki, Emmi; Ahvenainen, Patrik; Ehlers, Henrik; Svedström, Kirsi; Huotari, Simo; Yliruusi, Jouko

2016-07-11

In this paper we present a fast model system for monitoring the recrystallization of quench-cooled amorphous xylitol using Raman spectroscopy and wide-angle X-ray scattering. The use of these two methods enables comparison between surface and bulk crystallization. Non-ordered mesoporous silica micro-particles were added to the system in order to alter the rate of crystallization of the amorphous xylitol. Raman measurements showed that adding silica to the system increased the rate of surface crystallization, while X-ray measurements showed that the rate of bulk crystallization decreased. Using this model system it is possible to measure fast changes, which occur in minutes or within a few hours. Raman-spectroscopy and wide-angle X-ray scattering were found to be complementary techniques when assessing surface and bulk crystallization of amorphous xylitol. Copyright © 2016 Elsevier B.V. All rights reserved.
Direct ink writing of silica-bonded calcite scaffolds from preceramic polymers and fillers.

PubMed

Fiocco, L; Elsayed, H; Badocco, D; Pastore, P; Bellucci, D; Cannillo, V; Detsch, R; Boccaccini, A R; Bernardo, E

2017-05-11

Silica-bonded calcite scaffolds have been successfully 3D-printed by direct ink writing, starting from a paste comprising a silicone polymer and calcite powders, calibrated in order to match a SiO 2 /CaCO 3 weight balance of 35/65. The scaffolds, fabricated with two slightly different geometries, were first cross-linked at 350 °C, then fired at 600 °C, in air. The low temperature adopted for the conversion of the polymer into amorphous silica, by thermo-oxidative decomposition, prevented the decomposition of calcite. The obtained silica-bonded calcite scaffolds featured open porosity of about 56%-64% and compressive strength of about 2.9-5.5 MPa, depending on the geometry. Dissolution studies in SBF and preliminary cell culture tests, with bone marrow stromal cells, confirmed the in vitro bioactivity of the scaffolds and their biocompatibility. The seeded cells were found to be alive, well anchored and spread on the samples surface. The new silica-calcite composites are expected to be suitable candidates as tissue-engineering 3D scaffolds for regeneration of cancellous bone defects.
Aligned silica nanowires on the inner wall of bubble-like silica film: the growth mechanism and photoluminescence.

PubMed

Chen, Yiqing; Zhou, Qingtao; Jiang, Haifeng; Su, Yong; Xiao, Haihua; Zhu, Li-Ang; Xu, Liang

2006-02-28

Large area, aligned amorphous silica nanowires grow on the inner wall of bubble-like silica film, which is prepared by thermal evaporation of a molten gallium-silicon alloy in a flow of ammonia. These nanowires are 10-20 nm in diameter and 0.5-1.5 µm in length. The bubble-like silica film functions as a substrate, guiding the growth of silica nanowires by a vapour-solid process. This work helps us to clearly elucidate the growth mechanism of aligned amorphous silica nanowires, ruling out the possibility of liquid gallium acting as a nucleation substrate for the growth of the aligned silica nanowires. A broad emission band from 290 to 600 nm is observed in the photoluminescence (PL) spectrum of these nanowires. There are seven PL peaks: two blue emission peaks at 430 nm (2.88 eV) and 475 nm (2.61 eV); and five ultraviolet emission peaks at 325 nm (3.82 eV), 350 nm (3.54 eV), 365 nm (3.40 eV), 385 nm (3.22 eV) and 390 nm (3.18 eV), which may be related to various oxygen defects.
Control of Cr6+ emissions from gas metal arc welding using a silica precursor as a shielding gas additive.

PubMed

Topham, Nathan; Wang, Jun; Kalivoda, Mark; Huang, Joyce; Yu, Kuei-Min; Hsu, Yu-Mei; Wu, Chang-Yu; Oh, Sewon; Cho, Kuk; Paulson, Kathleen

2012-03-01

Hexavalent chromium (Cr(6+)) emitted from welding poses serious health risks to workers exposed to welding fumes. In this study, tetramethylsilane (TMS) was added to shielding gas to control hazardous air pollutants produced during stainless steel welding. The silica precursor acted as an oxidation inhibitor when it decomposed in the high-temperature welding arc, limiting Cr(6+) formation. Additionally, a film of amorphous SiO(2) was deposited on fume particles to insulate them from oxidation. Experiments were conducted following the American Welding Society (AWS) method for fume generation and sampling in an AWS fume hood. The results showed that total shielding gas flow rate impacted the effectiveness of the TMS process. Increasing shielding gas flow rate led to increased reductions in Cr(6+) concentration when TMS was used. When 4.2% of a 30-lpm shielding gas flow was used as TMS carrier gas, Cr(6+) concentration in gas metal arc welding (GMAW) fumes was reduced to below the 2006 Occupational Safety and Health Administration standard (5 μg m(-3)) and the efficiency was >90%. The process also increased fume particle size from a mode size of 20 nm under baseline conditions to 180-300 nm when TMS was added in all shielding gas flow rates tested. SiO(2) particles formed in the process scavenged nanosized fume particles through intercoagulation. Transmission electron microscopy imagery provided visual evidence of an amorphous film of SiO(2) on some fume particles along with the presence of amorphous SiO(2) agglomerates. These results demonstrate the ability of vapor phase silica precursors to increase welding fume particle size and minimize chromium oxidation, thereby preventing the formation of hexavalent chromium.
In vivo penetration of bare and lipid-coated silica nanoparticles across the human stratum corneum.

PubMed

Iannuccelli, Valentina; Bertelli, Davide; Romagnoli, Marcello; Scalia, Santo; Maretti, Eleonora; Sacchetti, Francesca; Leo, Eliana

2014-10-01

Skin penetration of silica nanoparticles (NP) currently used in pharmaceutical and cosmetic products is a topic of interest not only to evaluate their possible toxicity, but also to understand their behaviour upon contact with the skin and to exploit their potential positive effects in drug or cosmetic delivery field. Therefore, the present work aimed to elucidate the in vivo mechanism by which amorphous hydrophilic silica NP enter human stratum corneum (SC) through the evaluation of the role played by the nanoparticle surface polarity and the human hair follicle density. Two silica samples, bare hydrophilic silica (B-silica, 162±51nm in size) and hydrophobic lipid-coated silica (LC-silica, 363±74nm in size) were applied on both the volar and dorsal side of volunteer forearms. Twelve repetitive stripped tapes were removed from the human skin and evaluated for elemental composition by Energy Dispersive X-ray (EDX) analysis and for silicon content by Inductively Coupled Plasma quadrupole Mass Spectrometry (ICP-MS). All the stripped tapes revealed nanosized structures generally located in the broad spaces between corneocytes and characterized by the same elemental composition (relative weight percentage of silicon and silicon to oxygen weight ratio) than that of the applied samples. However, only about 10% B-silica permeated until the deepest SC layers considered in the study indicating a silica retention in the upper layers of SC, regardless of the hair follicle density. Otherwise, the exposure to LC-silica led to a greater silica skin penetration extent into the deeper SC layers (about 42% and 18% silica following volar and dorsal forearm application, respectively) indicating that the NP surface polarity played a predominant role on that of their size in determining the route and the extent of penetration. Copyright © 2014 Elsevier B.V. All rights reserved.
The radiolysis and radioracemization of amino acids on silica surfaces

NASA Technical Reports Server (NTRS)

Bonner, W. A.; Lemmon, R. M.

1981-01-01

Results are presented of experiments on the radioracemization of amino acids in the presence of silica surfaces such as may have been found on the prebiotic earth. L-leucine and a DL-leucine mixture deposited on samples of 1-quartz and an amorphous silica preparation (Syloid 63) was subjected to Co-60 gamma-ray irradiation, then analyzed by gas chromatography to determine the radiolysis and racemization rates. The quartz surface is found to have a marginal efficacy in enhancing radiolysis when compared with a crystalline L-leucine control, although enhancing radioracemization symmetrically by a factor of two. Both the radiolysis and radioracemization of L-leucine and DL-leucine on a Syloid-63 silica surface are observed to increase with increasing radiation dose, and to be substantially greater than in the crystalline controls. Additional experiments with the nonprotein amino acid isovaline deposited on Syloid 63 confirm the greater radiolysis susceptibility of amino acids deposited on silica with respect to the crystalline state, although racemization is not observed. The observations suggest that the presence of a silica surface would have a deleterious effect on any mechanism for the origin of molecular chirality relying on stereoselective beta-radiolysis.

Oral two-generation reproduction toxicity study with NM-200 synthetic amorphous silica in Wistar rats.

PubMed

Wolterbeek, André; Oosterwijk, Thies; Schneider, Steffen; Landsiedel, Robert; de Groot, Didima; van Ee, Renz; Wouters, Mariëlle; van de Sandt, Han

2015-08-15

Synthetic amorphous silica (SAS) like NM-200 is used in a wide variety of technological applications and consumer products. Although SAS has been widely investigated the available reproductive toxicity studies are old and do not cover all requirements of current OECD Guidelines. As part of a CEFIC-LRI project, NM-200 was tested in a two-generation reproduction toxicity study according to OECD guideline 416. Male and female rats were treated by oral gavage with NM-200 at dose levels of 0, 100, 300 and 1000mg/kg bw/day for two generations. Body weight and food consumption were measured throughout the study. Reproductive and developmental parameters were measured and at sacrifice (reproductive) organs and tissues were sampled for histopathological analysis. Oral administration of NM-200 up to 1000mg/kg bw/day had no adverse effects on the reproductive performance of rats or on the growth and development of the offspring into adulthood for two consecutive generations. The NOAEL was 1000mg/kg body weight per day. Copyright © 2015 Elsevier Inc. All rights reserved.
Coaxial carbon plasma gun deposition of amorphous carbon films

NASA Technical Reports Server (NTRS)

Sater, D. M.; Gulino, D. A.; Rutledge, S. K.

1984-01-01

A unique plasma gun employing coaxial carbon electrodes was used in an attempt to deposit thin films of amorphous diamond-like carbon. A number of different structural, compositional, and electrical characterization techniques were used to characterize these films. These included scanning electron microscopy, scanning transmission electron microscopy, X ray diffraction and absorption, spectrographic analysis, energy dispersive spectroscopy, and selected area electron diffraction. Optical absorption and electrical resistivity measurements were also performed. The films were determined to be primarily amorphous, with poor adhesion to fused silica substrates. Many inclusions of particulates were found to be present as well. Analysis of these particulates revealed the presence of trace impurities, such as Fe and Cu, which were also found in the graphite electrode material. The electrodes were the source of these impurities. No evidence of diamond-like crystallite structure was found in any of the film samples. Details of the apparatus, experimental procedure, and film characteristics are presented.
Silica nanoparticles on front glass for efficiency enhancement in superstrate-type amorphous silicon solar cells

NASA Astrophysics Data System (ADS)

Das, Sonali; Banerjee, Chandan; Kundu, Avra; Dey, Prasenjit; Saha, Hiranmay; Datta, Swapan K.

2013-10-01

Antireflective coating on front glass of superstrate-type single junction amorphous silicon solar cells (SCs) has been applied using highly monodispersed and stable silica nanoparticles (NPs). The silica NPs having 300 nm diameter were synthesized by Stober technique where the size of the NPs was controlled by varying the alcohol medium. The synthesized silica NPs were analysed by dynamic light scattering technique and Fourier transform infrared spectroscopy. The NPs were spin coated on glass side of fluorinated tin oxide (SnO2: F) coated glass superstrate and optimization of the concentration of the colloidal solution, spin speed and number of coated layers was done to achieve minimum reflection characteristics. An estimation of the distribution of the NPs for different optimization parameters has been done using field-emission scanning electron microscopy. Subsequently, the transparent conducting oxide coated glass with the layer having the minimum reflectance is used for fabrication of amorphous silicon SC. Electrical analysis of the fabricated cell indicates an improvement of 6.5% in short-circuit current density from a reference of 12.40 mA cm-2 while the open circuit voltage and the fill factor remains unaltered. A realistic optical model has also been proposed to gain an insight into the system.
New opportunities in the preparation of nanocomposites for biomedical applications: revised mechanosynthesis of magnetite-silica nanocomposites

NASA Astrophysics Data System (ADS)

Scano, Alessandra; Cabras, Valentina; Marongiu, Francesca; Peddis, Davide; Pilloni, Martina; Ennas, Guido

2017-02-01

Environmentally friendly preparation of functionalized magnetite-silica (Fe3O4/SiO2) nanocomposites (NCs) with different SiO2 content (6, 20 and 50 wt%) using revised mechanosynthesis is reported. High-energy ball milling of α-Fe2O3, Si and SiO2 mixtures was followed by hydrolysis and condensation of 3-aminopropyl-triethoxysilane. X-ray powder diffraction and transmission electron microscopy showed the formation of almost spherical Fe3O4 nanocrystals with a narrow size distribution (4-6 nm) uniformly dispersed in the amorphous 100-200 nm SiO2 agglomerates. Scanning electron microscopy and energy dispersive spectroscopy were used to study the elemental distribution in the sample. Fourier transform infrared spectroscopy confirmed the NC surface functionalization with amino groups. Magnetic properties were also explored, indicating a homogeneous distribution of magnetic nanoparticles in the silica matrix.
Determination of silica coating efficiency on metal particles using multiple digestion methods.

PubMed

Wang, Jun; Topham, Nathan; Wu, Chang-Yu

2011-10-15

Nano-sized metal particles, including both elemental and oxidized metals, have received significant interest due to their biotoxicity and presence in a wide range of industrial systems. A novel silica technology has been recently explored to minimize the biotoxicity of metal particles by encapsulating them with an amorphous silica shell. In this study, a method to determine silica coating efficiency on metal particles was developed. Metal particles with silica coating were generated using gas metal arc welding (GMAW) process with a silica precursor tetramethylsilane (TMS) added to the shielding gas. Microwave digestion and Inductively Coupled Plasma-Atomic Emission Spectroscopy (ICP-AES) were employed to solubilize the metal content in the particles and analyze the concentration, respectively. Three acid mixtures were tested to acquire the appropriate digestion method targeting at metals and silica coating. Metal recovery efficiencies of different digestion methods were compared through analysis of spiked samples. HNO(3)/HF mixture was found to be a more aggressive digestion method for metal particles with silica coating. Aqua regia was able to effectively dissolve metal particles not trapped in the silica shell. Silica coating efficiencies were thus calculated based on the measured concentrations following digestion by HNO(3)/HF mixture and aqua regia. The results showed 14-39% of welding fume particles were encapsulated in silica coating under various conditions. This newly developed method could also be used to examine the silica coverage on particles of silica shell/metal core structure in other nanotechnology areas. Copyright © 2011 Elsevier B.V. All rights reserved.
In-vitro and in-vivo study of amorphous spironolactone prepared by adsorption method using supercritical CO2.

PubMed

Jiang, Qikun; Li, Yuanyuan; Fu, Qiang; Geng, Yajie; Zhao, Juanhang; Ma, Panqin; Zhang, Tianhong

2015-02-01

The aim of this study was to improve the oral bioavailability of spironolactone (SP). SP was adsorbed on the fumed silica using supercritical CO2 (scCO2) technology and further compressed into tablets. The morphology was observed by scanning electron microscopy (SEM), and the crystalline form was investigated by differential scanning calorimetry (DSC) and powder X-ray diffraction (PXRD). The dissolution test was performed in water, 0.1 M HCl solution, pH 4.5 acetate buffers and pH 6.8 phosphate buffers using the paddle method. The pharmacokinetics was undertaken in six dogs in a crossover fashion. SP was successfully prepared into tablets and presented in amorphous state. SP-silica scCO2 tablets displayed higher dissolution profiles than SP-silica physical mixtures tablets in different media. The AUC0-t and Cmax of SP-silica supercritical CO2 was 1.61- and 1.52-fold greater than those of SP-silica physical mixtures (p < 0.05), respectively. It is a promising method in improving dissolution and bioavailability by adsorbing SP, a poorly soluble drug, on the fumed silica using rapid expansion of supercritical solutions.
Rare pneumoconiosis induced by long-term amorphous silica exposure: the histological characteristics and expression of cyclooxygenase-2 as an antifibrogenic mediator in macrophages.

PubMed

Kumasaka, Toshio; Akaike, Yasushi; Nakamura, Osamu; Yamazaki, Kazuma; Moriyama, Hiroshi; Takemura, Tamiko

2011-11-01

Pneumoconiosis induced by non-crystalline silica is considered rare, although silicosis resulting from contact with crystalline silica is a well-known hazard associated with progressive pulmonary fibrosis. Here we describe a patient with pneumoconiosis induced by diatomaceous earth composed of amorphous silica detected by two-dimensional imaging of chemical elements. The histology revealed that the disease was characterized by a granulomatous reaction in the lung. A large number of macrophages laden with yellow and black pigments accumulated in alveolar spaces and were incorporated into the interstitial sites. Bronchiolar walls were destroyed by palisade macrophages, suggesting airflow obstruction. Packed macrophages adhering to and covering the denuded interstitium indicated that macrophages might be incorporated into pulmonary interstitium in this fashion. Immunohistochemistry showed that cyclooxygenase-2, an antifibrogenic mediator, was intensely expressed in the macrophages compared with macrophages in control lungs. No birefringent material was found in the tissues. When two-dimensional analysis of chemical elements was performed using an electron probe microanalyzer with a wavelength-dispersive spectrometer, the resultant fine mapping of silicon and oxygen on the tissue indicated that the pigments phagocytosed by macrophages corresponded to amorphous silica. In conclusion, two-dimensional analysis of elements is very useful for pathologists in correlating the presence of chemical elements with histological changes. © 2011 The Authors. Pathology International © 2011 Japanese Society of Pathology and Blackwell Publishing Asia Pty Ltd.
Laboratory Thermal Infrared and Visible to Near-Infrared Spectral Analysis of Chert

NASA Astrophysics Data System (ADS)

McDowell, M. L.; Hamilton, V. E.

2007-12-01

Though basaltic materials dominate the composition of the Martian surface, a material with a relatively high silica component in an area of Eos Chasma was reported by [1] from thermal infrared (TIR) data. The spectrum of the silica phase resembles quartz or chert, but with the existing information it is difficult to tell which phase best fits the observations. Though quartz, chert, and amorphous silica are chemically identical (SiO2), their physical differences (e.g., microstructures) result in different TIR spectral characteristics. Previous studies have analyzed a limited number of chert samples using emission infrared spectroscopy [2] and transmission infrared spectroscopy [3]. We continue these preliminary studies with an investigation aiming to more completely understand and document the variation in spectral character of cherts. This knowledge may help to identify the silica phase in Eos Chasma and any future discoveries. Our study includes a more extensive sampling of geologic chert in hand sample (>15 samples) with various sources, methods of formation, surface textures, and crystallinities. We analyzed their visible to near-infrared (VNIR) reflectance spectra, as well as spectral features in TIR emission spectra. We measured multiple locations on each sample to determine spectral homogeneity across the sample and between various orientations. Where possible, natural, cut, and recently fractured surfaces were measured. We compared the collected TIR spectra for similarities and differences in shape and spectral contrast within each sample and between samples that may relate to variations in the samples' structure (e.g. crystallinity, and surface texture). VNIR measurements show features indicative of non-silica phases and water that may be present in the cherts. [1] Hamilton, V.E. (2005) Eos Trans. AGU, Fall Meeting Suppl., Abstract P24A-08. [2] Michalski, J.R. (2005) PhD Diss., ASU, Tempe. [3] Long, D. G. et al. (2001) Canadian Archaeological Assoc., 33rd Meeting.
Fused Silica Surface Coating for a Flexible Silica Mat Insulation System

NASA Technical Reports Server (NTRS)

Rhodes, W. H.

1973-01-01

Fused silica insulation coatings have been developed for application to a flexible mat insulation system. Based on crystalline phase nucleation and growth kinetics, a 99+% SiO2 glass was selected as the base composition. A coating was developed that incorporated the high emissivity phase NiCr2O4 as a two phase coating with goals of high emittance and minimum change in thermal expansion. A second major coating classification has a plasma sprayed emittance coating over a sealed pure amorphous SiO2 layer. A third area of development centered on extremely thin amorphous SiO2 coatings deposited by chemical vapor deposition. The coating characterization studies presented are mechanical testing of thin specimens extracted from the coatings, cyclic arc exposures, and emittance measurements before and after arc exposures.
Micelle-template synthesis of hollow silica spheres for improving water vapor permeability of waterborne polyurethane membrane

PubMed Central

Bao, Yan; Wang, Tong; Kang, Qiaoling; Shi, Chunhua; Ma, Jianzhong

2017-01-01

Hollow silica spheres (HSS) with special interior spaces, high specific surface area and excellent adsorption and permeability performance were synthesized via micelle-template method using cetyl trimethyl ammonium bromide (CTAB) micelles as soft template and tetraethoxysilane (TEOS) as silica precursor. SEM, TEM, FT-IR, XRD, DLS and BET-BJH were carried out to characterize the morphology and structure of as-obtained samples. The results demonstrated that the samples were amorphous with a hollow structure and huge specific surface area. The growth of HSS was an inward-growth mechanism along template. Notably, we have provided a new and interesting fundamental principle for HSS materials by precisely controlling the ethanol-to-water volume ratio. In addition, the as-obtained HSS were mixed with waterborne polyurethane (WPU) to prepare WPU/HSS composite membrane. Various characterizations (SEM, TEM, FT-IR and TGA) revealed the morphology, polydispersity and adherence between HSS and WPU. Performance tests showed that the introduction of HSS can improve the water vapor permeability of composite membrane, promoting its water resistance and mechanical performance at the same time. PMID:28429740
Micelle-template synthesis of hollow silica spheres for improving water vapor permeability of waterborne polyurethane membrane

NASA Astrophysics Data System (ADS)

Bao, Yan; Wang, Tong; Kang, Qiaoling; Shi, Chunhua; Ma, Jianzhong

2017-04-01

Hollow silica spheres (HSS) with special interior spaces, high specific surface area and excellent adsorption and permeability performance were synthesized via micelle-template method using cetyl trimethyl ammonium bromide (CTAB) micelles as soft template and tetraethoxysilane (TEOS) as silica precursor. SEM, TEM, FT-IR, XRD, DLS and BET-BJH were carried out to characterize the morphology and structure of as-obtained samples. The results demonstrated that the samples were amorphous with a hollow structure and huge specific surface area. The growth of HSS was an inward-growth mechanism along template. Notably, we have provided a new and interesting fundamental principle for HSS materials by precisely controlling the ethanol-to-water volume ratio. In addition, the as-obtained HSS were mixed with waterborne polyurethane (WPU) to prepare WPU/HSS composite membrane. Various characterizations (SEM, TEM, FT-IR and TGA) revealed the morphology, polydispersity and adherence between HSS and WPU. Performance tests showed that the introduction of HSS can improve the water vapor permeability of composite membrane, promoting its water resistance and mechanical performance at the same time.
Micelle-template synthesis of hollow silica spheres for improving water vapor permeability of waterborne polyurethane membrane.

PubMed

Bao, Yan; Wang, Tong; Kang, Qiaoling; Shi, Chunhua; Ma, Jianzhong

2017-04-21

Hollow silica spheres (HSS) with special interior spaces, high specific surface area and excellent adsorption and permeability performance were synthesized via micelle-template method using cetyl trimethyl ammonium bromide (CTAB) micelles as soft template and tetraethoxysilane (TEOS) as silica precursor. SEM, TEM, FT-IR, XRD, DLS and BET-BJH were carried out to characterize the morphology and structure of as-obtained samples. The results demonstrated that the samples were amorphous with a hollow structure and huge specific surface area. The growth of HSS was an inward-growth mechanism along template. Notably, we have provided a new and interesting fundamental principle for HSS materials by precisely controlling the ethanol-to-water volume ratio. In addition, the as-obtained HSS were mixed with waterborne polyurethane (WPU) to prepare WPU/HSS composite membrane. Various characterizations (SEM, TEM, FT-IR and TGA) revealed the morphology, polydispersity and adherence between HSS and WPU. Performance tests showed that the introduction of HSS can improve the water vapor permeability of composite membrane, promoting its water resistance and mechanical performance at the same time.
Prenatal toxicity of synthetic amorphous silica nanomaterial in rats.

PubMed

Hofmann, Thomas; Schneider, Steffen; Wolterbeek, André; van de Sandt, Han; Landsiedel, Robert; van Ravenzwaay, Bennard

2015-08-15

Synthetic amorphous silica is a nanostructured material, which is produced and used in a wide variety of technological applications and consumer products. No regulatory prenatal toxicity studies with this substance were reported yet. Therefore, synthetic amorphous silica was tested for prenatal toxicity, according to OECD guideline 414 in Wistar rats following oral (gavage) administration at the dose levels 0, 100, 300, or 1000mg/kg bw/d from gestation day 6-19. At gestation day 20, all pregnant animals were examined by cesarean section. Numbers of corpora lutea, implantations, resorptions, live and dead fetuses were counted. Fetal and placental weights were determined. Fetuses were examined for external, visceral and skeletal abnormalities. No maternal toxicity was observed at any dose level. Likewise, administration of the test compound did not alter cesarean section parameters and did not influence fetal or placental weights. No compound-related increase in the incidence of malformations or variations was observed in the fetuses. The no observed adverse effect level (NOAEL) was 1000mg/kg bw/d. Copyright © 2015 Elsevier Inc. All rights reserved.
Calculation of amorphous silica solubilities at 25° to 300°C and apparent cation hydration numbers in aqueous salt solutions using the concept of effective density of water

USGS Publications Warehouse

Fournier, Robert O.; Williams, Marshall L.

1983-01-01

The solubility of amorphous silica in aqueous salt solutions at 25° to 300°C can be calculated using information on its solubility in pure water and a model in which the activity of water in the salt solution is defined to equal the effective density. pe, of “free” water in that solution. At temperatures of 100°C and above, pe closely equals the product of the density of the solution times the weight fraction of water in the solution. At 25°C, a correction parameter must be applied to pe that incorporates a term called the apparent cation hydration number, h. Because of the many assumptions and other uncertainties involved in determining values of h, by the model used here, the reported numbers are not necessarily real hydration numbers even though they do agree with some published values determined by activity and diffusion methods. Whether or not h is a real hydration number, it would appear to be useful in its inclusion within a more extensive activity coefficient term that describes the departure of silica solubilities in concentrated salt solutions from expected behavior according to the model presented here. Values of h can be calculated from measured amorphous silica solubilities in salt solutions at 25°C provided there is no complexing of dissolved silica with the dissolved salt, or if the degree of complexing is known. The previously postulated aqueous silica-sulfate complexing in aqueous Na2SO4 solutions is supported by results of the present effective density of water model
High drug load, stable, manufacturable and bioavailable fenofibrate formulations in mesoporous silica: a comparison of spray drying versus solvent impregnation methods.

PubMed

Hong, Shiqi; Shen, Shoucang; Tan, David Cheng Thiam; Ng, Wai Kiong; Liu, Xueming; Chia, Leonard S O; Irwan, Anastasia W; Tan, Reginald; Nowak, Steven A; Marsh, Kennan; Gokhale, Rajeev

2016-01-01

Encapsulation of drugs in mesoporous silica using co-spray drying process has been recently explored as potential industrial method. However, the impact of spray drying on manufacturability, physiochemical stability and bioavailability in relation to conventional drug load processes are yet to be fully investigated. Using a 2(3) factorial design, this study aims to investigate the effect of drug-loading process (co-spray drying and solvent impregnation), mesoporous silica pore size (SBA-15, 6.5 nm and MCM-41, 2.5 nm) and percentage drug load (30% w/w and 50% w/w) on material properties, crystallinity, physicochemical stability, release profiles and bioavailability of fenofibrate (FEN) loaded into mesoporous silica. From the scanning electronic microscopy (SEM) images, powder X-ray diffraction and Differential scanning calorimetry measurements, it is indicated that the co-spray drying process was able to load up to 50% (w/w) FEN in amorphous form onto the mesoporous silica as compared to the 30% (w/w) for solvent impregnation. The in vitro dissolution rate of the co-spray dried formulations was also significantly (p = 0.044) better than solvent impregnated formulations at the same drug loading. Six-month accelerated stability test at 40 °C/75 RH in open dish indicated excellent physical and chemical stability of formulations prepared by both methods. The amorphous state of FEN and the enhanced dissolution profiles were well preserved, and very low levels of degradation were detected after storage. The dog data for the three selected co-spray-dried formulations revealed multiple fold increment in FEN bioavailability compared to the reference crystalline FEN. These results validate the viability of co-spray-dried mesoporous silica formulations with high amorphous drug load as potential drug delivery systems for poorly water soluble drugs.
Influence of Synthesis Mode of Supplement Based on Calcium Hydrosylicates on the Structure and Properties of Lime Compositions

NASA Astrophysics Data System (ADS)

Loganina, V. I.; Pyshkina, I. S.

2017-11-01

It was proposed to use synthesized calcium hydrosilicates in finishing lime dry mixes as a modifying supplement. The effect of substances containing amorphous silica which are used for synthesis on the activity of the modifying supplement was established. The effect of the synthesis mode of supplement on the structure formation of lime compositions was illustrated. It was found that the injection of supplements of hydrosilicates accelerates the increase of mechanical strength. The efficiency of the modifying supplements of amorphous silica, such as diatomite, in the synthesis was shown.
Manganese modified structural and optical properties of zinc soda lime silica glasses.

PubMed

Samsudin, Nur Farhana; Matori, Khamirul Amin; Wahab, Zaidan Abdul; Fen, Yap Wing; Liew, Josephine Ying Chi; Lim, Way Foong; Mohd Zaid, Mohd Hafiz; Omar, Nur Alia Sheh

2016-03-20

A series of MnO-doped zinc soda lime silica glass systems was prepared by a conventional melt and quenching technique. In this study, the x-ray diffraction analysis was applied to confirm the amorphous nature of the glasses. Fourier transform infrared spectroscopy shows the glass network consists of MnO₄, SiO₄, and ZnO₄ units as basic structural units. The glass samples under field emission scanning electron microscopy observation demonstrated irregularity in shape and size with glassy phase-like structure. The optical absorption studies revealed that the optical bandgap (E_opt) values decrease with an increase of MnO content. Through the results of various measurements, the doping of MnO in the glass matrix had effects on the performance of the glasses and significantly improved the properties of the glass sample as a potential host for phosphor material.
Effect of amorphous silica nanoparticles on in vitro RANKL-induced osteoclast differentiation in murine macrophages

NASA Astrophysics Data System (ADS)

Nabeshi, Hiromi; Yoshikawa, Tomoaki; Akase, Takanori; Yoshida, Tokuyuki; Tochigi, Saeko; Hirai, Toshiro; Uji, Miyuki; Ichihashi, Ko-Ichi; Yamashita, Takuya; Higashisaka, Kazuma; Morishita, Yuki; Nagano, Kazuya; Abe, Yasuhiro; Kamada, Haruhiko; Tsunoda, Shin-Ichi; Itoh, Norio; Yoshioka, Yasuo; Tsutsumi, Yasuo

2011-07-01

Amorphous silica nanoparticles (nSP) have been used as a polishing agent and/or as a remineralization promoter for teeth in the oral care field. The present study investigates the effects of nSP on osteoclast differentiation and the relationship between particle size and these effects. Our results revealed that nSP exerted higher cytotoxicity in macrophage cells compared with submicron-sized silica particles. However, tartrate-resistant acid phosphatase (TRAP) activity and the number of osteoclast cells (TRAP-positive multinucleated cells) were not changed by nSP treatment in the presence of receptor activator of nuclear factor κB ligand (RANKL) at doses that did not induce cytotoxicity by silica particles. These results indicated that nSP did not cause differentiation of osteoclasts. Collectively, the results suggested that nanosilica exerts no effect on RANKL-induced osteoclast differentiation of RAW264.7 cells, although a detailed mechanistic examination of the nSP70-mediated cytotoxic effect is needed.
Influence of processing parameters on microstructure and biocompatibility of surface laser sintered hydroxyapatite-SiO2 composites.

PubMed

Kivitz, E; Görke, R; Schilling, A F; Zhang, J; Heinrich, J G

2013-05-01

Silica-doped hydroxyapatite (HA) is a promising material concerning biocompatibility to natural bone, bioactivity and osteoconductive characteristics. HA exhibits phase transformations during sintering which are attendant to the change in volume and thermal strain. To avoid cracks during sintering, the exact knowledge of the phase transition temperatures is necessary. The sintering behavior of HA can be improved by adding amorphous silica with a low coefficient of thermal expansion. Therefore, the phase transformations in the system HA-SiO2 were analyzed by using differential scanning calorimetry followed by quantitative phase analysis by X-ray diffraction with the Riedveld method. The maximum sintering temperature without reversible phase transformation was defined as 1265°C. In laser surface sintered (LSS) samples, amorphous SiO2 , HA, and Si-α-TCP (or α-TCP) were detected. By comparison, only crystalline phases, such as cristobalite, HA, β-TCP, and Si-α-TCP (or α-TCP), were determined after furnace sintering. Scanning electron microscopy micrographs of furnace sintered and LSS samples show the differences in the resulting microstructures. Biocompatibility was determined by measuring cell activity of osteoblasts cultivated on four laser-sintered materials in the HA-SiO2 system in comparison to normal cell culture plastic. Cell proliferation was similar on all surfaces. The level of the cell activity on day 8 varied depending on the composition of the material and increased linearly as the amorphous SiO2 content rose. Taken together a laser-based method to develop novel biocompatible HA-SiO2 ceramics with adjustable properties and possible applications as orthopedic bioceramics are discussed. Copyright © 2012 Wiley Periodicals, Inc.
Improvements in geothermal electric power and silica production

DOEpatents

Hill, J.H.; Fulk, M.M.

Electricity is generated from hot geothermal solution by extracting heat therefrom, mineral solids which form in a so cooled geothermal solution are separated to recover minerals and facilitate reinjection of the solution into the ground. The separated solids are treated to recover silica by addition of an acid (amorphous silica precipitates) or a base (other minerals precipitate and soulble silicates are formed which are subsequently precipitated by acid neutralization). If desired, after silica is separated, other minerals can be separated and recovered.

Effect of concentrated epoxidised natural rubber and silica masterbatch for tyre application

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

Azira, A. A., E-mail: azira@lgm.gov.my; Kamal, M. M., E-mail: mazlina@lgm.gov.my; Verasamy, D., E-mail: devaraj@lgm.gov.my

The availability of concentrated epoxidised natural rubber (ENR-LC) has provided a better opportunity for using epoxidised natural rubber (ENR) with silica to reinforce natural rubber for tyre application. ENR-LC mixed directly with silica to rubber by high speed stirrer without using any coupling agent. Some rubber compounds were prepared by mixing a large amount of precipitated amorphous white silica with natural rubber. The silica was prepared in aqueous dispersion and the filler was perfectly dispersed in the ENR-LC. The performance of the composites was evaluated in this work for the viability of ENR-LC/Si in tyre compounding. Compounding was carried outmore » on a two roll mill, where the additives and curing agents was later mixed. Characterization of these composites was performed by Field Emission Scanning Electron Microscopy (FESEM) and Transmission Electron Microscopy (TEM) for dispersion as well as mechanical testing. C-ENR/Si showed efficient as primary reinforcing filler in ENR with regard to modulus and tensile strength, resulting on an increase in the stiffness of the rubbers compared to ENR latex. Overall improvement in the mechanical properties for the ENR-LC over the control crosslinked rubber sample was probably due to synergisms of silica reinforcement and crosslinking of the polymeric matrix phase.« less
Effect of concentrated epoxidised natural rubber and silica masterbatch for tyre application

NASA Astrophysics Data System (ADS)

Azira, A. A.; Verasamy, D.; Kamal, M. M.

2016-07-01

The availability of concentrated epoxidised natural rubber (ENR-LC) has provided a better opportunity for using epoxidised natural rubber (ENR) with silica to reinforce natural rubber for tyre application. ENR-LC mixed directly with silica to rubber by high speed stirrer without using any coupling agent. Some rubber compounds were prepared by mixing a large amount of precipitated amorphous white silica with natural rubber. The silica was prepared in aqueous dispersion and the filler was perfectly dispersed in the ENR-LC. The performance of the composites was evaluated in this work for the viability of ENR-LC/Si in tyre compounding. Compounding was carried out on a two roll mill, where the additives and curing agents was later mixed. Characterization of these composites was performed by Field Emission Scanning Electron Microscopy (FESEM) and Transmission Electron Microscopy (TEM) for dispersion as well as mechanical testing. C-ENR/Si showed efficient as primary reinforcing filler in ENR with regard to modulus and tensile strength, resulting on an increase in the stiffness of the rubbers compared to ENR latex. Overall improvement in the mechanical properties for the ENR-LC over the control crosslinked rubber sample was probably due to synergisms of silica reinforcement and crosslinking of the polymeric matrix phase.
The Role of Siliceous Hydrothermal Breccias in the Genesis of Volcanic Massive Sulphide Deposits - Ancient and Recent Systems

NASA Astrophysics Data System (ADS)

Costa, I. A.; Barriga, F. J.; Fouquet, Y.

2014-12-01

Siliceous hydrothermal breccias were sampled in two Mid-Atlantic Ridge active sites: Lucky Strike and Menez Gwen. These hydrothermal fields are located in the border of the Azorean plateau, southwest of the Azores islands where the alteration processes affecting basaltic rocks are prominent (Costa et al., 2003). The hydrothermal breccias are genetically related with the circulation of low temperature hydrothermal fluids in diffuse vents. The groundmass of these breccias precipitates from the fluid and consolidates the clastic fragments mostly composed of basalt. The main sources are the surrounding volcanic hills. Breccias are found near hydrothermal vents and may play an important role in the protection of subseafloor hydrothermal deposits forming an impermeable cap due to the high content in siliceous material. The amorphous silica tends to precipitate when the fluid is conductively cooled as proposed by Fouquet et al. (1998) after Fournier (1983). The process evolves gradually from an initial stage where we have just the fragments and circulating seawater. The ascending hydrothermal fluid mixes with seawater, which favours the precipitation of the sulphide components. Sealing of the initially loose fragments begins, the temperature rises below this crust, and the processes of mixing fluid circulation and conductive cooling are simultaneous. At this stage the fluid becomes oversaturated with respect to amorphous silica. This form of silica can precipitate in the open spaces of the porous sulphides and seal the system. Normally this can happen at low temperatures. At this stage the hydrothermal breccia is formed creating a progressively less permeable, eventually impermeable cap rock at the surface. Once the fluid is trapped under this impermeable layer, conductive cooling is enhanced and mixing with seawater is restricted, making the precipitation of amorphous silica more efficient. Since the first discovery and description of recent mineralized submarine hydrothermal deposits, comparison with ancient volcanic massive sulphide deposits is appropriate. The proposed model can explain some of the processes taking place in the early phase of formation of old deposits where equivalent siliceous material is found in the hanging wall of the ore bodies (e.g. Barriga and Fyfe, 1988).
High thermal behavior of a new glass ceramic developed from silica xerogel/SnO{sub 2} composite

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

Aripin, H., E-mail: aripin@unsil.ac.id; Mitsudo, Seitaro, E-mail: mitsudo@fir.u-fukui.ac.jp; Sudiana, I. Nyoman, E-mail: sudiana75@yahoo.com

2016-02-08

In this investigation, a new glass ceramics have been produced by mixing SnO{sub 2} and amorphous silica xerogel (ASX) extracted from sago waste ash. The composition has been prepared by adding 10 mol% of SnO{sub 2} into SX. The samples have been dry pressed and sintered in the temperature range between 800 °C and 1500 °C. The effects of temperature on the crystallization of silica xerogel after adding SnO{sub 2} and their relationship to bulk density have been studied. The crystallization process of the silica xerogel/SnO{sub 2} composite has been examined by an X-ray diffraction (XRD) and the bulk density hasmore » been characterized on the basis of the experimental data obtained using Archimedes′ principle. It has been found that an addition of SnO{sub 2} confers an appreciable effect on the grain and from the interpretation of XRD patterns allow one to explain the increase in the density by an increased crystallite size of SnO{sub 2} in the composite.« less
High thermal behavior of a new glass ceramic developed from silica xerogel/SnO2 composite

NASA Astrophysics Data System (ADS)

Aripin, H.; Mitsudo, Seitaro; Sudiana, I. Nyoman; Priatna, Edvin; Sabchevski, Svilen

2016-02-01

In this investigation, a new glass ceramics have been produced by mixing SnO2 and amorphous silica xerogel (ASX) extracted from sago waste ash. The composition has been prepared by adding 10 mol% of SnO2 into SX. The samples have been dry pressed and sintered in the temperature range between 800 °C and 1500 °C. The effects of temperature on the crystallization of silica xerogel after adding SnO2 and their relationship to bulk density have been studied. The crystallization process of the silica xerogel/SnO2 composite has been examined by an X-ray diffraction (XRD) and the bulk density has been characterized on the basis of the experimental data obtained using Archimedes' principle. It has been found that an addition of SnO2 confers an appreciable effect on the grain and from the interpretation of XRD patterns allow one to explain the increase in the density by an increased crystallite size of SnO2 in the composite.
Amorphous Silica-Promoted Lysine Dimerization: a Thermodynamic Prediction

NASA Astrophysics Data System (ADS)

Kitadai, Norio; Nishiuchi, Kumiko; Nishii, Akari; Fukushi, Keisuke

2018-03-01

It has long been suggested that mineral surfaces played a crucial role in the abiotic polymerization of amino acids that preceded the origin of life. Nevertheless, it remains unclear where the prebiotic process took place on the primitive Earth, because the amino acid-mineral interaction and its dependence on environmental conditions have yet to be understood adequately. Here we examined experimentally the adsorption of L-lysine (Lys) and its dimer (LysLys) on amorphous silica over a wide range of pH, ionic strength, adsorbate concentration, and the solid/water ratio, and determined the reaction stoichiometries and the equilibrium constants based on the extended triple-layer model (ETLM). The retrieved ETLM parameters were then used, in combination with the equilibrium constant for the peptide bond formation in bulk water, to calculate the Lys-LysLys equilibrium in the presence of amorphous silica under various aqueous conditions. Results showed that the silica surface favors Lys dimerization, and the influence varies greatly with changing environmental parameters. At slightly alkaline pH (pH 9) in the presence of a dilute NaCl (1 mM), the thermodynamically attainable LysLys from 0.1 mM Lys reached a concentration around 50 times larger than that calculated without silica. Because of the versatility of the ETLM, which has been applied to describe a wide variety of biomolecule-mineral interactions, future experiments with the reported methodology are expected to provide a significant constraint on the plausible geological settings for the condensation of monomers to polymers, and the subsequent chemical evolution of life.
Ordered nanoporous silica as carriers for improved delivery of water insoluble drugs: a comparative study between three dimensional and two dimensional macroporous silica

PubMed Central

Wang, Ying; Zhao, Qinfu; Hu, Yanchen; Sun, Lizhang; Bai, Ling; Jiang, Tongying; Wang, Siling

2013-01-01

The goal of the present study was to compare the drug release properties and stability of the nanoporous silica with different pore architectures as a matrix for improved delivery of poorly soluble drugs. For this purpose, three dimensional ordered macroporous (3DOM) silica with 3D continuous and interconnected macropores of different sizes (200 nm and 500 nm) and classic mesoporous silica (ie, Mobil Composition of Matter [MCM]-41 and Santa Barbara Amorphous [SBA]-15) with well-ordered two dimensional (2D) cylindrical mesopores were successfully fabricated and then loaded with the model drug indomethacin (IMC) via the solvent deposition method. Scanning electron microscopy (SEM), N2 adsorption, differential scanning calorimetry (DSC), and X-ray diffraction (XRD) were applied to systematically characterize all IMC-loaded nanoporous silica formulations, evidencing the successful inclusion of IMC into nanopores, the reduced crystallinity, and finally accelerated dissolution of IMC. It was worth mentioning that, in comparison to 2D mesoporous silica, 3DOM silica displayed a more rapid release profile, which may be ascribed to the 3D interconnected pore networks and the highly accessible surface areas. The results obtained from the stability test indicated that the amorphous state of IMC entrapped in the 2D mesoporous silica (SBA-15 and MCM-41) has a better physical stability than in that of 3DOM silica. Moreover, the dissolution rate and stability of IMC loaded in 3DOM silica was closely related to the pore size of macroporous silica. The colorimetric 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and Cell Counting Kit (CCK)-8 assays in combination with direct morphology observations demonstrated the good biocompatibility of nanoporous silica, especially for 3DOM silica and SBA-15. The present work encourages further study of the drug release properties and stability of drug entrapped in different pore architecture of silica in order to realize their potential in oral drug delivery. PMID:24174875
Presence of nano-sized silica during in vitro digestion of foods containing silica as a food additive.

PubMed

Peters, Ruud; Kramer, Evelien; Oomen, Agnes G; Rivera, Zahira E Herrera; Oegema, Gerlof; Tromp, Peter C; Fokkink, Remco; Rietveld, Anton; Marvin, Hans J P; Weigel, Stefan; Peijnenburg, Ad A C M; Bouwmeester, Hans

2012-03-27

The presence, dissolution, agglomeration state, and release of materials in the nano-size range from food containing engineered nanoparticles during human digestion is a key question for the safety assessment of these materials. We used an in vitro model to mimic the human digestion. Food products subjected to in vitro digestion included (i) hot water, (ii) coffee with powdered creamer, (iii) instant soup, and (iv) pancake which either contained silica as the food additive E551, or to which a form of synthetic amorphous silica or 32 nm SiO(2) particles were added. The results showed that, in the mouth stage of the digestion, nano-sized silica particles with a size range of 5-50 and 50-500 nm were present in food products containing E551 or added synthetic amorphous silica. However, during the successive gastric digestion stage, this nano-sized silica was no longer present for the food matrices coffee and instant soup, while low amounts were found for pancakes. Additional experiments showed that the absence of nano-sized silica in the gastric stage can be contributed to an effect of low pH combined with high electrolyte concentrations in the gastric digestion stage. Large silica agglomerates are formed under these conditions as determined by DLS and SEM experiments and explained theoretically by the extended DLVO theory. Importantly, in the subsequent intestinal digestion stage, the nano-sized silica particles reappeared again, even in amounts higher than in the saliva (mouth) digestion stage. These findings suggest that, upon consumption of foods containing E551, the gut epithelium is most likely exposed to nano-sized silica. © 2012 American Chemical Society
Water at silica/liquid water interfaces investigated by DFT-MD simulations

NASA Astrophysics Data System (ADS)

Gaigeot, Marie-Pierre

This talk is dedicated to probing the microscopic structural organization of water at silica/liquid water interfaces including electrolytes by first principles DFT-based molecular dynamics simulations (DFT-MD). We will present our very recent DFT-MD simulations of electrolytic (KCl, NaCl, NaI) silica/liquid water interfaces in order to unravel the intertwined structural properties of water and electrolytes at the crystalline quartz/liquid water and amorphous silica/liquid water interfaces. DFT-MD simulations provide direct knowledge of the structural organization of water and the H-Bond network formed between the water molecules within the different water layers above the silica surface. One can furthermore extract vibrational signatures of the water molecules within the interfacial layers from the DFT-MD simulations, especially non-linear SFG (Sum Frequency generation) signatures that are active at solid/liquid interfaces. The strength of the simulated spectra is that a detailed analysis of the signatures in terms of the water/water H-Bond networks formed within the interfacial water layers and in terms of the water/silica or water/electrolytes H-Bond networks can be given. Comparisons of SFG spectra between quartz/water/electrolytes and amorphous silica/water/electrolytes interfaces allow us to definitely conclude on how the structural arrangements of liquid water at these electrolytic interfaces modulate the final spectroscopic signatures. Invited speaker.
Tadalafil inclusion in microporous silica as effective dissolution enhancer: optimization of loading procedure and molecular state characterization.

PubMed

Mehanna, Mohammed M; Motawaa, Adel M; Samaha, Magda W

2011-05-01

Tadalafil is an efficient drug used to treat erectile dysfunction characterized by poor water solubility, which has a negative influence on its bioavailability. Utilization of microporous silica represents an effective and facile technology to increase the dissolution rate of poorly soluble drugs. Our strategy involved directly introducing tadalafil as guest molecule into microporous silica as host material by incipient wetness impregnation method. To optimize tadalafil inclusion, response surface methodology (RSM) using 3(3) factorial design was utilized. Furthermore, to investigate the molecular state of tadalafil, Fourier-transform infrared spectroscopy, differential scanning calorimetery, thermal gravimetrical analysis, nitrogen adsorption, and powder X-ray diffraction (PXRD) were carried out. The results obtained pointed out that the quantity of microporous silica was the predominant factor that increased the loading efficiency. For the optimized formula, the loading efficiency was 42.50 wt %. Adsorption-desorption experiments indicated that tadalafil has been introduced into the micropores. Powder XRD and differential scanning calorimetry analyses revealed that tadalafil is arranged in amorphous form. In addition, the dissolution rate of tadalafil from the microporous silica was faster than that of free drug. Amorphous tadalafil occluded in microporous silica did not crystallize over 3 months. These findings contributed in opening a new strategy concerning the utilization of porous silica for the dissolution rate enhancement. Copyright © 2010 Wiley-Liss, Inc.
Fabrication of amorphous silica nanowires via oxygen plasma treatment of polymers on silicon

NASA Astrophysics Data System (ADS)

Chen, Zhuojie; She, Didi; Chen, Qinghua; Li, Yanmei; Wu, Wengang

2018-02-01

We demonstrate a facile non-catalytic method of fabricating silica nanowires at room temperature. Different polymers including photoresists, parylene C and polystyrene are patterned into pedestals on the silicon substrates. The silica nanowires are obtained via the oxygen plasma treatment on those pedestals. Compared to traditional strategies of silica nanowire fabrication, this method is much simpler and low-cost. Through designing the proper initial patterns and plasma process parameters, the method can be used to fabricate various regiment nano-scale silica structure arrays in any laboratory with a regular oxygen-plasma-based cleaner or reactive-ion-etching equipment.
High Pressure Response of Siliceous Materials

DTIC Science & Technology

2013-02-01

iron-containing soda lime silicate glass, opal (a hydrated silicate glass), ROBAX glass ceramic, and others were single crystal (α-quartz) and...10 2.6. Opal (hydrated amorphous silica...Raman spectrum as a function of stress for opal (hydrated silica) glass. ................... 29 4.9. Raman spectrum as a function of stress for
Advanced Research Projects Agency on Materials Preparation and Characterization Research

DTIC Science & Technology

Briefly summarized is research concerned with such topics as: Preparation of silica glass from amorphous silica; Glass structure by Raman ...ferroelectrics; Silver iodide crystals; Vapor phase growth; Refractory optical host materials; Hydroxyapatite ; Calcite; Characterization of single crystals with a double crystal spectrometer; Characterization of residual strain.
Computer Simulation of Fracture in Aerogels

NASA Technical Reports Server (NTRS)

Good, Brian S.

2006-01-01

Aerogels are of interest to the aerospace community primarily for their thermal properties, notably their low thermal conductivities. While the gels are typically fragile, recent advances in the application of conformal polymer layers to these gels has made them potentially useful as lightweight structural materials as well. In this work, we investigate the strength and fracture behavior of silica aerogels using a molecular statics-based computer simulation technique. The gels' structure is simulated via a Diffusion Limited Cluster Aggregation (DLCA) algorithm, which produces fractal structures representing experimentally observed aggregates of so-called secondary particles, themselves composed of amorphous silica primary particles an order of magnitude smaller. We have performed multi-length-scale simulations of fracture in silica aerogels, in which the interaction b e e n two secondary particles is assumed to be described by a Morse pair potential parameterized such that the potential range is much smaller than the secondary particle size. These Morse parameters are obtained by atomistic simulation of models of the experimentally-observed amorphous silica "bridges," with the fracture behavior of these bridges modeled via molecular statics using a Morse/Coulomb potential for silica. We consider the energetics of the fracture, and compare qualitative features of low-and high-density gel fracture.
Low-temperature behavior of core-softened models: water and silica behavior.

PubMed

Jagla, E A

2001-06-01

A core-softened model of a glass forming fluid is numerically studied in the limit of very low temperatures. The model shows two qualitatively different behaviors depending on the strength of the attraction between particles. For no or low attraction, the changes of density as a function of pressure are smooth, although hysteretic due to mechanical metastabilities. For larger attraction, sudden changes of density upon compressing and decompressing occur. This global mechanical instability is correlated to the existence of a thermodynamic first-order amorphous-amorphous transition. The two different behaviors obtained correspond qualitatively to the different phenomenology observed in silica and water.
AFM-porosimetry: density and pore volume measurements of particulate materials.

PubMed

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.
Gold atoms and dimers on amorphous SiO(2): calculation of optical properties and cavity ringdown spectroscopy measurements.

PubMed

Del Vitto, Annalisa; Pacchioni, Gianfranco; Lim, Kok Hwa; Rösch, Notker; Antonietti, Jean-Marie; Michalski, Marcin; Heiz, Ulrich; Jones, Harold

2005-10-27

We report on the optical absorption spectra of gold atoms and dimers deposited on amorphous silica in size-selected fashion. Experimental spectra were obtained by cavity ringdown spectroscopy. Issues on soft-landing, fragmentation, and thermal diffusion are discussed on the basis of the experimental results. In parallel, cluster and periodic supercell density functional theory (DFT) calculations were performed to model atoms and dimers trapped on various defect sites of amorphous silica. Optically allowed electronic transitions were calculated, and comparisons with the experimental spectra show that silicon dangling bonds [[triple bond]Si(.-)], nonbridging oxygen [[triple bond]Si-O(.-)], and the silanolate group [[triple bond]Si-O(-)] act as trapping centers for the gold particles. The results are not only important for understanding the chemical bonding of atoms and clusters on oxide surfaces, but they will also be of fundamental interest for photochemical studies of size-selected clusters on surfaces.
A hydrothermal peroxo method for preparation of highly crystalline silica-titania photocatalysts.

PubMed

Krivtsov, Igor; Ilkaeva, Marina; Avdin, Viacheslav; Khainakov, Sergei; Garcìa, Jose R; Ordòñez, Salvador; Dìaz, Eva; Faba, Laura

2015-04-15

A new completely inorganic method of preparation of silica-titania photocatalyst has been described. It has been established that the addition of silica promotes crystallinity of TiO2 anatase phase. Relative crystallinity and TiO2 crystal size in the silica-titania particles increase with the silica content until SiO2/TiO2 molar ratio of 0.9, but at higher molar ratios they start to decrease. The single-source precursor containing peroxo titanic (PTA) and silicic acids has been proved to be responsible for high crystallinity of TiO2 encapsulated into amorphous silica. It has been proposed that peroxo groups enhance rapid formation of crystalline titania seeds, while silica controls their growth. It has been concluded from the TEM that the most morphologically uniform anatase crystallites covered with SiO2 particles are prepared at SiO2/TiO2 molar ratio of 0.4. This sample, according to (29)Si NMR, also shows the high content of hydroxylated silica Q(3) and Q(2) groups, and it is the most photocatalytically active in UV-assisted decomposition of methylene blue among the tested materials. It has been determined that the increase in the amount of the condensed Q(4) silica in the mixed oxides leads to the decrease in photocatalytic performance of the material, despite its better crystallinity. High crystallinity, low degree of incorporation of Ti atoms in SiO2 in the mixed oxide and adsorption of methylene blue in the vicinity of photoactive sites on the hydroxylated silica have been considered as the main factors determining the high degradation degree of methylene blue in the presence of silica-titania. Copyright © 2014 Elsevier Inc. All rights reserved.
Crystalline silicon growth in nickel/a-silicon bilayer

NASA Astrophysics Data System (ADS)

Mohiddon, Md Ahamad; Naidu, K. Lakshun; Dalba, G.; Rocca, F.; Krishna, M. Ghanashyam

2013-02-01

The effect of substrate temperature on amorphous Silicon crystallization, mediated by metal impurity is reported. Bilayers of Ni(200nm)/Si(400nm) are deposited on fused silica substrate by electron beam evaporator at 200 and 500 °C. Raman mapping shows that, 2 to 5 micron size crystalline silicon clusters are distributed over the entire surface of the sample. X-ray diffraction and X-ray absorption spectroscopy studies demonstrate silicon crystallizes over the metal silicide seeds and grow with the annealing temperature.
Characterizing Crystalline-Vitreous Structures: From Atomically Resolved Silica to Macroscopic Bubble Rafts

ERIC Educational Resources Information Center

Burson, Kristen M.; Schlexer, Philomena; Bu¨chner, Christin; Lichtenstein, Leonid; Heyde, Markus; Freund, Hans-Joachim

2015-01-01

A two-part experiment using bubble rafts to analyze amorphous structures is presented. In the first part, the distinctions between crystalline and vitreous structures are examined. In the second part, the interface between crystalline and amorphous regions is considered. Bubble rafts are easy to produce and provide excellent analogy to recent…

Novel 3-hydroxypropyl bonded phase by direct hydrosilylation of allyl alcohol on amorphous hydride silica

PubMed Central

Gómez, Jorge E.; Navarro, Fabián H.; Sandoval, Junior E.

2015-01-01

A novel 3-hydroxypropyl (propanol) bonded silica phase has been prepared by hydrosilylation of allyl alcohol on a hydride silica intermediate, in the presence of platinum (0)-divinyltetramethyldisiloxane (Karstedt's catalyst). The regio-selectivity of this synthetic approach had been correctly predicted by previous reports involving octakis(dimethylsiloxy)octasilsesquioxane (Q8M8H) and hydrogen silsesquioxane (T8H8), as molecular analogs of hydride amorphous silica. Thus, C-silylation predominated (~ 94%) over O-silylation, and high surface coverages of propanol groups (5±1 µmol/m2) were typically obtained in this work. The propanol-bonded phase was characterized by spectroscopic (IR and solid state NMR on silica microparticles), contact angle (on fused-silica wafers) and CE (on fused-silica tubes) techniques. CE studies of the migration behavior of pyridine, caffeine, tris(2,2’-bipyridine)Ru(II) chloride and lysozyme on propanol-modified capillaries were carried out. The adsorption properties of these select silanol-sensitive solutes were compared to those on the unmodified and hydride-modified tubes. It was found that hydrolysis of the SiH species underlying the immobilized propanol moieties leads mainly to strong ion-exchange based interactions with the basic solutes at pH 4, particularly with lysozyme. Interestingly, and in agreement with water contact angle and electroosmotic mobility figures, the silanol-probe interactions on the buffer-exposed (hydrolyzed) hydride surface are quite different from those of the original unmodified tube. PMID:24934906
Silica-rich deposits and hydrated minerals at Gusev Crater, Mars: Vis-NIR spectral characterization and regional mapping

USGS Publications Warehouse

Rice, M.S.; Bell, J.F.; Cloutis, E.A.; Wang, A.; Ruff, S.W.; Craig, M.A.; Bailey, D.T.; Johnson, J. R.; De Souza, P.A.; Farrand, W. H.

2010-01-01

The Mars Exploration Rover (MER) Spirit has discovered surprisingly high concentrations of amorphous silica in soil and nodular outcrops in the Inner Basin of the Columbia Hills. In Pancam multispectral observations, we find that an absorption feature at the longest Pancam wavelength (1009 nm) appears to be characteristic of these silica-rich materials; however, spectral analyses of amorphous silica suggest that the ???1009 nm spectral feature is not a direct reflection of their silica-rich nature. Based on comparisons with spectral databases, we hypothesize that the presence of H2O or OH, either free (as water ice), adsorbed or bound in a mineral structure, is responsible for the spectral feature observed by Pancam. The Gertrude Weise soil, which is nearly pure opaline silica, may have adsorbed water cold-trapped on mineral grains. The origin of the ???1009 nm Pancam feature observed in the silica-rich nodular outcrops may result from the presence of additional hydrated minerals (specific sulfates, halides, chlorides, sodium silicates, carbonates or borates). Using the ???1009 nm feature with other spectral parameters as a "hydration signature" we have mapped the occurrence of hydrated materials along the extent of Spirit's traverse across the Columbia Hills from West Spur to Home Plate (sols 155-1696). We have also mapped this hydration signature across large panoramic images to understand the regional distribution of materials that are spectrally similar to the silica-rich soil and nodular outcrops. Our results suggest that hydrated materials are common in the Columbia Hills. ?? 2009 Elsevier Inc.
Loading amorphous Asarone in mesoporous silica SBA-15 through supercritical carbon dioxide technology to enhance dissolution and bioavailability.

PubMed

Zhang, Zhengzan; Quan, Guilan; Wu, Qiaoli; Zhou, Chan; Li, Feng; Bai, Xuequn; Li, Ge; Pan, Xin; Wu, Chuanbin

2015-05-01

The aim of this study was to load amorphous hydrophobic drug into ordered mesoporous silica (SBA-15) by supercritical carbon dioxide technology in order to improve the dissolution and bioavailability of the drug. Asarone was selected as a model drug due to its lipophilic character and poor bioavailability. In vitro dissolution and in vivo bioavailability of the obtained Asarone-SBA-15 were significantly improved as compared to the micronized crystalline drug. This study offers an effective, safe, and environmentally benign means of solving the problems relating to the solubility and bioavailability of hydrophobic molecules. Copyright © 2015 Elsevier B.V. All rights reserved.
Raman study of opal at high pressure

NASA Astrophysics Data System (ADS)

Farfan, G.; Wang, S.; Mao, W. L.

2011-12-01

More commonly known for their beauty and lore as gemstones, opals are also intriguing geological materials which may have potential for materials science applications. Opal lacks a definite crystalline structure, and is composed of an amorphous packing of hydrated silica (SiO2) spheroids, which provides us with a unique nano-scaled mineraloid with properties unlike those of other amorphous materials like glass. Opals from different localities were studied at high pressure using a diamond anvil cell to apply pressure and Raman spectroscopy to look at changes in bonding as pressure was increased. We first tested different samples from Virgin Valley, NV, Spencer, ID, Juniper Ridge, OR, and Australia, which contain varying amounts of water at ambient conditions, using Raman spectroscopy to determine if they were opal-CT (semicrystalline cristobalite-trydimite volcanic origin) or opal-A (amorphous sedimentary origin). We then used x-ray diffraction and Raman spectroscopy in a diamond anvil cell to see how their bonding and structure changed under compression and to determine what effect water content had on their high pressure behavior. Comparison of our results on opal to other high pressure studies of amorphous materials like glass has implications from a geological and materials science standpoint.
Speciation and Health Risks of Atmospheric Nanoparticulates

NASA Astrophysics Data System (ADS)

Nguyen, Kennedy

Exposure to air pollution causes several adverse health effects such as asthma, respiratory disease, cardiovascular disease, cancer, and premature death; and the San Joaquin Valley is one of the most heavily polluted regions in the US. The mountains that surround the valley allow air pollution, including particulate matter, to remain stagnant, prolonging the exposure of valley populations to it. The primary sources of particulate matter for this region are aluminosilicate dust from agricultural activities, and soot emissions from diesel trucks and vehicular traffic. A substantial fraction of emitted material is nanoparticulate matter (<100 nm), which contains trace iron and polycyclic aromatic hydrocarbons that can traverse into human organs via the lungs, initiate inflammation, and lead to disease. The traditional approach of reducing the total mass of emitted material is beginning to reach its limit of effectiveness for mitigating the negative health impacts of particulate matter. There is a need for chemical speciation of particulate matter that will allow the identification of the chemical and physical properties of particulates by source, the creation of well-controlled proxy particles with those properties for testing in cell culture studies, and correlation of particulate properties and sources with their negative health impacts. These results can help identify the sources of air pollution to prioritize for mitigation for the greatest health benefit. In addition, further chemical speciation can help monitor the results of such mitigation efforts. Here, natural particulate matter samples from Merced and Fresno, two cities in the San Joaquin Valley, were analyzed. Ultrafine particles present were 40 to 50 nm in diameter and mostly composed of aluminum, silicon, oxygen, and iron hydroxide. XAS data confirmed the presence of the aluminosilicate as smectite clay and the iron hydroxide as ferrihydrite. Furthermore, a chemical speciation study investigated industrial emissions of air particulate matter. Samples were analyzed using electron microscopy for elemental composition and size distribution, and found to contain fine metal particulates (lead and iron) that can lead to lung inflammation. From characterization data, in order to create a simplified proxy particle system for cell culture studies, amorphous silica particles were synthesized using a modified Stober Synthesis and coated with iron hydroxide. A range of iron hydroxide concentrations (0.06 to 1.63 mmol of iron per gram of silica) were used to test the effect of iron contamination on THP-1 cells, and higher concentrations of iron with silica (0.43 and 1.63 mmol of iron per gram of silica) were found to increase production of pro-inflammatory mediators compared to silica alone. Iron alone did not induce an effect relative to the control, demonstrating a synergistic effect when iron is combined with silica at low doses. It was found that crystalline silica was more toxic than amorphous silica (70% vs 80% respectively at 100 mug/ml). In addition, mesoporous silica was found to be more toxic than solid silica (73% vs 82% respectively at 100 mug/ml), likely due to a higher surface area (60.2 m2/g for mesoporous external surface area without internal pores vs 1.72 m 2/g for solid 2 mum silica and 54.5 m2/g for 50 nm silica) and increased particle loading at the same dose. Finally, a preliminary investigation of Printex 90 as a proxy material for soot, with and without the addition of iron and quinones, was conducted.
Simultaneous utilization of soju industrial waste for silica production and its residue ash as effective cationic dye adsorbent

USDA-ARS?s Scientific Manuscript database

Soju industrial waste is an important biomass resource. The present study is aimed to utilize soju industrial waste for silica extraction, and residual ash as a low cost adsorbent for the removal of Methylene Blue (MB) from aqueous solution. High percentage of pure amorphous nanosilica was obtained ...
Different mechanisms for acid weathering of crystalline basalt vs. basaltic glass and implications for detection on Mars

NASA Astrophysics Data System (ADS)

Horgan, B. H. N.; Smith, R.; Christensen, P. R.; Cloutis, E.

2016-12-01

Silica-rich acid leached rinds and coatings occur in volcanic environments on Earth and have been identified using orbital spectroscopy on Mars, but their development is poorly understood. We simulated long-term open-system acid weathering in a laboratory by repeatedly submerging and rinsing crystalline and glassy basalts in pH 1 and 3 acidic solutions for 220 days. Visible/near-infrared (VNIR; 0.3-2.5 μm) and thermal-infrared (TIR; 5-50 μm) spectra of the samples were compared to their microscopic properties from scanning electron microscopy (SEM). While previous studies have shown that exposure to moderately low pH ( 3) solutions can produce mineral precipitates, we find that there is very little spectral or microphysical effect on the underlying parent material. In contrast, materials exposed to very low pH ( 1) solutions were visibly altered in SEM images, and contained regions enriched in amorphous silica. These samples exhibited clear silica VNIR and TIR spectral signatures that increased in intensity with their glass content. In addition, glass exposed to low pH solutions often exhibited blue and concave up VNIR slopes. SEM indicates that these spectral differences correspond to different modes of alteration. In glass, low pH alteration occurs only at the surface and produces a silica-enriched rind. In more crystalline samples, alteration penetrates the interior to cause dissolution and replacement by silica. Thus, along with the pH of the aqueous environment, the crystallinity of a rock can greatly affect the way and the degree to which it is weathered. Because alteration is restricted to the surface of glassy materials, bulk glass is more stable than crystalline basalt under long-term acidic leaching. Leached glasses are consistent with OMEGA and TES spectra of the martian northern lowlands, and may contribute to the high-silica phases detected globally in TES Surface Type 2. Thus, both glass-rich deposits and acidic weathering may have been widespread on Mars.
The electronic and optical properties of amorphous silica with hydrogen defects by ab initio calculations

NASA Astrophysics Data System (ADS)

Ren, Dahua; Xiang, Baoyan; Hu, Cheng; Qian, Kai; Cheng, Xinlu

2018-04-01

Hydrogen can be trapped in the bulk materials in four forms: interstitial molecular H2, interstitial atom H, O‑H+(2Si=O–H)+, Si‑H‑( {{4O}}\\bar \\equiv {{Si&x2212H}})‑ to affect the electronic and optical properties of amorphous silica. Therefore, the electronic and optical properties of defect-free and hydrogen defects in amorphous silica were performed within the scheme of density functional theory. Initially, the negative charged states hydrogen defects introduced new defect level between the valence band top and conduction band bottom. However, the neutral and positive charged state hydrogen defects made both the valence band and conduction band transfer to the lower energy. Subsequently, the optical properties such as absorption spectra, conductivity and loss functions were analyzed. It is indicated that the negative hydrogen defects caused the absorption peak ranging from 0 to 2.0 eV while the positive states produced absorption peaks at lower energy and two strong absorption peaks arose at 6.9 and 9.0 eV. However, the neutral hydrogen defects just improved the intensity of absorption spectrum. This may give insights into understanding the mechanism of laser-induced damage for optical materials. Project supported by the Science and Technology of Hubei Provincial Department of Education (No. B2017098).
Hierarchical structures of amorphous solids characterized by persistent homology

PubMed Central

Hiraoka, Yasuaki; Nakamura, Takenobu; Hirata, Akihiko; Escolar, Emerson G.; Matsue, Kaname; Nishiura, Yasumasa

2016-01-01

This article proposes a topological method that extracts hierarchical structures of various amorphous solids. The method is based on the persistence diagram (PD), a mathematical tool for capturing shapes of multiscale data. The input to the PDs is given by an atomic configuration and the output is expressed as 2D histograms. Then, specific distributions such as curves and islands in the PDs identify meaningful shape characteristics of the atomic configuration. Although the method can be applied to a wide variety of disordered systems, it is applied here to silica glass, the Lennard-Jones system, and Cu-Zr metallic glass as standard examples of continuous random network and random packing structures. In silica glass, the method classified the atomic rings as short-range and medium-range orders and unveiled hierarchical ring structures among them. These detailed geometric characterizations clarified a real space origin of the first sharp diffraction peak and also indicated that PDs contain information on elastic response. Even in the Lennard-Jones system and Cu-Zr metallic glass, the hierarchical structures in the atomic configurations were derived in a similar way using PDs, although the glass structures and properties substantially differ from silica glass. These results suggest that the PDs provide a unified method that extracts greater depth of geometric information in amorphous solids than conventional methods. PMID:27298351
Allophane on Mars: Evidence from IR Spectroscopy and TES Spectral Models

NASA Technical Reports Server (NTRS)

Ming, Douglas W.; Rampe, E. B.; Kraft, M. D.; Sharp. T. G.; Golden, D. C.; Christensen, P. C.

2010-01-01

Allophane is an alteration product of volcanic glass and a clay mineral precursor that is commonly found in basaltic soils on Earth. It is a poorly-crystalline or amorphous, hydrous aluminosilicate with Si/Al ratios ranging from approx.0.5-1 [Wada, 1989]. Analyses of thermal infrared (TIR) spectra of the Martian surface from TES show high-silica phases at mid-to-high latitudes that have been proposed to be primary volcanic glass [Bandfield et al., 2000; Bandfield, 2002; Rogers and Christensen, 2007] or poorly-crystalline secondary silicates such as allophane or aluminous amorphous silica [Kraft et al., 2003; Michalski et al., 2006; Rogers and Christensen, 2007; Kraft, 2009]. Phase modeling of chemical data from the APXS on the Mars Exploration Rover Spirit suggest the presence of allophane in chemically weathered rocks [Ming et al., 2006]. The presence of allophane on Mars has not been previously tested with IR spectroscopy because allophane spectra have not been available. We synthesized allophanes and allophanic gels with a range of Si/Al ratios to measure TIR emission and VNIR reflectance spectra and to test for the presence of allophane in Martian soils. VNIR reflectance spectra of the synthetic allophane samples have broad absorptions near 1.4 m from OH stretching overtones and 1.9 m from a combination of stretching and bending vibrations in H2O. Samples have a broad absorption centered near 2.25 microns, from AlAlOH combination bending and stretching vibrations, that shifts position with Si/Al ratio. Amorphous silica (opaline silica or primary volcanic glass) has been identified in CRISM spectra of southern highland terrains based on the presence of 1.4, 1.9, and broad 2.25 m absorptions [Mustard et al., 2008]; however, these absorptions are also consistent with the presence of allophane. TIR emission spectra of the synthetic allophanes show two spectrally distinct types: Si-rich and Al-rich. Si-rich allophanes have two broad absorptions centered near 1080 and 430 cm-1 from Si(Al)-O stretching and Si(Al)-O bending vibrations, respectively, and Al-rich allophanes have three broad absorptions centered near 950, 540, and 430 cm-1. We used a spectral library commonly used to deconvolve TES spectra and four allophane spectra to model nine spectrally distinct regions on Mars [from Rogers et al., 2007]. Regions previously modeled with high-silica phases contain significant amounts of allophane (>10 vol.%) in our models. Our models of northern Acidalia, the type locality for surface type 2 materials, contain 40 vol.% Si-rich allophane. The presence of allophane in multiple surface regions of Mars indicates a more widespread occurrence of low-temperature aqueous alteration at moderate pH than has been previously recognized. The regional variations in modeled abundances and the types of allophane (Si- vs. Al-rich) suggest regional differences in Mars weathering processes.
Light scattering by dust particles (PROGRA2 experiment): size and structure effects for transparent and absorbing materials

NASA Astrophysics Data System (ADS)

Hadamcik, E.; Renard, J.-B.; Lasue, J.; Levasseur-Regourd, A. C.

2007-08-01

1- Introduction Cometary and possibly interplanetary dust particles seem to be mainly made of agglomerates of submicron and micron-sized grains. These particles are among the most primitive in our solar system. Regoliths on asteroidal and planetary surfaces seem to be loose materials produced by impinging meteorites on the surface of small bodies. Comparing their physical properties is thus fundamental to understand their evolution. To interpret remote observations of solar light scattered by dust particles and regoliths, it is necessary to use numerical and experimental simulations [1,2,3]. 2- PROGRA2 experiment PROGRA2 instruments are polarimeters; the light sources are two randomly polarized lasers (632.8 nm and 543.5 nm). Levitating particles (in microgravity or lifted by an air-draught) are studied by imaging polarimetry. Details on the instruments can be found in [4,5]. 3- Samples Two kinds of samples are studied: compact particles in the (1-400) micrometer size range and fluffy aggregates in the same size range, made from submicron and micronsized grains. The materials are transparent silica and absorbing carbon. Some deposited particles are huge agglomerates of micron-sized grains produced by random ballistic deposition of single grains [6,7] or produced by evaporation of mixtures in alcohol of fluffy aggregates of submicron-sized grains. Two samples are made of silica spheres coated by a carbonaceous black compound. Cometary analogues are mixtures of silica and amorphous carbon or Mg-Fe silicates mixed with amorphous carbon. 4- Results Phase curves and their main parameters (negative polarization at small phase angles and maximum polarization, Pmax, at 90-100° phase angle) for the different materials will be compared and related to the physical properties. For example, it is well known by numerical simulations and/or by experiments that the maximum polarization decreases when the size (submicrometer range) of the grains increases [2,8,9]. An inverse rule is found for compact grains, larger than the wavelength. Mixtures of fluffy silica and fined grained amorphous carbon or better Mg-Fe silicates with amorphous carbon are excellent cometary particles analogues (as light scattering is concerned) if they are mixed with some compact micron-sized grains [9]. Nevertheless the structure of the aggregates seems to play a major role to obtain the negative branch found on the polarimetric phase curves for comets [10]. 5- Discussion and conclusions The experiments purpose is to help to disentangle the different physical properties of dust particles that can be deduced from remote observations (cometary dust, regoliths). Differences between the main parameters influencing the variations of Pmax and the presence of a negative branch on the polarimetric phase curves for lifted and deposited particles (in huge agglomerates or not) will be discussed. Acknowledgments: Technische Universität Carolo-Wilhelmina, Braunschweig, Deutschland (Pr Blum, Dr Schräpler); University of New Mexico, Albuquerque, USA (Pr Rietmeijer); NASA Goddard Space Flight Center, Maryland, USA (Dr Nuth) References [1] A.C. Levasseur-Regourd, E. Hadamcik, JQSRT 79-80, 903 (2003) [2] J. Lasue, A.C. Levasseur-Regourd, JQSRT 100, 220 (2006) [3] J.-B. Renard et al., ASR 31, 2511 (2003) [4] J.-B. Renard et al., Appl. Opt. 91, 609 (2002) [5] E. Hadamcik et al., JQSRT 106, 74 (2007) [6] J. Blum, R. Schreapler, Phys. Rev Let 93:115031 (2004) [7] J. Blum et al., Astrophys J 652, 1768 (2006) [8] R. West, Appl. Opt. 30, 5216 (1991) [9] E. Hadamcik et al., JQSRT 100, 143 (2006) [10] E. Hadamcik et al., Icarus, in press (2007)
Ceramic materials under high temperature heat transfer conditions

NASA Astrophysics Data System (ADS)

Mittenbühler, A.; Jung, J.

1990-04-01

Ceramic materials for application in a High-Temperature Reactor coupled with the steam gasification of coal were investigated. The study concentrated on the hot gas duct and their thermal insulation. Materials examined for the inner lining of the tubes were graphite, carbon fibre reinforced carbon and amorphous silica, while fibres, porous alumina and bonded alumina fibres were tested as insulating materials. During material investigations qualification was performed on samples and in component tests. For two carbon fibre reinforced carbon qualities with different graphitizing temperatures, the bending strength was determined as a function of volume corrosion. Devitrification of amorphous silica can be tolerated up to operating temperatures of about 950°C. The resilience of fibre materials depends on the Al2O3/ SiO2 ratio. It decreases according to the different fibre composition with increasing temperature and limits the maximum operating temperature for long term operation. The porous hollow spherical corundum inserted in the form of bricks fulfilled the thermal shock and mechanical requirements but led to an insulation exhibiting gaps in component tests. An advanced insulation on the basis of bonded alumina fibre showed a quasi-elastic material behaviour. Resistance to abrasion was achieved with a protective ceramic coating. The different materials and design concepts are compared and the results provide a good solution for the project.
Colloidal and physical transport textures exhibited by electrum and naumannite in bonanza epithermal veins from western USA, and their significance

USGS Publications Warehouse

Saunders, James A.; Vikre, Peter G.; Unger, Derick L.; Beasley, Lee

2010-01-01

It is reasonably clear that disequilibrium or “far-from equilibrium” conditions lead to the formation of silica colloids and their deposition in many epithermal deposits. This implies ore-forming solutions had elevated concentrations of dissolved silica, well in excess of amorphous silica saturation. We have previously demonstrated that such colloidal silica particles were deposited in epithermal veins as silica gels and opal, which may later progress along a path to crystallize into more thermodynamically favored (less-soluble) silica phases such as quartz and chalcedony. Also, in some deposits, amorphous silica is co-deposited with precious-metal minerals, such as electrum in the banded super-bonanza ores of the Sleeper deposit (NV). Ore-mineral textures from some western USA bonanza epithermal ores indicate that two precious-metal phases (electrum and naumannite, Ag2Se) form colloidal particles that are transported by ore-forming fluids and are deposited either by aggregation (by sticking to other precious metal-particles) to make dendrites, or are deposited on the “lee” side of protrusion along vein walls (or perhaps by both processes). We can infer by analogy to silica that this also implies that ore-forming solutions contained elevated (supersaturated) dissolved concentrations of both gold and silver that formed colloidal particles under disequilibrium (often chaotic) conditions. Thus physical transport and deposition textures seem to indicate the presence of strongly precious-metal-enriched ore forming fluids, which led to (not surprisingly) the bonanza grades of these remarkable ores. What causes such a precious-metal-rich solution is debatable, but that is the subject of our continued investigations.
Silica Debris Disk Evidence for Giant Planet Forming Impacts

NASA Astrophysics Data System (ADS)

Lisse, C.

2014-04-01

Giant impacts are major formation events in the history of our solar system. The final assembly of the planets, as we understand it, had to include massive fast collision events as the planets grew to objects with large escape velocities or in regions of high Keplerian velocities (Chambers 2004; Kenyon & Bromley 2004a,b, 2006; Fegley & Schaefer 2005). These massive impact events should create large amounts of glassy silica material derived from the rapid melting, vaporization, and refreezing of normal silicate rich primitive rocky material. We report here the detection of 4 bright silica-rich debris disks in the Spitzer IRS spectral archive, and the possible identification of 7 others. The stellar types of the system primaries span from A5V to G0V, their ages are 10 - 100 Myr, and the dust is warm, 280 - 480 K, and is located between 1.5 and 6 AU, well inside the systems' terrestrial planet regions. The minimum amount of detected 0.1 - 20 dust mass ranges from 10^21 - 10^23 kg; assuming < 10% dust formation efficiency (Benz 2009, 2011) this implies collisions involving impactors massing at least 10^22 - 10^24 kg, i.e. from Moon to Earth mass. We find possible trends in the mineralogy of the silica, with predominantly amorphous silica found in the 2 younger systems, and crystalline silica in the older systems. We speculate this is due higher velocity impacts found in younger, hotter systems, coupled with the effects of energetic photon annealing of small amorphous silica grains. All of these measures are consistent with the creation of silica rich rubble, or construction debris, during the terrestrial planet formation era of giant impacts.
Silica substrate or portion formed from oxidation of monocrystalline silicon

DOEpatents

Matzke, Carolyn M.; Rieger, Dennis J.; Ellis, Robert V.

2003-07-15

A method is disclosed for forming an inclusion-free silica substrate using a monocrystalline silicon substrate as the starting material and oxidizing the silicon substrate to convert it entirely to silica. The oxidation process is performed from both major surfaces of the silicon substrate using a conventional high-pressure oxidation system. The resulting product is an amorphous silica substrate which is expected to have superior etching characteristics for microfabrication than conventional fused silica substrates. The present invention can also be used to convert only a portion of a monocrystalline silicon substrate to silica by masking the silicon substrate and locally thinning a portion the silicon substrate prior to converting the silicon portion entirely to silica. In this case, the silica formed by oxidizing the thinned portion of the silicon substrate can be used, for example, as a window to provide optical access through the silicon substrate.
Diagenetic silica enrichment and late-stage groundwater activity in Gale crater, Mars

USGS Publications Warehouse

Frydenvang, Jens; Gasda, Patrick J.; Hurowitz, Joel A.; Grotzinger, John P.; Wiens, Roger C.; Newsom, Horton E.; Edgett, Ken S.; Watkins, Jessica; Bridges, John C.; Maurice, Sylvestre; Fisk, Martin R.; Johnson, Jeffrey R.; Rapin, William; Stein, Nathan; Clegg, Sam M.; Schwenzer, S. P.; Bedford, C.; Edwards, P.; Mangold, Nicolas; Cousin, Agnes; Anderson, Ryan; Payre, Valerie; Vaniman, David; Blake, David; Lanza, Nina L.; Gupta, Sanjeev; Van Beek, Jason; Sautter, Violaine; Meslin, Pierre-Yves; Rice, Melissa; Milliken, Ralf; Gellert, Ralf; Thompson, Lucy; Clark, Ben C.; Sumner, Dawn Y.; Fraeman, Abigail A.; Kinch, Kjartan M; Madsen, Morten B.; Mitofranov, Igor; Jun, Insoo; Calef, Fred J.; Vasavada, Ashwin R.

2017-01-01

Diagenetic silica enrichment in fracture-associated halos that crosscut lacustrine and unconformably overlying aeolian sedimentary bedrock is observed on the lower north slope of Aeolis Mons in Gale crater, Mars. The diagenetic silica enrichment is colocated with detrital silica enrichment observed in the lacustrine bedrock yet extends into a considerably younger, unconformably draping aeolian sandstone, implying that diagenetic silica enrichment postdates the detrital silica enrichment. A causal connection between the detrital and diagenetic silica enrichment implies that water was present in the subsurface of Gale crater long after deposition of the lacustrine sediments and that it mobilized detrital amorphous silica and precipitated it along fractures in the overlying bedrock. Although absolute timing is uncertain, the observed diagenesis likely represents some of the most recent groundwater activity in Gale crater and suggests that the timescale of potential habitability extended considerably beyond the time that the lacustrine sediments of Aeolis Mons were deposited.
Coherent anti-Stokes Raman scattering microscopy driving the future of loaded mesoporous silica imaging.

PubMed

Fussell, Andrew L; Mah, Pei Ting; Offerhaus, Herman; Niemi, Sanna-Mari; Salonen, Jarno; Santos, Hélder A; Strachan, Clare

2014-11-01

This study reports the use of variants of coherent anti-Stokes Raman scattering (CARS) microscopy as a novel method for improved physicochemical characterization of drug-loaded silica particles. Ordered mesoporous silica is a biomaterial that can be loaded to carry a number of biochemicals, including poorly water-soluble drugs, by allowing the incorporation of drug into nanometer-sized pores. In this work, the loading of two poorly water-soluble model drugs, itraconazole and griseofulvin, in MCM-41 silica microparticles is characterized qualitatively, using the novel approach of CARS microscopy, which has advantages over other analytical approaches used to date and is non-destructive, rapid, label free, confocal and has chemical and physical specificity. The study investigated the effect of two solvent-based loading methods, namely immersion and rotary evaporation, and microparticle size on the three-dimensional (3-D) distribution of the two loaded drugs. Additionally, hyperspectral CARS microscopy was used to confirm the amorphous nature of the loaded drugs. Z-stacked CARS microscopy suggested that the drug, but not the loading method or particle size range, affected 3-D drug distribution. Hyperspectral CARS confirmed that the drug loaded in the MCM-41 silica microparticles was in an amorphous form. The results show that CARS microscopy and hyperspectral CARS microscopy can be used to provide further insights into the structural nature of loaded mesoporous silica microparticles as biomaterials. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Production of colourful pigments consisting of amorphous arrays of silica particles.

PubMed

Yoshioka, Shinya; Takeoka, Yukikazu

2014-08-04

It is desirable to produce colourful pigments that have anti-fading properties and are environmentally friendly. In this Concept, we describe recently developed pigments that exhibit such characteristics. The pigments consist of amorphous arrays of submicron silica particles, and they exhibit saturated and angle-independent structural colours. Variously coloured pigments can be produced by changing the size of the particles, and the saturation of the colour can be controlled by incorporating small amounts of black particles. We review a simple analysis that is useful for interpreting the angular independence of the structural colours and discuss the remaining tasks that must be accomplished for the realistic application of these pigments. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
High-temperature synthesis of silica particles by the chloride method in the regime of counter flow jet quenching

NASA Astrophysics Data System (ADS)

Kartaev, E. V.; Emel'kin, V. A.; Aul'chenko, S. M.

2017-10-01

The experimental and numerical investigations of synthesis of silica (SiO2) nanoparticles from premixed gaseous silicon tetrachloride (SiCl4) and oxygen of dry air in the high-temperature nitrogen flow of plasma-chemical reactor have been carried out. The regime of counter flow jet quenching of high-temperature heterogeneous flow has been utilized. The latter provided a rapid cooling of silica particles under nonequilibrium conditions with substantial temperature gradients. Synthesized silica particles were amorphous, with surface-average size being about 28 nm. The results of numerical calculations are found to agree qualitatively with experimental data.
Studying the loading effect of acidic type antioxidant on amorphous silica nanoparticle carriers

NASA Astrophysics Data System (ADS)

Ravinayagam, Vijaya; Rabindran Jermy, B.

2017-06-01

The study investigates the suitable nanosilica carriers to transport acidic type cargo molecules for potential targeted drug delivery application. Using phenolic acidic type antioxidant gallic acid (GA) as model compound, the present study investigates the loading effect of GA (0.3-15.9 mmol GA g-1 support) on textural characteristics of amorphous silica nanoparticles such as Q10 silica (1D), structured two-dimensional Si-MCM-41 (2D), and three-dimensional Si-SBA-16 (3D). The variation in the nature of textures after GA loading was analyzed using X-ray diffraction, N2 adsorption, FT-IR, scanning electron microscopy with energy dispersive X-ray spectroscopy, and high-resolution transmission electron microscopy. Among the nanocarriers, high adsorption of GA was found in the following order: Si-SBA-16 (3D)˜Si-KIT-6 (3D) > Si-MCM-41 (2D) > ultralarge pore FDU-12 (ULPFDU-12; 3D) > Q10 (1D)˜mesostructured cellular silica foam (MSU-F). 3D-type silicas Si-SBA-16 and KIT-6 were shown to maintain structural integrity at acidic condition (pH ˜3) and accommodate GA in non-crystalline form. In the case of ULPFDU-12 and MSU-F cellular foam, only crystalline deposition of GA occurs with a significant variation in the surface area and pore volume. [Figure not available: see fulltext.

3D-Printed Transparent Glass

DOE PAGES

Nguyen, Du T.; Meyers, Cameron; Yee, Timothy D.; ...

2017-04-28

In this study, silica inks are developed, which may be 3D printed and thermally processed to produce optically transparent glass structures with sub-millimeter features in forms ranging from scaffolds to monoliths. The inks are composed of silica powder suspended in a liquid and are printed using direct ink writing. The printed structures are then dried and sintered at temperatures well below the silica melting point to form amorphous, solid, transparent glass structures. This technique enables the mold-free formation of transparent glass structures previously inaccessible using conventional glass fabrication processes.
Conversion of glucose to sorbose

DOEpatents

Davis, Mark E.; Gounder, Rajamani

2016-02-09

The present invention is directed to methods for preparing sorbose from glucose, said method comprising: (a) contacting the glucose with a silica-containing structure comprising a zeolite having a topology of a 12 membered-ring or larger, an ordered mesoporous silica material, or an amorphous silica, said structure containing Lewis acidic Ti.sup.4+ or Zr.sup.4+ or both Ti.sup.4+ and Zr.sup.4+ framework centers, said contacting conducted under reaction conditions sufficient to isomerize the glucose to sorbose. The sorbose may be (b) separated or isolated; or (c) converted to ascorbic acid.
3D-Printed Transparent Glass

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

Nguyen, Du T.; Meyers, Cameron; Yee, Timothy D.

In this study, silica inks are developed, which may be 3D printed and thermally processed to produce optically transparent glass structures with sub-millimeter features in forms ranging from scaffolds to monoliths. The inks are composed of silica powder suspended in a liquid and are printed using direct ink writing. The printed structures are then dried and sintered at temperatures well below the silica melting point to form amorphous, solid, transparent glass structures. This technique enables the mold-free formation of transparent glass structures previously inaccessible using conventional glass fabrication processes.
High-Temperature, Perhaps Silicic, Volcanism on Mars Evidenced by Tridymite Detection in High-SiO2 Sedimentary Rock at Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Morris, R. V.; Vaniman, D. T.; Blake, D. F.; Gellert, R.; Chipera, S. J.; Rampe, E. B.; Ming, D. W.; Morrison, S. M.; Downs, R. T.; Treiman, A. H.;

2016-01-01

The Mars Science Laboratory (MSL) rover, Curiosity, has been exploring sedimentary rocks within Gale crater since landing in August, 2012. On the lower slopes of Aeolis Mons (a.k.a. Mount Sharp), drill powder was collected from a high-silica (74 wt% SiO2) outcrop named Buckskin (BK). It was a surprise to find that the Buckskin sample contained significant amounts of the relatively rare silica polymorph tridymite. We describe the setting of the Buckskin sample, the detection of tridymite by the MSL Chemistry and Mineralogy (CheMin) X-ray diffraction instrument, and detection implications. Geologic setting: The Buckskin outcrop is part of the Murray formation exposed in the Marias Pass area. The formation was previously studied by CheMin in the Pahrump Hills member [1] where three samples of drill fines were analyzed (Confidence Hills (CH), Mojave2 (MJ) and Telegraph Peak (TP) [2]). Assuming approximately horizontal bedding, the Buckskin outcrop is approx.15 m stratigraphically above the bottom of the Pahrump Hills member. Mudstone, generally characterized by fine lamination, is the dominant depositional facies [1]. Buckskin Mineralogical and Chemical Composition: The CheMin instrument and XRD pattern analysis procedures have been previously discussed [3-6]. The diffraction pattern used for quantitative XRD analysis (Fig. 1) is the sum of the first 4 of 45 diffraction images. The remaining images are all characterized by both on-ring and off-ring diffraction spots that we attributed to poor grain motion and particle clumping. Coincident with particle clumping was a significant decrease in the intensity of the tridymite diffraction peaks (Fig. 2a). The derived mineralogical composition of the crystalline component (derived from the first 4 diffraction images) is given in Table 1. The tridymite is well-crystalline and its pattern is refined as monoclinic tridymite (Fig 1). Mineral chemical compositions were derived from XRD unit cell parameters or obtained from stoichiometry. The XRD-calculated amorphous component was 50 +/- 15 wt%. We constrained the value to 60 wt% because it is the minimum value necessary to give a positive Al2O3 concentration for the amorphous component using APXS data for the post-sieve dump pile (Table 2). The amorphous component has high SiO2 (approx.77 wt%) and high anion (SO3+P2O5+Cl 10 wt%) concentrations. Calculation shows that a cation-anion balance is achieved if the cations in the amorphous component except SiO2 and TiO2, which do not readily form salts, are assumed to be present as amorphous mixed-cation sulfates, phosphates, and chlorides (or perchlorates/ chlorates).

Picosecond amorphization of SiO2 stishovite under tension.

PubMed

Misawa, Masaaki; Ryuo, Emina; Yoshida, Kimiko; Kalia, Rajiv K; Nakano, Aiichiro; Nishiyama, Norimasa; Shimojo, Fuyuki; Vashishta, Priya; Wakai, Fumihiro

2017-05-01

It is extremely difficult to realize two conflicting properties-high hardness and toughness-in one material. Nano-polycrystalline stishovite, recently synthesized from Earth-abundant silica glass, proved to be a super-hard, ultra-tough material, which could provide sustainable supply of high-performance ceramics. Our quantum molecular dynamics simulations show that stishovite amorphizes rapidly on the order of picosecond under tension in front of a crack tip. We find a displacive amorphization mechanism that only involves short-distance collective motions of atoms, thereby facilitating the rapid transformation. The two-step amorphization pathway involves an intermediate state akin to experimentally suggested "high-density glass polymorphs" before eventually transforming to normal glass. The rapid amorphization can catch up with, screen, and self-heal a fast-moving crack. This new concept of fast amorphization toughening likely operates in other pressure-synthesized hard solids.
Mineralogy of Rocks and Sediments at Gale Crater, Mars

NASA Astrophysics Data System (ADS)

Achilles, Cherie; Downs, Robert; Blake, David; Vaniman, David; Ming, Doug; Rampe, Elizabeth; Morris, Dick; Morrison, Shaunna; Treiman, Allan; Chipera, Steve; Yen, Albert; Bristow, Thomas; Craig, Patricia; Hazen, Robert; Crisp, Joy; Grotzinger, John; Des Marias, David; Farmer, Jack; Sarrazin, Philippe; Morookian, John Michael

2017-04-01

The Mars Science Laboratory rover, Curiosity, is providing in situ mineralogical, geochemical, and sedimentological assessments of rocks and soils in Gale crater. Since landing in 2012, Curiosity has traveled over 15 km, providing analyses of mudstones and sandstones to build a stratigraphic history of the region. The CheMin X-ray diffraction (XRD) instrument is the first instrument on Mars to provide quantitative mineralogical analyses of drilled powders and scooped sediment based on X-ray crystallography. CheMin identifies and determines mineral abundances and unit-cell parameters of major crystalline phases, and identifies minor phases at abundances >1 wt%. In conjunction with elemental analyses, CheMin-derived crystal chemistry allows for the first calculations of crystalline and amorphous material compositions. These mineralogy, crystal chemistry, and amorphous chemistry datasets are playing central roles in the characterization of Gale crater paleoenvironments. CheMin has analyzed 17 rock and sediment samples. In the first phase of the mission, Curiosity explored the sedimentary units of Aeolis Palus (Bradbury group), including two mudstones from Yellowknife Bay. CheMin analyses of the Yellowknife Bay mudstones identified clay minerals among an overall basaltic mineral assemblage. These mineralogical results, along with imaging and geochemical analyses, were used to characterize an ancient lacustrine setting that is thought to have once been a habitable environment. Following the investigations of the Bradbury group, Curiosity arrived at the lower reaches of Aeolis Mons, commonly called Mt. Sharp. A strategic sample campaign was initiated, drilling bedrock at <25 m elevation intervals in order to compile a comprehensive stratigraphic column of Mt. Sharp sedimentary units. Two formations have been sampled thus far, the lower-most Murray formation and the Stimson formation, which lies unconformably over the Murray. The Stimson formation is a cross-bedded sandstone interpreted as ancient, lithified eolian dunes. The mineralogy of this sandstone is dominated by plagioclase, pyroxene, magnetite and X-ray amorphous phases. Adjacent to fractures, light-toned, halo-like zones are thought to result from significant aqueous alteration of the primary sandstone and show decreased abundances of feldspar and pyroxene, and an increase in the amorphous component, specifically high-silica phases. The Murray formation is the most sampled stratigraphic unit in Gale crater. Composed mainly of finely laminated mudstones and interpreted as lacustrine deposits, the mineralogy of Murray rocks reveals a complex aqueous history. Within the lower Murray strata, CheMin identified clay minerals, crystalline and amorphous silica, hematite, magnetite, and jarosite. The mineralogy suggests a paleolake that experienced variable redox conditions and sediment influx from multiple sources. Younger Murray strata have high abundances of clay minerals, hematite, and calcium sulfate but show lower variability in mineralogy compared to the older bedforms. CheMin's identification of tridymite in one of the Murray mudstone samples led to the first in situ identification of silicic volcanism on Mars. This presentation will discuss the mineralogy of sedimentary samples analyzed by CheMin and how these data are used to characterize the depositional and diagenetic environment of Gale crater's long-lived lake system.
Thermochemistry of amorphous and crystalline zirconium and hafnium silicates.

NASA Astrophysics Data System (ADS)

Ushakov, S.; Brown, C. E.; Navrotsky, Alexandra; Boatner, L. A.; Demkov, A. A.; Wang, C.; Nguyen, B.-Y.

2003-03-01

Calorimetric investigation of amorphous and crystalline zirconium and hafnium silicates was performed as part of a research program on thermochemistry of alternative gate dielectrics. Amorphous hafnium and zirconium silicates with varying SiO2 content were synthesized by a sol-gel process. Crystalline zirconium and hafnium silicates (zircon and hafnon) were synthesized by solid state reaction at 1450 °C from amorphous gels and grown as single crystals from flux. High temperature oxide melt solution calorimetry in lead borate (2PbO.B2O3) solvent at 800 oC was used to measure drop solution enthalpies for amorphous and crystalline zirconium and hafnium silicates and corresponding oxides. Applying appropriate thermochemical cycles, formation enthalpy of crystalline ZrSiO4 (zircon) from binary oxides (baddeleite and quartz) at 298 K was calculated as -23 +/-2 kJ/mol and enthalpy difference between amorphous and crystalline zirconium silicate (vitrification enthalpy) was found to be 61 +/-3 kJ/mol. Crystallization onset temperatures of amorphous zirconium and hafnium silicates, as measured by differential scanning calorimetry (DSC), increased with silica content. The resulting crystalline phases, as characterized by X-ray diffraction (XRD), were tetragonal HfO2 and ZrO2. Critical crystallite size for tetragonal to monoclinic transformation of HfO2 in the gel was estimated as 6 +/-2 nm from XRD data Crystallization enthalpies per mole of hafnia and zirconia in gels decrease slightly together with crystallite size with increasing silica content, for example from -22 to -15 +/-1 kJ per mol of HfO2 crystallized at 740 and 1006 °C from silicates with 10 and 70 mol Applications of thermal analyses and solution calorimetry techniques together with first-principles density functional calculations to estimate interface and surface energies are discussed.
Photocatalytic performance of highly amorphous titania-silica aerogels with mesopores: The adverse effect of the in situ adsorption of some organic substrates during photodegradation

NASA Astrophysics Data System (ADS)

Lázár, István; Kalmár, József; Peter, Anca; Szilágyi, Anett; Győri, Enikő; Ditrói, Tamás; Fábián, István

2015-11-01

Titania-silica composite aerogels with 16-29% Ti-content by the mass were synthesized by the sol-gel method from different Ti-precursors, and calcined at 500 °C. These aerogels are highly amorphous as no crystalline TiO2 phase can be detected in them by X-ray diffraction methods, and show the dominating presence of either mesopores or macropores. The incorporation of Ti into the silica structure is shown by the appearance of characteristic IR transitions of Sisbnd Osbnd Ti vibrations. The characteristic band-gap energies of the different aerogels are estimated to be between 3.6 and 3.9 eV from UV reflection spectra. Band-gap energy decreases with decreasing pore-size. When suspended in solution, even these highly amorphous aerogels accelerate the photodegradation of salicylic acid and methylene blue compared to simple photolysis. Kinetic experiments were conducted under illumination, and also in the dark to study the adsorption of the substrates onto the suspended aerogels. We assume that the fast in situ adsorption of the organic substrates mask the suspended aerogel particles from UV photons, which reduces the rate of photocatalysis. We managed to mathematically separate the parallel processes of photocatalysis and adsorption, and develop a simple kinetic model to describe the reaction system.
Trace element and isotope geochemistry of geothermal fluids, East Rift Zone, Kilauea, Hawaii

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

West, H.B.; Delanoy, G.A.; Thomas, D.M.

1992-01-01

A research program has been undertaken in an effort to better characterize the composition and the precipitation characteristic of the geothermal fluids produced by the HGP-A geothermal well located on the Kilauea East Rift Zone on the Island of Hawaii. The results of these studies have shown that the chemical composition of the fluids changed over the production life of the well and that the fluids produced were the result of mixing of at least two, and possibly three, source fluids. These source fluids were recognized as: a sea water composition modified by high temperature water-rock reactions; meteoric recharge; andmore » a hydrothermal fluid that had been equilibrated with high temperature reservoir rocks and magmatic volatiles. Although the major alkali and halide elements show clearly increasing trends with time, only a few of the trace transition metals show a similar trend. The rare earth elements, were typically found at low concentrations and appeared to be highly variable with time. Studies of the precipitation characteristics of silica showed that amorphous silica deposition rates were highly sensitive to fluid pH and that increases in fluid pH above about 8.5 could flocculate more than 80% of the suspended colloidal silica in excess of its solubility. Addition of transition metal salts were also found to enhance the recovery fractions of silica from solution. The amorphous silica precipitate was also found to strongly scavenge the alkaline earth and transition metal ions naturally present in the brines; mild acid treatments were shown to be capable of removing substantial fractions of the scavenged metals from the silica flocs yielding a moderately pure gelatinous by-product. Further work on the silica precipitation process is recommended to improve our ability to control silica scaling from high temperature geothermal fluids or to recover a marketable silica by-product from these fluids prior to reinjection.« less
Trace element and isotope geochemistry of geothermal fluids, East Rift Zone, Kilauea, Hawaii

NASA Astrophysics Data System (ADS)

West, H. B.; Delanoy, G. A.; Thomas, D. M.; Gerlach, D. C.; Chen, B.; Takahashi, P.; Thomas, D. M.

1992-03-01

A research program has been undertaken in an effort to better characterize the composition and the precipitation characteristic of the geothermal fluids produced by the HGP-A geothermal well located on the Kilauea East Rift Zone on the island of Hawaii. The results of these studies have shown that the chemical composition of the fluids changed over the production life of the well and that the fluids produced were the result of the mixing of at least two, and possibly three, source fluids. These source fluids were recognized as a sea water composition modified by high temperature water-rock reactions; meteoric recharge; and a hydrothermal fluid that had been equilibriated with high temperature reservoir rocks and magmatic volatiles. Although the major alkali and halide elements show clearly increasing trends with time, only a few of the trace transition metals show a similar trend. The rare earth elements were typically found at low concentrations and appeared to be highly variable with time. Studies of the precipitation characteristics of silica showed that amorphous silica deposition rates were highly sensitive to fluid pH and that increases in fluid pH above about 8.5 could flocculate more than 80 percent of the suspended colloidal silica in excess of its solubility. Addition of transition metal salts were also found to enhance the recovery fractions of silica from solution. The amorphous silica precipitate was also found to strongly scavenge the alkaline earth and transition metal ions naturally present in the brines; mild acid treatments were shown to be capable of removing substantial fractions of the scavenged metals from the silica flocs, yielding a moderately pure gelatinous by-product. Further work on the silica precipitation process is recommended to improve our ability to control silica scaling from high temperature geothermal fluids or to recover a marketable silica by-product from these fluids prior to reinjection.
Numerical modeling of mineral dissolution - precipitation kinetics integrating interfacial processes

NASA Astrophysics Data System (ADS)

Azaroual, M. M.

2016-12-01

The mechanisms of mineral dissolution/precipitation are complex and interdependent. Within a same rock, the geochemical modelling may have to manage kinetic reactions with high ratios between the most reactive minerals (i.e., carbonates, sulfate salts, etc.) and less reactive minerals (i.e., silica, alumino-silicates, etc.). These ratios (higher than 10+6) induce numerical instabilities for calculating mass and energy transfers between minerals and aqueous phases at the appropriate scales of time and space. The current scientific debate includes: i) changes (or not) of the mineral reactive surface with the progress of the dissolution/precipitation reactions; ii) energy jumps (discontinuity) in the thermodynamic affinity function of some dissolution/precipitation reactions and iii) integration of processes at the "mineral - aqueous solution" interfaces for alumino-silicates, silica and carbonates. In recent works dealing with the specific case of amorphous silica, measurements were performed on nano-metric cross-sections indicating the presence of surface layer between the bulk solution and the mineral. This thin layer is composed by amorphous silica and hydrated silica "permeable" to the transfer of water and ionic chemical constituents. The boundary/interface between the initial mineral and the silica layer is characterized by a high concentration jump of chemical products at the nanoscale and some specific interfacial dissolution/precipitation processes.In this study, the results of numerical simulations dealing with different mechanisms of silicate and carbonate dissolution/precipitation reactions and integrating interfacial processes will be discussed. The application of this approach to silica precipitation is based on laboratory experiments and it highlights the significant role of the "titration" surface induced by surface complexation reactions in the determination of the kinetics of precipitation.
High-efficiency cogeneration boiler bagasse-ash geochemistry and mineralogical change effects on the potential reuse in synthetic zeolites, geopolymers, cements, mortars, and concretes.

PubMed

Clark, Malcolm W; Despland, Laure M; Lake, Neal J; Yee, Lachlan H; Anstoetz, Manuela; Arif, Elisabeth; Parr, Jeffery F; Doumit, Philip

2017-04-01

Sugarcane bagasse ash re-utilisation has been advocated as a silica-rich feed for zeolites, pozzolans in cements and concretes, and geopolymers. However, many papers report variable success with the incorporation of such materials in these products as the ash can be inconsistent in nature. Therefore, understanding what variables affect the ash quality in real mills and understanding the processes to characterise ashes is critical in predicting successful ash waste utilisation. This paper investigated sugarcane bagasse ash from three sugar mills (Northern NSW, Australia) where two are used for the co-generation of electricity. Data shows that the burn temperatures of the bagasse in the high-efficiency co-generation boilers are much higher than those reported at the temperature measuring points. Silica polymorph transitions indicate the high burn temperatures of ≈1550 °C, produces ash dominated α -quartz rather than expected α-cristobilite and amorphous silica; although α-cristobilite, and amorphous silica are present. Furthermore, burn temperatures must be ≤1700 °C, because of the absence of lechatelierite where silica fusing and globulisation dominates. Consequently, silica-mineralogy changes deactivate the bagasse ash by reducing silica solubility, thus making bagasse ash utilisation in synthetic zeolites, geopolymers, or a pozzolanic material in mortars and concretes more difficult. For the ashes investigated, use as a filler material in cements and concrete has the greatest potential. Reported mill boiler temperatures discrepancies and the physical characteristics of the ash, highlight the importance of accurate temperature monitoring at the combustion seat if bagasse ash quality is to be prioritised to ensure a usable final ash product.
Formation of siliceous sediments in brandy after diatomite filtration.

PubMed

Gómez, J; Gil, M L A; de la Rosa-Fox, N; Alguacil, M

2015-03-01

Brandy is quite a stable spirit but sometimes light sediment appears. This sediment was separated and analysed by IR and SEM-EDX. It was revealed that the sediment is composed mostly of silica and residual organic matter. Silica was present as an amorphous phase and as microparticles. In an attempt to reproduce the formation of the sediment, a diatomite extract was prepared with an ethanol/water mixture (36% vol.) and a calcined diatomite similar to that used in brandy filtration. This extract was added to unfiltered brandy in different amounts. After 1 month, the Si concentration decreased in all samples and sediments with similar compositions and features to those found in the unstable brandy appeared. The amounts of sediment obtained were directly related to the decrease in Si concentration in solution. Consequently, it can be concluded that siliceous sediment in brandy originates from Si released during diatomite filtration. Copyright © 2014 Elsevier Ltd. All rights reserved.
Shock-wave equation-of-state measurements in fused silica up to 1600 GPa

DOE PAGES

McCoy, C. A.; Gregor, M. C.; Polsin, D. N.; ...

2016-06-02

The properties of silica are important to geophysical and high-pressure equation of state research. The most prevalent crystalline form, α-quartz, has been extensively studied to TPa pressures. Recent experiments with amorphous silica, commonly referred to as fused silica, provided Hugoniot and reflectivity data up to 630 GPa using magnetically-driven aluminum impactors. This article presents measurements of the fused silica Hugoniot over the range from 200 to 1600 GPa using laser-driven shocks with a quartz standard. These results extend the measured Hugoniot of fused silica to higher pressures, but more importantly, in the 200-600 GPa range, the data are very goodmore » agreement with those obtained with a different driver and standard material. As a result, a new shock velocity-particle velocity relation is derived to fit the experimental data.« less
Mineralization dynamics of metakaolin-based alkali-activated cements

USGS Publications Warehouse

Gevaudan, Juan Pablo; Campbell, Kate M.; Kane, Tyler; Shoemaker, Richard K.; Srubar, Wil V.

2017-01-01

This paper investigates the early-age dynamics of mineral formation in metakaolin-based alkali-activated cements. The effects of silica availability and alkali content on mineral formation were investigated via X-ray diffraction and solid-state 29Si magic-angle spinning nuclear magnetic resonance spectroscopy at 2, 7, 14, and 28 days. Silica availability was controlled by using either liquid- (immediate) or solid-based (gradual) sodium silicate supplements. Mineral (zeolitic) and amorphous microstructural characteristics were correlated with observed changes in bulk physical properties, namely shrinkage, density, and porosity. Results demonstrate that, while alkali content controls the mineralization in immediately available silica systems, alkali content controls the silica availability in gradually available silica systems. Immediate silica availability generally leads to a more favorable mineral formation as demonstrated by correlated improvements in bulk physical properties.
Investigating the Origin of Silica Occurrences on Mars through Laboratory Observations

NASA Astrophysics Data System (ADS)

Ruff, S. W.; Milliken, R. E.; Farmer, J. D.; Mills, V. W.; Robertson, K.

2012-12-01

Natural amorphous "opaline" silica is a non-crystalline, typically hydrated phase of nearly pure SiO2 that is a common product of aqueous alteration of basaltic materials [e.g., 1]. It has been identified on Mars with orbital spectral data [2] and in situ measurements from the Spirit rover [3]. On Earth, opaline silica is produced over a range of temperature, pH, and water-to-rock ratio conditions that occur in hot springs, fumaroles, volcanic exhalations, low temperature weathering, and diagenesis [e.g., 4 and references therein]. The mere identification of silica on Mars therefore does not indicate a unique geologic environment or setting. However, various attributes of a given silica occurrence can be used to narrow or perhaps uniquely define the conditions in which it formed. Field relationships, microtexture, bulk and trace element chemistry, and spectral characteristics provide clues to the geologic environment in which the silica formed. Here we focus on the opaline silica in outcrops and soil at the Home Plate feature in Gusev crater where there is good evidence for past hydrothermal processes [3]. Unresolved is whether fumaroles, hot springs, geysers, or some combination of these features were present and responsible for the emplacement of opaline silica there. Knowing the answer has implications for understanding ancient climate and habitability of Mars. We have begun an investigation involving a range of laboratory measurements on natural silica-rich samples collected from various settings in Yellowstone and Hawaii Volcanoes National Parks. Visible and near infrared (VNIR) and thermal infrared (TIR) spectral measurements are supplemented with X-ray powder diffraction, scanning electron microscopy, petrographic microscopy, and ultimately with bulk and trace element measurements. Among our emerging results: 1) both VNIR and TIR spectra can detect the presence of <2 μm silica coatings on altered basalts; 2) VNIR spectra of silica from different environments exhibit only subtle differences, likely controlled primarily by variations in water content; and 3) fumarolic silica appears to have TIR spectral characteristics distinct from hot spring silica. This last result applies to samples of basaltic rocks enriched in silica by acid-sulfate leaching from Sulfur Banks, HI, which has been suggested as an analog for the Home Plate silica [3]. TIR spectra of four samples display only a weak feature near 8 μm related to high emission angle compared to that observed in hot spring silica sinter from Yellowstone. This spectral behavior may arise from microtextural or contaminant differences between the two kinds of silica. TIR spectra of Home Plate silica display a strong 8-μm feature like those of hot spring silica. If this preliminary result survives subsequent scrutiny, it may provide additional insight into the nature of the Home Plate hydrothermal system, the first to be investigated in situ on Mars. [1] McLennan, S. M. (2003), Geology, 31, 4, 315-318, [2] Milliken, R. E., et al. (2008), Geology, 36, 11, 847-850, 10.1130/G24967A.1. [3] Squyres, S. W., et al. (2008), Science, 320, 1063-1067, [4] Ruff, S. W., et al. (2011), J. Geophys. Res., 116, E00F23, 10.1029/2010JE003767.
Gas phase condensation of superparamagnetic iron oxide-silica nanoparticles - control of the intraparticle phase distribution

NASA Astrophysics Data System (ADS)

Stötzel, C.; Kurland, H.-D.; Grabow, J.; Müller, F. A.

2015-04-01

Spherical, softly agglomerated and superparamagnetic nanoparticles (NPs) consisting of maghemite (γ-Fe2O3) and amorphous silica (SiO2) were prepared by CO2 laser co-vaporization (CoLAVA) of hematite powder (α-Fe2O3) and quartz sand (SiO2). The α-Fe2O3 portion of the homogeneous starting mixtures was gradually increased (15 mass%-95 mass%). It was found that (i) with increasing iron oxide content the NPs' morphology changes from a nanoscale SiO2 matrix with multiple γ-Fe2O3 inclusions to Janus NPs consisting of a γ-Fe2O3 and a SiO2 hemisphere to γ-Fe2O3 NPs each carrying one small SiO2 lens on its surface, (ii) the multiple γ-Fe2O3 inclusions accumulate at the NPs' inner surfaces, and (iii) all composite NPs are covered by a thin layer of amorphous SiO2. These morphological characteristics are attributed to (i) the phase segregation of iron oxide and silica within the condensed Fe2O3-SiO2 droplets, (ii) the temperature gradient within these droplets which arises during rapid cooling in the CoLAVA process, and (iii) the significantly lower surface energy of silica when compared to iron oxide. The proposed growth mechanism of these Fe2O3-SiO2 composite NPs during gas phase condensation can be transferred to other systems comprising a glass-network former and another component that is insoluble in the regarding glass. Thus, our model will facilitate the development of novel functional composite NPs for applications in biomedicine, optics, electronics, or catalysis.Spherical, softly agglomerated and superparamagnetic nanoparticles (NPs) consisting of maghemite (γ-Fe2O3) and amorphous silica (SiO2) were prepared by CO2 laser co-vaporization (CoLAVA) of hematite powder (α-Fe2O3) and quartz sand (SiO2). The α-Fe2O3 portion of the homogeneous starting mixtures was gradually increased (15 mass%-95 mass%). It was found that (i) with increasing iron oxide content the NPs' morphology changes from a nanoscale SiO2 matrix with multiple γ-Fe2O3 inclusions to Janus NPs consisting of a γ-Fe2O3 and a SiO2 hemisphere to γ-Fe2O3 NPs each carrying one small SiO2 lens on its surface, (ii) the multiple γ-Fe2O3 inclusions accumulate at the NPs' inner surfaces, and (iii) all composite NPs are covered by a thin layer of amorphous SiO2. These morphological characteristics are attributed to (i) the phase segregation of iron oxide and silica within the condensed Fe2O3-SiO2 droplets, (ii) the temperature gradient within these droplets which arises during rapid cooling in the CoLAVA process, and (iii) the significantly lower surface energy of silica when compared to iron oxide. The proposed growth mechanism of these Fe2O3-SiO2 composite NPs during gas phase condensation can be transferred to other systems comprising a glass-network former and another component that is insoluble in the regarding glass. Thus, our model will facilitate the development of novel functional composite NPs for applications in biomedicine, optics, electronics, or catalysis. Electronic supplementary information (ESI) available: Infrared absorption of the raw powders hematite and quartz (section S1), TEM investigation of the spatial distribution of the γ-Fe2O3 inclusions (section S2), particle size distributions of the Fe2O3@SiO2 nanopowder samples (section S3), ζ-potentials of aqueous dispersions of all γ-Fe2O3@SiO2 nanopowder samples (section S4), silanization of Fe2O3@SiO2 composite nanopowders with [3-(2,3-epoxypropoxy)-propyl]trimethoxysilane (section S5), and animation composed of TEM micrographs of Fe2O3@SiO2 NPs recorded at incrementally altered tilt angles (``Rotating Fe2O3@SiO2 NP.avi''). See DOI: 10.1039/c5nr00845j
Chrysocolla Redefined as Spertiniite

NASA Astrophysics Data System (ADS)

Farges, François; Benzerara, Karim; Brown, Gordon E.

2007-02-01

XAFS and μ-XAFS spectra were collected at the Cu K-edge for seven chrysocolla samples (Peru, USA, and Congo). The results suggest that that the local structure around Cu is similar to that in Cu(OH)2 (spertiniite). Cu-L3 STXM imaging and spectroscopy confirm that the chrysocolla samples examined here consist of mesoscopic Cu(II)-rich domains surrounded by Si-rich domains (in agreement with results from infra-red spectroscopy). Hence, we suggest that chrysocolla, which is generally considered to be orthorhombic with composition (Cu,Al)2H2Si2O5(OH)4ṡnH2O, is in actually a mesoscopic assemblage composed dominantly of spertiniite (Cu(OH)2), water and amorphous silica (SiO2).
Crystallized alkali-silica gel in concrete from the late 1890s

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

Peterson, Karl; Gress, David; Van Dam, Tom

The Elon Farnsworth Battery, a concrete structure completed in 1898, is in an advanced state of disrepair. To investigate the potential for rehabilitation, cores were extracted from the battery. Petrographic examination revealed abundant deposits of alkali silica reaction products in cracks associated with the quartz rich metasedimentary coarse aggregate. The products of the alkali silica reaction are variable in composition and morphology, including both amorphous and crystalline phases. The crystalline alkali silica reaction products are characterized by quantitative X-ray energy dispersive spectrometry (EDX) and X-ray diffraction (XRD). The broad extent of the reactivity is likely due to elevated alkali levelsmore » in the cements used.« less
Silica in alkaline brines

USGS Publications Warehouse

Jones, B.F.; Rettig, S.L.; Eugster, H.P.

1967-01-01

Analysis of sodium carbonate-bicarbonate brines from closed basins in volcanic terranes of Oregon and Kenya reveals silica contents of up to 2700 parts per million at pH's higher than 10. These high concentrations of SiO 2 can be attributed to reaction of waters with silicates, and subsequent evaporative concentration accompanied by a rise in pH. Supersaturation with respect to amorphous silica may occur and persist for brines that are out of contact with silicate muds and undersaturated with respect to trona; correlation of SiO2 with concentration of Na and total CO2 support this interpretation. Addition of moredilute waters to alkaline brines may lower the pH and cause inorganic precipitation of substantial amounts of silica.

Silica problem in the design of geothermal power plants

NASA Astrophysics Data System (ADS)

Dipippo, R.

1985-02-01

The silica problem is examined from the perspective of the power plant designer to develop a procedure to enable a quick estimate to be made of the potential seriousness of the silica deposition problem for a wide variety of resources and for selected types of power plant. The method employs correlations for the equilibrium solubilities of quartz and amorphous silica and for the saturated liquid enthalpy and the latent heat of water substance. Single- and double-flash plants optimized for highest thermodynamic efficiency are considered. Binary-type plants are included generically without mention of cycle specifics. The results are presented both graphically and in tabular form, and the governing equations will be given in an easily-programmable form.
Preparation and characterization of oriented silica nanowires

NASA Astrophysics Data System (ADS)

Sun, S. H.; Meng, G. W.; Zhang, M. G.; Tian, Y. T.; Xie, T.; Zhang, L. D.

2003-11-01

Large-scale of oriented closely packed silica nanowire bunches have been synthesized by using large size (1-10 μm in diameter), low melting point tin droplets as catalyst on silicon wafers at 980 °C. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analyses show that the amorphous silica nanowires have lengths of 50-100 μm and diameters of 100-200 nm. Unlike any previous observed results using high melting point metal (such as gold and iron) as catalyst, the Sn catalyst growth exhibits many interesting phenomena. Each Sn ball can simultaneously catalyze the growth of many silica nanowires, which is quite different from the conventional vapor-liquid-solid process.
Amorphous silica as a versatile supermolecular ligand for Ni(II) amine complexes: toward interfacial molecular recognition.

PubMed

Boujday, Souhir; Lambert, Jean-François; Che, Michel

2004-07-19

Selective adsorption of Ni(II) amine complexes used as precursors for supported catalysts was studied on amorphous silica surfaces. The nature of the adsorption sites was probed by [Ni(en)(dien) (H2O)]2+, [Ni(en)2(H2O)2]2+, and [Ni(dien)(H2O)3]2+ (en = ethylenediamine, dien = diethylenetriamine), which respectively contain one, two, and three labile aqua ligands. The silica surface acts as a mono- or polydentate ligand that can substitute the aqua ligands of the Ni(II) complexes in an inner-sphere adsorption mechanism. Room-temperature adsorption isotherms indicate that each nickel complex selects a limited number of adsorption sites; different sites are recognised by the three complexes, even though they have the same charge and comparable sizes. Several spectroscopic techniques (UV/Vis/NIR, EXAFS, and 29Si NMR) were used to confirm the selective character of the interaction of Ni(II) amine complexes with the silica surface. The specific sites include both silanol/silanolate groups in the same number as the original labile ligands and other surface groups that probably act as hydrogen-bond acceptors. These two types of groups cooperate to result in interfacial molecular-recognition phenomena with interactional complementarity.
Picosecond amorphization of SiO2 stishovite under tension

PubMed Central

Misawa, Masaaki; Ryuo, Emina; Yoshida, Kimiko; Kalia, Rajiv K.; Nakano, Aiichiro; Nishiyama, Norimasa; Shimojo, Fuyuki; Vashishta, Priya; Wakai, Fumihiro

2017-01-01

It is extremely difficult to realize two conflicting properties—high hardness and toughness—in one material. Nano-polycrystalline stishovite, recently synthesized from Earth-abundant silica glass, proved to be a super-hard, ultra-tough material, which could provide sustainable supply of high-performance ceramics. Our quantum molecular dynamics simulations show that stishovite amorphizes rapidly on the order of picosecond under tension in front of a crack tip. We find a displacive amorphization mechanism that only involves short-distance collective motions of atoms, thereby facilitating the rapid transformation. The two-step amorphization pathway involves an intermediate state akin to experimentally suggested “high-density glass polymorphs” before eventually transforming to normal glass. The rapid amorphization can catch up with, screen, and self-heal a fast-moving crack. This new concept of fast amorphization toughening likely operates in other pressure-synthesized hard solids. PMID:28508056
Adsorption of Water on Simulated Moon Dust Samples

NASA Technical Reports Server (NTRS)

Goering, John P.; Sah, Shweta; Burghaus, Uwe; Street, Kenneth W., Jr.

2008-01-01

A lunar regolith simulant dust sample (JSC-1a) supported on a silica wafer (SiO2/Si(111)) has been characterized by scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDX), and Auger electron spectroscopy (AES). The adsorption kinetics of water has been studied primarily by thermal desorption spectroscopy (TDS) and also by collecting isothermal adsorption transients. The support has been characterized by water TDS. JSC-1a consists mostly of aluminosilicate glass and other minerals containing Fe, Na, Ca, and Mg. The particle sizes span the range from a few microns up to 100 microns. At small exposures, H2O TDS is characterized by broad (100 to 450 K) structures; at large exposures distinct TDS peaks emerge that are assigned to amorphous solid water (145 K) and crystalline ice (165 K). Water dissociates on JSC-1a at small exposures but not on the bare silica support. It appears that rather porous condensed ice layers form at large exposures. At thermal impact energies, the initial adsorption probability amounts to 0.92+/-0.05.
Variability of the health effects of crystalline silica: Fe speciation in industrial quartz reagents and suspended dusts—insights from XAS spectroscopy

NASA Astrophysics Data System (ADS)

Di Benedetto, Francesco; D'Acapito, Francesco; Capacci, Fabio; Fornaciai, Gabriele; Innocenti, Massimo; Montegrossi, Giordano; Oberhauser, Werner; Pardi, Luca A.; Romanelli, Maurizio

2014-03-01

We investigated the speciation of Fe in bulk and in suspended respirable quartz dusts coming from ceramic and iron-casting industrial processes via X-ray absorption spectroscopy, with the aim of contributing to a better understanding of the variability of crystalline silica toxicity. Four different bulk industrial quartz powders, nominally pure quartz samples with Fe contents below 200 ppm, and three respirable dusts filters were selected. Fe speciation was determined in all samples through a coupled study of the X-ray absorption near-edge structure and extended X-ray absorption fine structure regions, operating at the Fe-K edge. Fe speciation revealed common features at the beginning of the different production processes, whereas significant differences were observed on both respirable dusts and bulk dusts exiting from the production process. Namely, a common pollution of the raw quartz dusts by elemental Fe was evidenced and attributed to residuals of the industrial production of quartz materials. Moreover, the respirable samples indicated that reactivity occurs after the suspension of the powders in air. The gravitational selection during the particle suspension consistently allowed us to clearly discriminate between suspended and bulk dusts. On the basis of the obtained results, we provide an apparent spectroscopic discrimination between the raw materials used in the considered industrial processes, and those that are effectively inhaled by workers. In particular, an amorphous FeIII oxide, with an unsaturated coordination sphere, can be related to silica reactivity (and health consequences).
Intracellularly Biodegradable Polyelectrolyte/Silica Composite Microcapsules as Carriers for Small Molecules.

PubMed

Gao, Hui; Goriacheva, Olga A; Tarakina, Nadezda V; Sukhorukov, Gleb B

2016-04-20

Microcapsules that can be efficiently loaded with small molecules and effectively released at the target area through the degradation of the capsule shells hold great potential for treating diseases. Traditional biodegradable polyelectrolyte (PE) capsules can be degraded by cells and eliminated from the body but fail to encapsulate drugs with small molecular weight. Here, we report a poly-l-arginine hydrochloride (PARG)/dextran sulfate sodium salt (DEXS)/silica (SiO2) composite capsule that can be destructed in cells and of which the in situ formed inorganic SiO2 enables loading of small model molecules, Rhodamine B (Rh-B). The composite capsules were fabricated based on the layer-by-layer (LbL) technique and the hydrolysis of tetraethoxysilane (TEOS). Capsules composed of nondegradable PEs and SiO2, polyllamine hydrochloride (PAH)/poly(sodium 4-styrenesulfonate) (PSS)/silica (the control sample), were prepared and briefly compared with the degradable composite capsules. An intracellular degradation study of both types of composite capsules revealed that PARG/DEXS/silica capsules were degraded into fragments and lead to the release of model molecules in a relatively short time (2 h), while the structure of PAH/PSS/silica capsules remained intact even after 3 days incubation with B50 cells. Such results indicated that the polymer components played a significant role in the degradability of the SiO2. Specifically, PAH/PSS scaffolds blocked the degradation of SiO2. For PARG/DEXS/silica capsules, we proposed the effects of both hydrolytic degradation of amorphous silica and enzymatic degradation of PARG/DEXS polymers as a cell degradation mechanism. All the results demonstrated a new type of functional composite microcapsule with low permeability, good biocompatibility, and biodegradability for potential medical applications.
New Silica Magnetite Sorbent: The Influence of Variations of Sodium Silicate Concentrations on Silica Magnetite Character

NASA Astrophysics Data System (ADS)

Azmiyawati, C.; Pratiwi, P. I.; Darmawan, A.

2018-04-01

The adsorption capacity of an adsorbent is determined by the adsorbent and the adsorbate properties. The character of the adsorbent will play a major role in its ability to adsorb the corresponding adsorbate. Therefore, in this study we looked at the effects of variations of sodium silicate concentrations on the resulting magnetite silica adsorbent properties. The application of silica coating on the magnetite was carried out through a sol-gel process with sodium silicate and HCl precursors. Based on the characterization data obtained, it was found that the silica coating on magnetite can increase the resistance to acid leaching, increase the particle size, but decrease the magnetic properties of the magnetite. Based on Gas Sorption Analyzer (GSA) and X-ray Difraction (XRD) data it can successively be determined that increase in concentration of sodium silicate will increase the surface area and amorphous structure of the Silica Magnetie.
Poisson's ratio and the densification of glass under high pressure.

PubMed

Rouxel, T; Ji, H; Hammouda, T; Moréac, A

2008-06-06

Because of a relatively low atomic packing density, (Cg) glasses experience significant densification under high hydrostatic pressure. Poisson's ratio (nu) is correlated to Cg and typically varies from 0.15 for glasses with low Cg such as amorphous silica to 0.38 for close-packed atomic networks such as in bulk metallic glasses. Pressure experiments were conducted up to 25 GPa at 293 K on silica, soda-lime-silica, chalcogenide, and bulk metallic glasses. We show from these high-pressure data that there is a direct correlation between nu and the maximum post-decompression density change.
Preparation and Characterization of Hydroxyapatite-Silica Composite Nanopowders

NASA Astrophysics Data System (ADS)

Latifi, S. M.; Fathi, M. H.; Golozar, M. A.

One of the most important objectives in the field of biomaterials science and engineering is development of new materials as bone substitutes. Silica (SiO2) has an important role in the biomineralization and biological responses. The aim of this research was to prepare and characterize hydroxyapatite-silica (HA-SiO2) composite nanopowder with different content of silica. Hydroxyapatite-silica composite nanopowders with 20 and 40 wt% silica were prepared using a sol-gel method at 600°C with phosphoric pentoxide and calcium nitrate tetrahydrate as a source of hydroxyapatite; also, tetraethylorthosilicate and methyltriethoxisilane as a source of silica. Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray analysis (EDX) techniques were used for characterization and evaluation of the products. The results indicated the presence of nanocrystalline hydroxyapatite phase beside amorphous silica phase in prepared composite nanopowders. Moreover, by increasing the content of silica in composite nanopowders, the crystallinity will be decreased,and the ability of the product as a bone substitute material might be controlled by changing the content of the ingredients and subsequently its structure.
Refractory ceramic has wide usage, low fabrication cost

NASA Technical Reports Server (NTRS)

1964-01-01

Particulate, fused amorphous silica is formed into complex shapes by casting in plaster molds. High temperature firing is not required. This ceramic is resistant to thermal shock and exhibits good strength properties.
Light induced dielectric constant of Alumina doped lead silicate glass based on silica sands

NASA Astrophysics Data System (ADS)

Diantoro, Markus; Natalia, Desi Ayu; Mufti, Nandang; Hidayat, Arif

2016-04-01

Numerous studies on glass ceramic compounds have been conducted intensively. Two major problems to be solved are to simplify the fabrication process by reducing melting temperature as well as improving various properties for various fields of technological application. To control the dielectric constant, the researchers generally use a specific dopant. So far there is no comprehensive study to control the dielectric constant driven by both of dopant and light intensity. In this study it is used Al2O3 dopant to increase the light induced dielectric constant of the glass. The source of silica was taken from local silica sands of Bancar Tuban. The sands were firstly leached using hydrochloric acid to improve the purity of silica which was investigated by means of XRF. Fabricating the glass samples were performed by using melting-glass method. Silica powder was mixed with various ratio of SiO2:Na2CO3:PbO:Al2O3. Subsequently, a mixture of various Al2O3 doped lead silicate glasses were melted at 970°C and directy continued by annealed at 300°C. The samples were investigated by XRD, FTIR, SEM-EDX and measuring dielectric constant was done using dc-capacitance meter with various light intensities. The investigation result of XRD patterns showed that the crystal structures of the samples are amorphous state. The introduction of Al2O3 does not alter the crystal structure, but significantly change the structure of the functional glass bonding PbO-SiO2 which was shown by the FTIR spectra. It was noted that some new peak peaks were exist in the doped samples. Measuring result of dielectricity shows that the dielectric constant of glass increases with the addition of Al2O3. Increasing the light intensity gives rise to increase their dielectric constant in general. A detail observation of the dielectric seen that there are discontinuous step-like of dielectric. Most likely a specific quantization mechanism occurs when glass exposed under light.
Polyamorphism in tetrahedral substances: Similarities between silicon and ice

NASA Astrophysics Data System (ADS)

Garcez, K. M. S.; Antonelli, A.

2015-07-01

Tetrahedral substances, such as silicon, water, germanium, and silica, share various unusual phase behaviors. Among them, the so-called polyamorphism, i.e., the existence of more than one amorphous form, has been intensively investigated in the last three decades. In this work, we study the metastable relations between amorphous states of silicon in a wide range of pressures, using Monte Carlo simulations. Our results indicate that the two amorphous forms of silicon at high pressures, the high density amorphous (HDA) and the very high density amorphous (VHDA), can be decompressed from high pressure (˜20 GPa) down to the tensile regime, where both convert into the same low density amorphous. Such behavior is also observed in ice. While at high pressure (˜20 GPa), HDA is less stable than VHDA, at the pressure of 10 GPa both forms exhibit similar stability. On the other hand, at much lower pressure (˜5 GPa), HDA and VHDA are no longer the most stable forms, and, upon isobaric annealing, an even less dense form of amorphous silicon emerges, the expanded high density amorphous, again in close similarity to what occurs in ice.
Study of ice cluster impacts on amorphous silica using the ReaxFF reactive force field molecular dynamics simulation method

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

Rahnamoun, A.; Duin, A. C. T. van

We study the dynamics of the collisions between amorphous silica structures and amorphous and crystal ice clusters with impact velocities of 1 km/s, 4 km/s, and 7 km/s using the ReaxFF reactive molecular dynamics simulation method. The initial ice clusters consist of 150 water molecules for the amorphous ice cluster and 128 water molecules for the crystal ice cluster. The ice clusters are collided on the surface of amorphous fully oxidized and suboxide silica. These simulations show that at 1 km/s impact velocities, all the ice clusters accumulate on the surface and at 4 km/s and 7 km/s impact velocities, some of the ice cluster moleculesmore » bounce back from the surface. At 4 km/s and 7 km/s impact velocities, few of the water molecules dissociations are observed. The effect of the second ice cluster impacts on the surfaces which are fully covered with ice, on the mass loss/accumulation is studied. These studies show that at 1 km/s impacts, the entire ice cluster accumulates on the surface at both first and second ice impacts. At higher impact velocities, some ice molecules which after the first ice impacts have been attached to the surface will separate from the surface after the second ice impacts at 7 km/s impact velocity. For the 4 km/s ice cluster impact, ice accumulation is observed for the crystal ice cluster impacts and ice separation is observed for the amorphous ice impacts. Observing the temperatures of the ice clusters during the collisions indicates that the possibility of electron excitement at impact velocities less than 10 km/s is minimal and ReaxFF reactive molecular dynamics simulation can predict the chemistry of these hypervelocity impacts. However, at impact velocities close to 10 km/s the average temperature of the impacting ice clusters increase to about 2000 K, with individual molecules occasionally reaching temperatures of over 8000 K and thus it will be prudent to consider the concept of electron excitation at these higher impact velocities, which goes beyond the current ReaxFF ability.« less
Silica supported TiO{sub 2} nanostructures for highly efficient photocatalytic application under visible light irradiation

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

Pal, A.; Jana, T.K.; Chatterjee, K., E-mail: kuntal2k@gmail.com

2016-04-15

Highlights: • Synthesis of silica–titania nanocomposite by simple and facile chemical route and characterization of the materials. • Excellent catalytic activity on organic pollutant methylene blue under the visible light irradiation. • Photocatalytic rate is much higher than commercial P25 TiO{sub 2} catalyst powder. • The higher activity is attributed to the special structure and synergistic effect of the materials which has immense application potential. - Abstract: Titanium dioxide decorated silica nanospheres have been synthesized by a simple wet chemical approach. X-ray diffraction, electron microscopy and energy dispersive X-ray analysis revealed that anatase phase of TiO{sub 2} nanostructures, with exposedmore » {0 0 1} and {1 0 1} facets, are anchored onto the amorphous silica spheres of ∼60 nm diameter. The photocatalytic activity of the sample under visible light irradiation was examined. It is found that photocatalytic efficiency of the material is better than commercial P25 TiO{sub 2} photocatalyst and the result is attributed to the unique synergistic effect of SiO{sub 2}–TiO{sub 2} nanocomposite structure resulting enhanced charge separation and charge transfer.« less
Reactive molecular dynamics simulation on the disintegration of Kapton, POSS polyimide, amorphous silica, and teflon during atomic oxygen impact using the ReaxFF reactive force-field method.

PubMed

Rahnamoun, A; van Duin, A C T

2014-04-17

Atomic oxygen (AO) is the most abundant element in the low Earth orbit (LEO). It is the result of the dissociation of molecular oxygen by ultraviolet radiation from the sun. In the LEO, it collides with the materials used on spacecraft surfaces and causes degradation of these materials. The degradation of the materials on the surface of spacecrafts at LEO has been a significant problem for a long time. Kapton polyimide, polyhedral oligomeric silsesquioxane (POSS), silica, and Teflon are the materials extensively used in spacecraft industry, and like many other materials used in spacecraft industry, AO collision degradation is an important issue in their applications on spacecrafts. To investigate the surface chemistry of these materials in exposure to space AO, a computational chemical evaluation of the Kapton polyimide, POSS, amorphous silica, and Teflon was performed in separate simulations under similar conditions. For performing these simulations, the ReaxFF reactive force-field program was used, which provides the computational speed required to perform molecular dynamics (MD) simulations on system sizes sufficiently large to describe the full chemistry of the reactions. Using these simulations, the effects of AO impact on different materials and the role of impact energies, the content of material, and temperature of material on the behavior of the materials are studied. The ReaxFF results indicate that Kapton is less resistant than Teflon toward AO damage. These results are in good agreement with experiment. These simulations indicate that the amorphous silica shows the highest stability among these materials before the start of the highly exothermic silicon oxidation. We have verified that adding silicon to the bulk of the Kapton structure enhances the stability of the Kapton against AO impact. Our canonical MD simulations demonstrate that an increase in the heat transfer in materials during AO impact can provide a considerable decrease in the disintegration of the material. This effect is especially relevant in silica AO collision. Considerable experimental efforts have been undertaken to minimize such AO-based degradations. As our simulations demonstrate, ReaxFF can provide a cost-effective screening tool for future material optimization.
Probing the chemistry, structure, and dynamics of the water-silica interface

NASA Astrophysics Data System (ADS)

Lockwood, Glenn K.

Despite its natural abundance and wide-ranging technological relevance, much remains unknown or unclear about water-silica interfaces. Computer simulation stands to bridge the gaps of knowledge left by experiment, and a recently developed Dissociative Water Potential has enabled the simulation of large amorphous silica surfaces in contact with water without having to impose a model of surface chemistry a priori. Earlier work with this model has revealed the existence of several protonated surface sites such as SiOH2 + and Si-(OH+)-Si that have yet to be extensively characterized. However, both experiment and quantum mechanical simulation have provided an increasing body of evidence that suggests these sites exist, and these sites may play key roles in some of the unexplained phenomena observed in water-silica systems. To this end, this Dissociative Water Potential has been applied to develop a comprehensive picture of the chemistry, structure, and dynamics of the water-silica interface that is unbiased by any expectation of what sites should form. The bridging OH site, Si-(OH+)-Si, does form and is characterized as a highly acidic site that occurs predominantly on strained Si-O-Si bridges near the interface. Similarly, the transient formation of SiOH2 + is observed, and this site is found to be more acidic than Si-(OH +)-Si. In addition to H3O+ that forms near the interface, all of these sites readily deprotonate and are expected to play a role in the enhanced proton conductivity experimentally observed in hydrated mesoporous silica. The reactions between water and silica are particularly relevant to the engineering of nuclear waste forms, and the role of water-silica interactions are also explored within the context of the degradation of silica-based waste forms exposed to radiation. Despite the significant simulation effort employed in glassy waste form research, no molecular models of radiation damage in silica include the effects of moisture. This deficiency is addressed, and water is found to play a significant role in accelerating the degradation of amorphous silica under irradiation. Water inhibits healing of the network and promotes the formation of voids into which more water can penetrate, giving way to new damage accumulation mechanisms not seen in any past simulations.
Synthesis of biogenic silicon/silica (Si/SiO2) nanocomposites from rice husks and wheat bran through various microorganisms

NASA Astrophysics Data System (ADS)

Kaur, Taranjot; Pal Singh, Gurwinder; Kaur, Gurneet; Kaur, Sukhvir; Gill, Prabhjot Kaur

2016-08-01

Biosilification is an economically viable, energy saving and green approach for the commercial scale synthesis of oxide nanomaterials. The room temperature synthesis of oxide nanocomposites from cost effective agro-based waste is a particular example of biosilification. In this study, synthesis of Si/SiO2 nanocomposites from inexpensive agro-based waste material i.e. rice husks (RH) and wheat bran (WB) has been carried out by means of various eukaryotic microorganisms, i.e. Actinomycete, Fusarium oxysporum, Aspergillus niger, Trichoderma sp. and Penicillium sp., under ambient conditions. The XRD diffrectrograms represents that the synthesized nanomaterials exhibits silicon, amorphous silica and other crystal arrays such as cristobalite, trydimite and quartz, depending upon the type microorganism and time period used for extraction. All of the aforesaid microorganism bio transformed the naturally occurring amorphous silica to crystalline structures within the period of 24 h. However, the Actinomycete and Trichoderma sp. took 48 h in case of rice husks for biotransformation of naturally occurring plant silica to crystalline nanocomposite. While in case of wheat bran, Actinomycete and Trichoderma sp. took 24 h for biotransformation. The extracted nanocomposites exhibits band edge in the range 230-250 nm and blue emission. The procedure described in study can be used for commercial level production of Si/SiO2 nanocomposites from agro based waste materials.
Preparation and Characterization of WS2@SiO2 and WS2@PANI Core-Shell Nanocomposites

PubMed Central

Sade, Hagit

2018-01-01

Two tungsten disulfide (WS2)-based core-shell nanocomposites were fabricated using readily available reagents and simple procedures. The surface was pre-treated with a surfactant couple in a layer-by-layer approach, enabling good dispersion of the WS2 nanostructures in aqueous media and providing a template for the polymerization of a silica (SiO2) shell. After a Stöber-like reaction, a conformal silica coating was achieved. Inspired by the resulting nanocomposite, a second one was prepared by reacting the surfactant-modified WS2 nanostructures with aniline and an oxidizing agent in an aqueous medium. Here too, a conformal coating of polyaniline (PANI) was obtained, giving a WS2@PANI nanocomposite. Both nanocomposites were analyzed by electron microscopy, energy dispersive X-ray spectroscopy (EDS) and FTIR, verifying the core-shell structure and the character of shells. The silica shell was amorphous and mesoporous and the surface area of the composite increases with shell thickness. Polyaniline shells slightly differ in their morphologies dependent on the acid used in the polymerization process and are amorphous like the silica shell. Electron paramagnetic resonance (EPR) spectroscopy of the WS2@PANI nanocomposite showed variation between bulk PANI and the PANI shell. These two nanocomposites have great potential to expand the use of transition metals dichalcogenides (TMDCs) for new applications in different fields. PMID:29534426
Bio-Inspired Bright Structurally Colored Colloidal Amorphous Array Enhanced by Controlling Thickness and Black Background.

PubMed

Iwata, Masanori; Teshima, Midori; Seki, Takahiro; Yoshioka, Shinya; Takeoka, Yukikazu

2017-07-01

Inspired by Steller's jay, which displays angle-independent structural colors, angle-independent structurally colored materials are created, which are composed of amorphous arrays of submicrometer-sized fine spherical silica colloidal particles. When the colloidal amorphous arrays are thick, they do not appear colorful but almost white. However, the saturation of the structural color can be increased by (i) appropriately controlling the thickness of the array and (ii) placing the black background substrate. This is similar in the case of the blue feather of Steller's jay. Based on the knowledge gained through the biomimicry of structural colored materials, colloidal amorphous arrays on the surface of a black particle as the core particle are also prepared as colorful photonic pigments. Moreover, a structural color on-off system is successfully built by controlling the background brightness of the colloidal amorphous arrays. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Poisson's Ratio and the Densification of Glass under High Pressure

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

Rouxel, T.; Ji, H.; Hammouda, T.

2008-06-06

Because of a relatively low atomic packing density, (C{sub g}) glasses experience significant densification under high hydrostatic pressure. Poisson's ratio ({nu}) is correlated to C{sub g} and typically varies from 0.15 for glasses with low C{sub g} such as amorphous silica to 0.38 for close-packed atomic networks such as in bulk metallic glasses. Pressure experiments were conducted up to 25 GPa at 293 K on silica, soda-lime-silica, chalcogenide, and bulk metallic glasses. We show from these high-pressure data that there is a direct correlation between {nu} and the maximum post-decompression density change.
Elucidation of Compression-Induced Surface Crystallization in Amorphous Tablets Using Sum Frequency Generation (SFG) Microscopy.

PubMed

Mah, Pei T; Novakovic, Dunja; Saarinen, Jukka; Van Landeghem, Stijn; Peltonen, Leena; Laaksonen, Timo; Isomäki, Antti; Strachan, Clare J

2017-05-01

To investigate the effect of compression on the crystallization behavior in amorphous tablets using sum frequency generation (SFG) microscopy imaging and more established analytical methods. Tablets containing neat amorphous griseofulvin with/without excipients (silica, hydroxypropyl methylcellulose acetate succinate (HPMCAS), microcrystalline cellulose (MCC) and polyethylene glycol (PEG)) were prepared. They were analyzed upon preparation and storage using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, scanning electron microscopy (SEM) and SFG microscopy. Compression-induced crystallization occurred predominantly on the surface of the neat amorphous griseofulvin tablets, with minimal crystallinity being detected in the core of the tablets. The presence of various types of excipients was not able to mitigate the compression-induced surface crystallization of the amorphous griseofulvin tablets. However, the excipients affected the crystallization rate of amorphous griseofulvin in the core of the tablet upon compression and storage. SFG microscopy can be used in combination with ATR-FTIR spectroscopy and SEM to understand the crystallization behaviour of amorphous tablets upon compression and storage. When selecting excipients for amorphous formulations, it is important to consider the effect of the excipients on the physical stability of the amorphous formulations.
New Evidence from Silica Debris Exo-Systems for Planet Building Hypervelocity Impacts

NASA Astrophysics Data System (ADS)

Lisse, Carey

2010-05-01

There is abundant inferential evidence for massive collisions in the early solar system [1]: Mercury's high density; Venus' retrograde spin; Earth's Moon; Mars' North/South hemispherical cratering anisotropy; Vesta's igneous origin [2]; brecciation in meteorites [3]; and Uranus' spin axis located near the plane of the ecliptic. Recent work [4] analyzing Spitzer mid-IR spectra has demonstrated the presence of large amounts of amorphous silica and SiO gas produced by a recent (within 103 - 104 yrs) large (MExcess > MPluto) hypervelocity impact collision around the young (~12 Myr old) nearby star HD172555, at the right age to form rocky planets. Many questions still remain concerning the location, lifetime, and source of the detected silica/SiO gas, which should not be stable in orbit at the estimated 5.8 AU from the HD172555 A5V primary for more than a few decades, yet it is also highly unlikely that we are fortuitously observing these systems immediately after silica formation A tabulation of the amount counts in the fine silica dust is decidedly Fe and Mg-atom poor compared to solar [4]. Three possible origins for the observed silica/SiO gas seem currently plausible : (1) A single hyperevelocity impact (>10km/s in order to produce silica and vaporize SiO at impact) creating an optically thick circumplanetary debris ring which is overflowing or releasing silica-rich material from its Hill sphere. Like terrestrial tektites, the Fe/Mg poor amorphous silica rubble is formed from quick-quenched molten/vaporized rock created during the impact. The amount of dust detected in the HD172555 system is easily enough to fill and overflow the Hill sphere radius of 0.03 AU for a Pluto-sized body at 5.8 AU from an A5 star, unless it is optically thick (> 1 cm in physical depth). Such a disk would provide a substantial fraction of the observed IR flux, and will be dense enough to self-shield its SiO gas, greatly extending its photolytic lifetime. The lifetime for such a system versus re-condensation into a solid body like the Moon is short, though, ~ 103 to 104 yrs [5]. Credence is lent to this scenario by observations of the Jovian impact in July 2009 [6], where absorption features due to silica have been found superimposed on those of hot ammonia at the > 60 km/s impact site (Fig. 1). (2) Ongoing multiple small hypervelocity impacts continuously grinding down a distribution of large circumstellar particles above the blowout size limit (the 'rubble' identified in [4]) and releasing silica rich material and SiO gas. This model would require a massive (>1 MMoon) belt of 10 μm - 1 cm particles with inclinations spread out over at least ±45o [4] or dust on highly eccentric orbits [7]. The amount of material implied by the relative amplitude of the rubble spectral feature is consistent with the amount needed to collisionally produce the fine silica dust [4, 8]. A body rapidly re-accreting in a debris ring after collisional disruption (like the Moon) would have similar behavior (lots of impacts for some time, producing gas and little melt droplets). (3) A single impact onto a silica-rich object with already highly differentiated surface layers. For a very young system at 10 - 20 Myr when we expect planets to be rapidly accreting, a Mercury or larger-sized rocky body covered in an SiO rich magma ocean is very likely by the Jeans energy criterion [9], even without considering additional heating input by 26Al and other radioactives. For the lowest expected impact velocities,v MercuryEscape = 4 km/s, a pre-existing magma ocean in equilibrium with a surrounding SiO atmosphere would be required; at higher velocities the impacting body could be the formative mechanism for the magma ocean [10]. Further evidence for excess circumstellar emission due to silica dust have now been found. The youngest of these, HD154263, at ~20 Myr age shows evidence for SiO gas and amorphous + crystalline silica. The 2 older systems, HD23514 at ~100 Myr age, and HD15407 at ~2 Gyr, conspicuously do not show any evidence for SiO gas while exhibiting strong features mainly due to crystalline silica. HD23514 also shows evidence for large amounts of amorphous carbon, PAHs, and nanodiamonds, due to a strongly enhanced C-atom abundance in impactor or impactee. HD15407, the oldest system, also does not show any conclusive evidence for the presence of large dark particles ('rubble').
Controlled release of chlorhexidine antiseptic from microporous amorphous silica applied in open porosity of an implant surface.

PubMed

Verraedt, Els; Braem, Annabel; Chaudhari, Amol; Thevissen, Karin; Adams, Erwin; Van Mellaert, Lieve; Cammue, Bruno P A; Duyck, Joke; Anné, Jozef; Vleugels, Jef; Martens, Johan A

2011-10-31

Amorphous microporous silica (AMS) serving as a reservoir for controlled release of a bioactive agent was applied in the open porosity of a titanium coating on a Ti-6Al-4V metal substrate. The pores of the AMS emptied by calcination were loaded with chlorhexidine diacetate (CHX) via incipient wetness impregnation with CHX solution, followed by solvent evaporation. Using this CHX loaded AMS system on titanium substrate sustained release of CHX into physiological medium was obtained over a 10 day-period. CHX released from the AMS coating was demonstrated to be effective in killing planktonic cultures of the human pathogens Candida albicans and Staphylococcus epidermidis. This surface modification of titanium bodies with AMS controlled release functionality for a bioactive compound potentially can be applied on dental and orthopaedic implants to abate implant-associated microbial infection. Copyright © 2011 Elsevier B.V. All rights reserved.
High-harmonic generation in amorphous solids

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

You, Yong Sing; Yin, Yanchun; Wu, Yi

High-harmonic generation in isolated atoms and molecules has been widely utilized in extreme ultraviolet photonics and attosecond pulse metrology. Recently, high-harmonic generation has been observed in solids, which could lead to important applications such as all-optical methods to image valance charge density and reconstruct electronic band structures, as well as compact extreme ultraviolet light sources. So far these studies are confined to crystalline solids; therefore, decoupling the respective roles of long-range periodicity and high density has been challenging. Here we report the observation of high-harmonic generation from amorphous fused silica. We also decouple the role of long-range periodicity by comparingmore » harmonics generated from fused silica and crystalline quartz, which contain the same atomic constituents but differ in long-range periodicity. These results advance current understanding of the strong-field processes leading to high-harmonic generation in solids with implications for the development of robust and compact extreme ultraviolet light sources.« less
High-harmonic generation in amorphous solids

DOE PAGES

You, Yong Sing; Yin, Yanchun; Wu, Yi; ...

2017-09-28

High-harmonic generation in isolated atoms and molecules has been widely utilized in extreme ultraviolet photonics and attosecond pulse metrology. Recently, high-harmonic generation has been observed in solids, which could lead to important applications such as all-optical methods to image valance charge density and reconstruct electronic band structures, as well as compact extreme ultraviolet light sources. So far these studies are confined to crystalline solids; therefore, decoupling the respective roles of long-range periodicity and high density has been challenging. Here we report the observation of high-harmonic generation from amorphous fused silica. We also decouple the role of long-range periodicity by comparingmore » harmonics generated from fused silica and crystalline quartz, which contain the same atomic constituents but differ in long-range periodicity. These results advance current understanding of the strong-field processes leading to high-harmonic generation in solids with implications for the development of robust and compact extreme ultraviolet light sources.« less
Numerical Simulation of Tuff Dissolution and Precipitation Experiments: Validation of Thermal-Hydrologic-Chemical (THC) Coupled-Process Modeling

NASA Astrophysics Data System (ADS)

Dobson, P. F.; Kneafsey, T. J.

2001-12-01

As part of an ongoing effort to evaluate THC effects on flow in fractured media, we performed a laboratory experiment and numerical simulations to investigate mineral dissolution and precipitation. To replicate mineral dissolution by condensate in fractured tuff, deionized water equilibrated with carbon dioxide was flowed for 1,500 hours through crushed Yucca Mountain tuff at 94° C. The reacted water was collected and sampled for major dissolved species, total alkalinity, electrical conductivity, and pH. The resulting steady-state fluid composition had a total dissolved solids content of about 140 mg/L; silica was the dominant dissolved constituent. A portion of the steady-state reacted water was flowed at 10.8 mL/hr into a 31.7-cm tall, 16.2-cm wide vertically oriented planar fracture with a hydraulic aperture of 31 microns in a block of welded Topopah Spring tuff that was maintained at 80° C at the top and 130° C at the bottom. The fracture began to seal within five days. A 1-D plug-flow model using the TOUGHREACT code developed at Berkeley Lab was used to simulate mineral dissolution, and a 2-D model was developed to simulate the flow of mineralized water through a planar fracture, where boiling conditions led to mineral precipitation. Predicted concentrations of the major dissolved constituents for the tuff dissolution were within a factor of 2 of the measured average steady-state compositions. The fracture-plugging simulations result in the precipitation of amorphous silica at the base of the boiling front, leading to a hundred-fold decrease in fracture permeability in less than 6 days, consistent with the laboratory experiment. These results help validate the use of the TOUGHREACT code for THC modeling of the Yucca Mountain system. The experiment and simulations indicate that boiling and concomitant precipitation of amorphous silica could cause significant reductions in fracture porosity and permeability on a local scale. The TOUGHREACT code will be used to evaluate larger-scale silica sealing observed in a portion of the Yellowstone geothermal system, a natural analog for the precipitation-experiment processes.
A molecular dynamics study of ambient and high pressure phases of silica: structure and enthalpy variation with molar volume.

PubMed

Rajappa, Chitra; Sringeri, S Bhuvaneshwari; Subramanian, Yashonath; Gopalakrishnan, J

2014-06-28

Extensive molecular dynamics studies of 13 different silica polymorphs are reported in the isothermal-isobaric ensemble with the Parrinello-Rahman variable shape simulation cell. The van Beest-Kramer-van Santen (BKS) potential is shown to predict lattice parameters for most phases within 2%-3% accuracy, as well as the relative stabilities of different polymorphs in agreement with experiment. Enthalpies of high-density polymorphs - CaCl2-type, α-PbO2-type, and pyrite-type - for which no experimental data are available as yet, are predicted here. Further, the calculated enthalpies exhibit two distinct regimes as a function of molar volume-for low and medium-density polymorphs, it is almost independent of volume, while for high-pressure phases a steep dependence is seen. A detailed analysis indicates that the increased short-range contributions to enthalpy in the high-density phases arise not only from an increased coordination number of silicon but also shorter Si-O bond lengths. Our results indicate that amorphous phases of silica exhibit better optimization of short-range interactions than crystalline phases at the same density while the magnitude of Coulombic contributions is lower in the amorphous phase.
Identification And Characterization Of The Solids Found In Extraction Contactor SEP-401 In June 2012

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

Fondeur, F. F.; Fink, S. D.

2012-12-10

The Modular Caustic-Side Solvent Extraction Unit (MCU) recently conducted an outage that included maintenance on the centrifugal contactors. Operations personnel observed solids or deposits in two contactors and attempted to collect samples for analyses by Savannah River National Laboratory (SRNL). The residues found in Extraction Contactor SEP-401 are a mixture of amorphous silica, aluminosilicate, titanium, and debris from low alloy steel. The solids contain low concentrations of plutonium and strontium. These isotopes are associated with the titanium that came from the monosodium titanate (MST) added in the Actinide Removal Process (ARP) most likely as leached Ti from the MST thatmore » precipitated subsequently in MCU. An attempt was also made to obtain samples from the contents of Wash Contactor SEP-702. However, sampling provide ineffective.« less
Formation of magnesium silicate hydrate (M-S-H) cement pastes using sodium hexametaphosphate

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

Zhang, Tingting; Department of Materials, Centre for Advanced Structural Ceramics, Imperial College London, South Kensington Campus, London SW7 2AZ; Department of Civil and Environmental Engineering, Imperial College London, South Kensington Campus, London SW7 2AZ

2014-11-15

Magnesium silicate hydrate (M-S-H) gel is formed by the reaction of brucite with amorphous silica during sulphate attack in concrete and M-S-H is therefore regarded as having limited cementing properties. The aim of this work was to form M-S-H pastes, characterise the hydration reactions and assess the resulting properties. It is shown that M-S-H pastes can be prepared by reacting magnesium oxide (MgO) and silica fume (SF) at low water to solid ratio using sodium hexametaphosphate (NaHMP) as a dispersant. Characterisation of the hydration reactions by x-ray diffraction and thermogravimetric analysis shows that brucite and M-S-H gel are formed andmore » that for samples containing 60 wt.% SF and 40 wt.% MgO all of the brucites react with SF to form M-S-H gel. These M-S-H cement pastes were found to have compressive strengths in excess of 70 MPa.« less
Silica deposits on Mars with features resembling hot spring biosignatures at El Tatio in Chile

PubMed Central

Ruff, Steven W.; Farmer, Jack D.

2016-01-01

The Mars rover Spirit encountered outcrops and regolith composed of opaline silica (amorphous SiO2·nH2O) in an ancient volcanic hydrothermal setting in Gusev crater. An origin via either fumarole-related acid-sulfate leaching or precipitation from hot spring fluids was suggested previously. However, the potential significance of the characteristic nodular and mm-scale digitate opaline silica structures was not recognized. Here we report remarkably similar features within active hot spring/geyser discharge channels at El Tatio in northern Chile, where halite-encrusted silica yields infrared spectra that are the best match yet to spectra from Spirit. Furthermore, we show that the nodular and digitate silica structures at El Tatio that most closely resemble those on Mars include complex sedimentary structures produced by a combination of biotic and abiotic processes. Although fully abiotic processes are not ruled out for the Martian silica structures, they satisfy an a priori definition of potential biosignatures. PMID:27853166
Hyphenation of Raman spectroscopy with gravimetric analysis to interrogate water-solid interactions in pharmaceutical systems.

PubMed

Gift, Alan D; Taylor, Lynne S

2007-01-04

A moisture sorption gravimetric analyzer has been combined with a Raman spectrometer to better understand the various modes of water-solid interactions relevant to pharmaceutical systems. A commercial automated moisture sorption balance was modified to allow non-contact monitoring of the sample properties by interfacing a Raman probe with the sample holder. This hybrid instrument allows for gravimetric and spectroscopic changes to be monitored simultaneously. The utility of this instrument was demonstrated by investigating different types of water-solid interactions including stoichiometric and non-stoichiometric hydrate formation, deliquescence, amorphous-crystalline transformation, and capillary condensation. In each of the model systems, sulfaguanidine, cromolyn sodium, ranitidine HCl, amorphous sucrose and silica gel, spectroscopic changes were observed during the time course of the moisture sorption profile. Analysis of spectroscopic data provided information about the origin of the observed changes in moisture content as a function of relative humidity. Furthermore, multivariate data analysis techniques were employed as a means of processing the spectroscopic data. Principle components analysis was found to be useful to aid in data processing, handling and interpretation of the spectral changes that occurred during the time course of the moisture sorption profile.
Creep of Hi-Nicalon S Ceramic Fiber Tows at 800 deg C in Air and in Silicic Acid-Saturated Steam

DTIC Science & Technology

2015-12-26

earliest recorded instances is that of Egyptian brick making. As far back as approximately 1500 BC, Egyptians added straw to clay for bricks [3]. This...The accuracy of this calculation method depends on the accuracy of amorphous silica viscosity data, which, in turn, are affected by impurities in...the SiC fiber. Lack of availability of viscosity data for crystobalite and tridymite pre- cluded calculation of growth stresses in crystallized silica
The Structure and Properties of Silica Glass Nanostructures using Novel Computational Systems

NASA Astrophysics Data System (ADS)

Doblack, Benjamin N.

The structure and properties of silica glass nanostructures are examined using computational methods in this work. Standard synthesis methods of silica and its associated material properties are first discussed in brief. A review of prior experiments on this amorphous material is also presented. Background and methodology for the simulation of mechanical tests on amorphous bulk silica and nanostructures are later presented. A new computational system for the accurate and fast simulation of silica glass is also presented, using an appropriate interatomic potential for this material within the open-source molecular dynamics computer program LAMMPS. This alternative computational method uses modern graphics processors, Nvidia CUDA technology and specialized scientific codes to overcome processing speed barriers common to traditional computing methods. In conjunction with a virtual reality system used to model select materials, this enhancement allows the addition of accelerated molecular dynamics simulation capability. The motivation is to provide a novel research environment which simultaneously allows visualization, simulation, modeling and analysis. The research goal of this project is to investigate the structure and size dependent mechanical properties of silica glass nanohelical structures under tensile MD conditions using the innovative computational system. Specifically, silica nanoribbons and nanosprings are evaluated which revealed unique size dependent elastic moduli when compared to the bulk material. For the nanoribbons, the tensile behavior differed widely between the models simulated, with distinct characteristic extended elastic regions. In the case of the nanosprings simulated, more clear trends are observed. In particular, larger nanospring wire cross-sectional radii (r) lead to larger Young's moduli, while larger helical diameters (2R) resulted in smaller Young's moduli. Structural transformations and theoretical models are also analyzed to identify possible factors which might affect the mechanical response of silica nanostructures under tension. The work presented outlines an innovative simulation methodology, and discusses how results can be validated against prior experimental and simulation findings. The ultimate goal is to develop new computational methods for the study of nanostructures which will make the field of materials science more accessible, cost effective and efficient.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Farges, Francois; /Museum Nat. Hist., Paris /Stanford U., Geo. Environ. Sci.; Benzerara, Karim

XAFS and {mu}-XAFS spectra were collected at the Cu K-edge for seven chrysocolla samples (Peru, USA, and Congo). The results suggest that the local structure around Cu is similar to that in Cu(OH){sub 2} (spertiniite). Cu-L{sub 3} STXM imaging and spectroscopy confirm that the chrysocolla samples examined here consist of mesoscopic Cu(II)-rich domains surrounded by Si-rich domains (in agreement with results from infra-red spectroscopy). Hence, we suggest that chrysocolla, which is generally considered to be orthorhombic with composition (Cu,Al){sub 2}H{sub 2}Si{sub 2}O{sub 5}(OH){sub 4} {center_dot} nH{sub 2}O, is in actually a mesoscopic assemblage composed dominantly of spertiniite (Cu(OH){sub 2}), watermore » and amorphous silica (SiO{sub 2}).« less
Silicon in Imperata cylindrica (L.) P. Beauv: content, distribution, and ultrastructure.

PubMed

Rufo, Lourdes; Franco, Alejandro; de la Fuente, Vicenta

2014-07-01

Silicon concentration, distribution, and ultrastructure of silicon deposits in the Poaceae Imperata cylindrica (L.) P. Beauv. have been studied. This grass, known for its medicinal uses and also for Fe hyperaccumulation and biomineralization capacities, showed a concentration of silicon of 13,705 ± 9,607 mg/kg dry weight. Silicon was found as an important constituent of cell walls of the epidermis of the whole plant. Silica deposits were found in silica bodies, endodermis, and different cells with silicon-collapsed lumen as bulliforms, cortical, and sclerenchyma cells. Transmission electron microscope observations of these deposits revealed an amorphous material of an ultrastructure similar to that previously reported in silica bodies of other Poaceae.
In vitro effects of cisplatin-functionalized silica nanoparticles on chondrocytes

NASA Astrophysics Data System (ADS)

Bhowmick, Tridib Kumar; Yoon, Diana; Patel, Minal; Fisher, John; Ehrman, Sheryl

2010-10-01

In this study, we evaluated the combined effect of a known toxic molecule, cisplatin, in combination with relatively nontoxic nanoparticles, amorphous fumed silica, on chondrocyte cells. Cisplatin was attached to silica nanoparticles using aminopropyltriethoxy silane as a linker molecule, and characterized in terms of size, shape, specific surface area, as well as the dissolution of cisplatin from the silica surface. The primary particle diameter of the as-received silica nanoparticles ranged from 7.1 to 61 nm, estimated from measurements of specific surface area, and the primary particles were aggregated. The effects of cisplatin-functionalized silica particles with different specific surface areas (41, 85, 202, 237, and 297 m2/g) were compared in vitro on chondrocytes, the parenchymal cell of hyaline cartilage. The results show that adverse effects on cell function, as evidenced by reduced metabolic activity measured by the MTT assay and increased membrane permeability observed using the Live/Dead stain, can be correlated with specific surface area of the silica. Cisplatin-functionalized silica nanoparticles with the highest specific surface area incited the greatest response, which was almost equivalent to that induced by free cisplatin. This result suggests the importance of particle specific surface area in interactions between cells and surface-functionalized nanomaterials.
Water Contact Angle Dependence with Hydroxyl Functional Groups on Silica Surfaces under CO2 Sequestration Conditions.

PubMed

Chen, Cong; Zhang, Ning; Li, Weizhong; Song, Yongchen

2015-12-15

Functional groups on silica surfaces under CO2 sequestration conditions are complex due to reactions among supercritical CO2, brine and silica. Molecular dynamics simulations have been performed to investigate the effects of hydroxyl functional groups on wettability. It has been found that wettability shows a strong dependence on functional groups on silica surfaces: silanol number density, space distribution, and deprotonation/protonation degree. For neutral silica surfaces with crystalline structure (Q(3), Q(3)/Q(4), Q(4)), as silanol number density decreases, contact angle increases from 33.5° to 146.7° at 10.5 MPa and 318 K. When Q(3) surface changes to an amorphous structure, water contact angle increases 20°. Water contact angle decreases about 12° when 9% of silanol groups on Q(3) surface are deprotonated. When the deprotonation degree increases to 50%, water contact angle decreases to 0. The dependence of wettability on silica surface functional groups was used to analyze contact angle measurement ambiguity in literature. The composition of silica surfaces is complicated under CO2 sequestration conditions, the results found in this study may help to better understand wettability of CO2/brine/silica system.
Synthesis and adsorption of silica gel modified 3-aminopropyltriethoxysilane (APTS) from corn cobs against Cu(II) in water

NASA Astrophysics Data System (ADS)

Purwanto, Agung; Yusmaniar, Ferdiani, Fatmawati; Damayanti, Rachma

2017-03-01

Silica gel modified APTS was synthesized from silica gel which was obtained from corn cobs via sol-gel process. Silica gel was synthesized from corn cobs and then chemically modified with silane coupling agent which has an amine group (NH2). This process resulting modified silica gel 3-aminopropyltriethoxysilane (APTS). Characterization of silica gel modified APTS by SEM-EDX showed that the size of the particles of silica gel modified APTS was 20µm with mass percentage of individual elements were nitrogen (N) 15.56%, silicon (Si) 50.69% and oxygen (O) 33.75%. In addition, silica gel modified APTS also showed absorption bands of functional groups silanol (Si-OH), siloxane (Si-O-Si), and an aliphatic chain (-CH2-), as well as amine (NH2) from FTIR spectra. Based on the characterization of XRD, silica gel 2θ of 21.094° and 21.32° respectively. It indicated that both material were amorphous. Determination of optimum pH and contact time on adsorption of silica gel 3-aminopropyltriethoxysilane (APTS) against Cu(II). The optimum pH and contact time was measured by using AAS. Optimum pH of adsorption silica gel modified APTS against metal Cu(II) could be obtained at pH 6 while optimum contact time was at 30 minutes, with the process of adsorption metal Cu(II) occured based on the model Freundlich isotherm.
Time-resolved microscopy of fs-laser-induced heat flows in glasses

NASA Astrophysics Data System (ADS)

Bonse, Jörn; Seuthe, Thomas; Grehn, Moritz; Eberstein, Markus; Rosenfeld, Arkadi; Mermillod-Blondin, Alexandre

2018-01-01

Time-resolved phase-contrast microscopy is employed to visualize spatio-temporal thermal transients induced by tight focusing of a single Ti:sapphire fs-laser pulse into a solid dielectric sample. This method relies on the coupling of the refractive index change and the sample temperature through the thermo-optic coefficient d n/d T. The thermal transients are studied on a timescale ranging from 10 ns up to 0.1 ms after laser excitation. Beyond providing direct insights into the laser-matter interaction, analyzing the results obtained also enables quantifying the local thermal diffusivity of the sample on a micrometer scale. Studies conducted in different solid dielectrics, namely amorphous fused silica (a-SiO2), a commercial borosilicate glass (BO33, Schott), and a custom alkaline earth silicate glass (NaSi66), illustrate the applicability of this approach to the investigation of various glassy materials.

Tetragonal zirconia quantum dots in silica matrix prepared by a modified sol-gel protocol

NASA Astrophysics Data System (ADS)

Verma, Surbhi; Rani, Saruchi; Kumar, Sushil

2018-05-01

Tetragonal zirconia quantum dots (t-ZrO2 QDs) in silica matrix with different compositions ( x)ZrO2-(100 - x)SiO2 were fabricated by a modified sol-gel protocol. Acetylacetone was added as a chelating agent to zirconium propoxide to avoid precipitation. The powders as well as thin films were given thermal treatment at 650, 875 and 1100 °C for 4 h. The silica matrix remained amorphous after thermal treatment and acted as an inert support for zirconia quantum dots. The tetragonal zirconia embedded in silica matrix transformed into monoclinic form due to thermal treatment ≥ 1100 °C. The stability of tetragonal phase of zirconia is found to enhance with increase in silica content. A homogenous dispersion of t-ZrO2 QDs in silica matrix was indicated by the mapping of Zr, Si and O elements obtained from scanning electron microscope with energy dispersive X-ray analyser. The transmission electron images confirmed the formation of tetragonal zirconia quantum dots embedded in silica. The optical band gap of zirconia QDs (3.65-5.58 eV) was found to increase with increase in zirconia content in silica. The red shift of PL emission has been exhibited with increase in zirconia content in silica.
Characteristics, distribution, origin, and significance of opaline silica observed by the Spirit rover in Gusev crater, Mars

USGS Publications Warehouse

Ruff, S.W.; Farmer, J.D.; Calvin, W.M.; Herkenhoff, K. E.; Johnson, J. R.; Morris, R.V.; Rice, M.S.; Arvidson, R. E.; Bell, J.F.; Christensen, P.R.; Squyres, S. W.

2011-01-01

The presence of outcrops and soil (regolith) rich in opaline silica (???65-92 wt % SiO2) in association with volcanic materials adjacent to the "Home Plate" feature in Gusev crater is evidence for hydrothermal conditions. The Spirit rover has supplied a diverse set of observations that are used here to better understand the formation of silica and the activity, abundance, and fate of water in the first hydrothermal system to be explored in situ on Mars. We apply spectral, chemical, morphological, textural, and stratigraphic observations to assess whether the silica was produced by acid sulfate leaching of precursor rocks, by precipitation from silica-rich solutions, or by some combination. The apparent lack of S enrichment and the relatively low oxidation state of the Home Plate silica-rich materials appear inconsistent with the originally proposed Hawaiian analog for fumarolic acid sulfate leaching. The stratiform distribution of the silica-rich outcrops and their porous and brecciated microtextures are consistent with sinter produced by silica precipitation. There is no evidence for crystalline quartz phases among the silica occurrences, an indication of the lack of diagenetic maturation following the production of the amorphous opaline phase. Copyright ?? 2011 by the American Geophysical Union.
Kinetics and pathways for crystallization of amorphous mullite and YAG

NASA Astrophysics Data System (ADS)

Johnson, Bradley Richard

The crystallization behavior of quenched mullite (3Al2O 3•2SiO2) and YAG (Y3Al5O 12) composition glasses (made using containerless methods) were characterized with the ultimate goal of producing single crystal, structural, ceramic oxide fibers from these materials. The kinetics for crystallization were determined from thermal analysis experiments. From the results, time-temperature-transformation (TTT) curves were calculated. The crystallization pathways were determined by examining the crystal structure, microstructure, and chemical composition of heat treated specimens using x-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). A machine was also designed and built to facilitate controlled crystallization of amorphous fibers. Quenched, Y3Al5O12 composition beads crystallized at temperatures as low as 840°C. The as-received specimens contained a few, small YAG crystals, in addition to a mixture of different amorphous phases. The coexistence of two different amorphous phases of the same composition, but having different densities is termed polyamorphism, and this has been reported to occur in Y3Al5O12 composition quenched melts. Although various crystallization pathways have been reported for chemically synthesized YAG precursors, these specimens crystallized directly into YAG, which was the only phase formed. Quenched, 3Al2O3•2SiO2 composition mullite beads and fibers crystallized at temperatures as low as 920°C. Due to phase separation in the quenched melts, multiple phases with slightly different compositions and different crystallization activation energies crystallized. These phases were not equilibrium, 3:2 mullite, but metastable, alumina-rich, pseudotetragonal mullite. The residual, amorphous, silica-rich phase existed as numerous, 7--10 nm sized inclusions embedded within pseudotetragonal mullite. A large amount of internal strain was detected in pseudotetragonal mullite, and the source of this strain was suggested to be the embedded, silica-rich inclusions. Pseudotetragonal mullite gradually converted to equilibrium, orthorhombic, 3:2 mullite between 1000--1400°C. This was characterized by assimilation of the embedded, silica-rich inclusions and the elimination of internal strain. Additionally, recrystallization of numerous, small, strain- and inclusion-free, 3:2 mullite grains was observed to occur as the process proceeded to completion.
Soil Biogeochemical and Biophysical Footprint of Forest to Pasture Conversion in the Western Pyrenees Mountains, France

NASA Astrophysics Data System (ADS)

Leigh, D.; Gragson, T. L.

2017-12-01

Summits of the humid-temperate western Pyrenees were converted from mixed forests to managed grasslands thousands of years ago, including use of fire. We hypothesize differences in soil chemical and physical traits evolved because of this transformation. Paired forest versus grassland soils were sampled at four separate hillslope sites having a clear boundary between the two vegetation types. Factors of climate, topography, parent material, and time of soil formation were essentially identical in the forests and pastures of each site, but the time of soil under grassland vegetation may have varied. Each paired hillslope site included five core samples from the upper 7.6 cm of the mineral soil within each vegetation type and the A horizon thickness was recorded at each core hole. In addition, one complete soil profile was sampled in each vegetation type at each site, making a total of 20 core samples and 4 complete profiles from each respective vegetation type. Analyses included bulk density, pH, plant-available nutrients, organic matter, fulvic versus humic acids, total carbon and nitrogen, amorphous silica, and charcoal content. Results indicate pastured A horizons are about three times as thick as forested soils, contain more organic matter, and have lower bulk densities. These traits favor much greater infiltration and water holding capacities of the pastured soils, which we validated with saturated hydraulic conductivity tests. Melanization has been more pronounced in the managed pastures, which contain significantly more humic acids than forests. Significantly more charcoal (black carbon) is present in the pastured soils from long-term use of fire, and having implications for sequestration of carbon. Pastures register significantly higher soil magnetic susceptibility than forests, also related to past use of fire as a management tool. Pastures contain greater contents of amorphous silica due to more rapid phytolith production from grasses as opposed to trees. Anthropic manipulation of the biotic factor of pedogenesis has created new soil materials, processes, and functions. Our results indicate better soil quality in pastured soils, counter to stereotypical concepts of soil degradation due to grazing, and having important implications for soil sustainability
Optical and Gravimetric Partitioning of Coastal Ocean Suspended Particulate Inorganic Matter (PIM)

NASA Astrophysics Data System (ADS)

Stavn, R. H.; Zhang, X.; Falster, A. U.; Gray, D. J.; Rick, J. J.; Gould, R. W., Jr.

2016-02-01

Recent work on the composition of suspended particulates of estuarine and coastal waters increases our capabilities to investigate the biogeochemal processes occurring in these waters. The biogeochemical properties associated with the particulates involve primarily sorption/desorption of dissolved matter onto the particle surfaces, which vary with the types of particulates. Therefore, the breakdown into chemical components of suspended matter will greatly expand the biogeochemistry of the coastal ocean region. The gravimetric techniques for these studies are here expanded and refined. In addition, new optical inversions greatly expand our capabilities to study spatial extent of the components of suspended particulate matter. The partitioning of a gravimetric PIM determination into clay minerals and amorphous silica is aided by electron microprobe analysis. The amorphous silica is further partitioned into contributions by detrital material and by the tests of living diatoms based on an empirical formula relating the chlorophyll content of cultured living diatoms in log phase growth to their frustules determined after gravimetric analysis of the ashed diatom residue. The optical inversion of composition of suspended particulates is based on the entire volume scattering function (VSF) measured in the field with a Multispectral Volume Scattering Meter and a LISST 100 meter. The VSF is partitioned into an optimal combination of contributions by particle subpopulations, each of which is uniquely represented by a refractive index and a log-normal size distribution. These subpopulations are aggregated to represent the two components of PIM using the corresponding refractive indices and sizes which also yield a particle size distribution for the two components. The gravimetric results of partitioning PIM into clay minerals and amorphous silica confirm the optical inversions from the VSF.
Effect of silicon and oxygen dopants on the stability of hydrogenated amorphous carbon under harsh environmental conditions

DOE PAGES

Mangolini, Filippo; Krick, Brandon A.; Jacobs, Tevis D. B.; ...

2017-12-27

Harsh environments pose materials durability challenges across the automotive, aerospace, and manufacturing sectors, and beyond. While amorphous carbon materials have been used as coatings in many environmentally-demanding applications owing to their unique mechanical, electrical, and optical properties, their limited thermal stability and high reactivity in oxidizing environments have impeded their use in many technologies. Silicon- and oxygen-containing hydrogenated amorphous carbon (a-C:H:Si:O) films are promising for several applications because of their higher thermal stability and lower residual stress compared to hydrogenated amorphous carbon (a-C:H). However, an understanding of their superior thermo-oxidative stability compared to a-C:H is lacking, as it has beenmore » inhibited by the intrinsic challenge of characterizing an amorphous, multi-component material. Here, we show that introducing silicon and oxygen in a-C:H slightly enhances the thermal stability in vacuum, but tremendously increases the thermo-oxidative stability and the resistance to degradation upon exposure to the harsh conditions of low Earth orbit (LEO). The latter is demonstrated by having mounted samples of a-C:H:Si:O on the exterior of the International Space Station via the Materials International Space Station (MISSE) mission 7b. Exposing lightly-doped a-C:H:Si:O to elevated temperatures under aerobic conditions or to LEO causes carbon volatilization in the near-surface region, producing a silica surface layer that protects the underlying carbon from further removal. In conclusion, these findings provide a novel physically-based understanding of the superior stability of a-C:H:Si:O in harsh environments compared to a-C:H.« less
Effect of silicon and oxygen dopants on the stability of hydrogenated amorphous carbon under harsh environmental conditions

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

Mangolini, Filippo; Krick, Brandon A.; Jacobs, Tevis D. B.

Harsh environments pose materials durability challenges across the automotive, aerospace, and manufacturing sectors, and beyond. While amorphous carbon materials have been used as coatings in many environmentally-demanding applications owing to their unique mechanical, electrical, and optical properties, their limited thermal stability and high reactivity in oxidizing environments have impeded their use in many technologies. Silicon- and oxygen-containing hydrogenated amorphous carbon (a-C:H:Si:O) films are promising for several applications because of their higher thermal stability and lower residual stress compared to hydrogenated amorphous carbon (a-C:H). However, an understanding of their superior thermo-oxidative stability compared to a-C:H is lacking, as it has beenmore » inhibited by the intrinsic challenge of characterizing an amorphous, multi-component material. Here, we show that introducing silicon and oxygen in a-C:H slightly enhances the thermal stability in vacuum, but tremendously increases the thermo-oxidative stability and the resistance to degradation upon exposure to the harsh conditions of low Earth orbit (LEO). The latter is demonstrated by having mounted samples of a-C:H:Si:O on the exterior of the International Space Station via the Materials International Space Station (MISSE) mission 7b. Exposing lightly-doped a-C:H:Si:O to elevated temperatures under aerobic conditions or to LEO causes carbon volatilization in the near-surface region, producing a silica surface layer that protects the underlying carbon from further removal. In conclusion, these findings provide a novel physically-based understanding of the superior stability of a-C:H:Si:O in harsh environments compared to a-C:H.« less
Sub-chronic toxicity study in rats orally exposed to nanostructured silica

PubMed Central

2014-01-01

Background Synthetic Amorphous Silica (SAS) is commonly used in food and drugs. Recently, a consumer intake of silica from food was estimated at 9.4 mg/kg bw/day, of which 1.8 mg/kg bw/day was estimated to be in the nano-size range. Food products containing SAS have been shown to contain silica in the nanometer size range (i.e. 5 – 200 nm) up to 43% of the total silica content. Concerns have been raised about the possible adverse effects of chronic exposure to nanostructured silica. Methods Rats were orally exposed to 100, 1000 or 2500 mg/kg bw/day of SAS, or to 100, 500 or 1000 mg/kg bw/day of NM-202 (a representative nanostructured silica for OECD testing) for 28 days, or to the highest dose of SAS or NM-202 for 84 days. Results SAS and NM-202 were extensively characterized as pristine materials, but also in the feed matrix and gut content of the animals, and after in vitro digestion. The latter indicated that the intestinal content of the mid/high-dose groups had stronger gel-like properties than the low-dose groups, implying low gelation and high bioaccessibility of silica in the human intestine at realistic consumer exposure levels. Exposure to SAS or NM-202 did not result in clearly elevated tissue silica levels after 28-days of exposure. However, after 84-days of exposure to SAS, but not to NM-202, silica accumulated in the spleen. Biochemical and immunological markers in blood and isolated cells did not indicate toxicity, but histopathological analysis, showed an increased incidence of liver fibrosis after 84-days of exposure, which only reached significance in the NM-202 treated animals. This observation was accompanied by a moderate, but significant increase in the expression of fibrosis-related genes in liver samples. Conclusions Although only few adverse effects were observed, additional studies are warranted to further evaluate the biological relevance of observed fibrosis in liver and possible accumulation of silica in the spleen in the NM-202 and SAS exposed animals respectively. In these studies, dose-effect relations should be studied at lower dosages, more representative of the current exposure of consumers, since only the highest dosages were used for the present 84-day exposure study. PMID:24507464
The nanosilica hazard: another variable entity

PubMed Central

2010-01-01

Silica nanoparticles (SNPs) are produced on an industrial scale and are an addition to a growing number of commercial products. SNPs also have great potential for a variety of diagnostic and therapeutic applications in medicine. Contrary to the well-studied crystalline micron-sized silica, relatively little information exists on the toxicity of its amorphous and nano-size forms. Because nanoparticles possess novel properties, kinetics and unusual bioactivity, their potential biological effects may differ greatly from those of micron-size bulk materials. In this review, we summarize the physico-chemical properties of the different nano-sized silica materials that can affect their interaction with biological systems, with a specific emphasis on inhalation exposure. We discuss recent in vitro and in vivo investigations into the toxicity of nanosilica, both crystalline and amorphous. Most of the in vitro studies of SNPs report results of cellular uptake, size- and dose-dependent cytotoxicity, increased reactive oxygen species levels and pro-inflammatory stimulation. Evidence from a limited number of in vivo studies demonstrates largely reversible lung inflammation, granuloma formation and focal emphysema, with no progressive lung fibrosis. Clearly, more research with standardized materials is needed to enable comparison of experimental data for the different forms of nanosilicas and to establish which physico-chemical properties are responsible for the observed toxicity of SNPs. PMID:21126379
Facile synthesis of functionalized ionic surfactant templated mesoporous silica for incorporation of poorly water-soluble drug.

PubMed

Li, Jing; Xu, Lu; Yang, Baixue; Wang, Hongyu; Bao, Zhihong; Pan, Weisan; Li, Sanming

2015-08-15

The present paper reported amino group functionalized anionic surfactant templated mesoporous silica (Amino-AMS) for loading and release of poorly water-soluble drug indomethacin (IMC) and carboxyl group functionalized cationic surfactant templated mesoporous silica (Carboxyl-CMS) for loading and release of poorly water-soluble drug famotidine (FMT). Herein, Amino-AMS and Carboxyl-CMS were facilely synthesized using co-condensation method through two types of silane coupling agent. Amino-AMS was spherical nanoparticles, and Carboxyl-CMS was well-formed spherical nanosphere with a thin layer presented at the edge. Drug loading capacity was obviously enhanced when using Amino-AMS and Carboxyl-CMS as drug carriers due to the stronger hydrogen bonding force formed between surface modified carrier and drug. Amino-AMS and Carboxyl-CMS had the ability to transform crystalline state of loaded drug from crystalline phase to amorphous phase. Therefore, IMC loaded Amino-AMS presented obviously faster release than IMC because amorphous phase of IMC favored its dissolution. The application of asymmetric membrane capsule delayed FMT release significantly, and Carboxyl-CMS favored sustained release of FMT due to its long mesoporous channels and strong interaction formed between its carboxyl group and amino group of FMT. Copyright © 2015 Elsevier B.V. All rights reserved.
Study of interaction in silica glass via model potential approach

NASA Astrophysics Data System (ADS)

Mann, Sarita; Rani, Pooja

2016-05-01

Silica is one of the most commonly encountered substances in daily life and in electronics industry. Crystalline SiO2 (in several forms: quartz, cristobalite, tridymite) is an important constituent of many minerals and gemstones, both in pure form and mixed with related oxides. Cohesive energy of amorphous SiO2 has been investigated via intermolecular potentials i.e weak Van der Waals interaction and Morse type short-range interaction. We suggest a simple atom-atom based Van der Waals as well as Morse potential to find cohesive energy of glass. It has been found that the study of silica structure using two different model potentials is significantly different. Van der Waals potential is too weak (P.E =0.142eV/molecule) to describe the interaction between silica molecules. Morse potential is a strong potential, earlier given for intramolecular bonding, but if applied for intermolecular bonding, it gives a value of P.E (=-21.92eV/molecule) to appropriately describe the structure of silica.
Application of DFT-Derived Relationships Between Chemical Environment and 29Si Nuclear Magnetic Resonance Spectroscopy to Determine Structure in Silicon Oxycarbide Ceramics

NASA Astrophysics Data System (ADS)

Nimmo, John Paul, II

Silicon oxycarbide (SiCO) is an amorphous ceramic material widely used in industrial applications, for its useful electronic and biologically-compatible properties. SiCO is resistant to crystallization, remaining amorphous even above temperatures at which amorphous SiO2 would crystallize. Though silica (SiO2) and silicon carbide (SiC) are almost immiscible, it is useful to consider the material as a phase composition of these along with carbon, according to the formula below. The first two terms in braces can be considered as being the "SiCO glass" into which a third term representing excess or "free" carbon is incorporated as graphite-like nano-flakes and bands.
New transformations between crystalline and amorphous ice

NASA Technical Reports Server (NTRS)

Hemley, R. J.; Chen, L. C.; Mao, H. K.

1989-01-01

High-pressure optical and spectroscopic techniques were used to obtain directly the ice I(h) - hda-ice transformation in a diamond-anvil cell, and the stability of the amorphous form is examined as functions of pressure and temperature. It is demonstrated that hda-ice transforms abruptly at 4 GPa and 77 K to a crystalline phase close in structure to orientationally disordered ice-VII and to a more highly ordered, ice-VIII-like structure at higher temperatures. This is the first time that an amorphous solid is observed to convert to a crystalline solid at low temperatures by compression alone. Phase transitions of this type may be relevant on icy planetary satellites, and there may also be implications for the high-pressure behavior of silica.
Preparation and Characterization of ZnO Nanoparticles Supported on Amorphous SiO2

PubMed Central

Chen, Ying; Ding, Hao; Sun, Sijia

2017-01-01

In order to reduce the primary particle size of zinc oxide (ZnO) and eliminate the agglomeration phenomenon to form a monodisperse state, Zn2+ was loaded on the surface of amorphous silica (SiO2) by the hydrogen bond association between hydroxyl groups in the hydrothermal process. After calcining the precursors, dehydration condensation among hydroxyl groups occurred and ZnO nanoparticles supported on amorphous SiO2 (ZnO–SiO2) were prepared. Furthermore, the SEM and TEM observations showed that ZnO nanoparticles with a particle size of 3–8 nm were uniformly and dispersedly loaded on the surface of amorphous SiO2. Compared with pure ZnO, ZnO–SiO2 showed a much better antibacterial performance in the minimum inhibitory concentration (MIC) test and the antibacterial properties of the paint adding ZnO–SiO2 composite. PMID:28796157
How Nano are Nanocomposites (Preprint)

DTIC Science & Technology

2007-02-01

with λ being the wavelength of the radiation . Based on this Fourier transform, r and q are conjugate variables. Although Eqs. (1) and (2) are...generation material is produced from porcellanite, a mineral rich in amorphous silica that is found in the Negev desert in southern Israel (Dimosil
Understanding and simulating the material behavior during multi-particle irradiations

PubMed Central

Mir, Anamul H.; Toulemonde, M.; Jegou, C.; Miro, S.; Serruys, Y.; Bouffard, S.; Peuget, S.

2016-01-01

A number of studies have suggested that the irradiation behavior and damage processes occurring during sequential and simultaneous particle irradiations can significantly differ. Currently, there is no definite answer as to why and when such differences are seen. Additionally, the conventional multi-particle irradiation facilities cannot correctly reproduce the complex irradiation scenarios experienced in a number of environments like space and nuclear reactors. Therefore, a better understanding of multi-particle irradiation problems and possible alternatives are needed. This study shows ionization induced thermal spike and defect recovery during sequential and simultaneous ion irradiation of amorphous silica. The simultaneous irradiation scenario is shown to be equivalent to multiple small sequential irradiation scenarios containing latent damage formation and recovery mechanisms. The results highlight the absence of any new damage mechanism and time-space correlation between various damage events during simultaneous irradiation of amorphous silica. This offers a new and convenient way to simulate and understand complex multi-particle irradiation problems. PMID:27466040
A novel composite material based on antimony(III) oxide and amorphous silica

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

Zemnukhova, Ludmila A.; Panasenko, Alexander E., E-mail: panasenko@ich.dvo.ru

2013-05-01

The composite material nSb₂O₃·mSiO₂·xH₂O was prepared by hydrolysis of SbCl₃ and Na₂SiO₃ in an aqueous medium. It has been shown that the composition of the material is influenced by the ratio of the initial components and the acidity of the reaction medium. The morphology of the material particles and its specific surface area have been determined. The thermal and optic properties were also investigated. - Graphical abstract: Novel composite material containing amorphous silica and crystal antimony(III) oxide has been synthesized by hydrolysis of SbCl₃ and Na₂SiO₃ in an aqueous medium. Highlights: • The composite material nSb₂O₃·mSiO₂·xH₂O was prepared in anmore » aqueous medium. • The composition of the material is controllable by a synthesis conditions. • The morphology of the material and its optic properties have been determined.« less
Application of a hybrid ordered mesoporous silica as sorbent for solid-phase multi-residue extraction of veterinary drugs in meat by ultra-high-performance liquid chromatography coupled to ion-trap tandem mass spectrometry.

PubMed

Casado, Natalia; Morante-Zarcero, Sonia; Pérez-Quintanilla, Damián; Sierra, Isabel

2016-08-12

A quick, sensitive and selective analytical reversed-phase multi-residue method using ultra-high performance liquid chromatography coupled to an ion-trap mass spectrometry detector (UHPLC-IT-MS/MS) operating in both positive and negative ion mode was developed for the simultaneous determination of 23 veterinary drug residues (β-blockers, β-agonists and Non-Steroidal Anti-inflammatory Drugs (NSAIDs)) in meat samples. The sample treatment involved a liquid-solid extraction followed by a solid-phase extraction (SPE) procedure. SBA-15 type mesoporous silica was synthetized and modified with octadecylsilane, and the resulting hybrid material (denoted as SBA-15-C18) was applied and evaluated as SPE sorbent in the purification of samples. The materials were comprehensively characterized, and they showed a high surface area, high pore volume and a homogeneous distribution of the pores. Chromatographic conditions and extraction procedure were optimized, and the method was validated according to the Commission Decision 2002/657/EC. The method detection limits (MDLs) and the method quantification limits (MQLs) were determined for all the analytes in meat samples and found to range between 0.01-18.75μg/kg and 0.02-62.50μg/kg, respectively. Recoveries for 15 of the target analytes ranged from 71 to 98%. In addition, for comparative purpose SBA-15-C18 was evaluated towards commercial C18 amorphous silica. Results revealed that SBA-15-C18 was clearly more successful in the multi-residue extraction of the 23 mentioned analytes with higher recovery values. The method was successfully tested to analyze prepacked preparations of mince bovine meat. Traces of propranolol, ketoprofen and diclofenac were detected in some samples. Copyright © 2016 Elsevier B.V. All rights reserved.
Two-dimensional silica opens new perspectives

NASA Astrophysics Data System (ADS)

Büchner, Christin; Heyde, Markus

2017-12-01

In recent years, silica films have emerged as a novel class of two-dimensional (2D) materials. Several groups succeeded in epitaxial growth of ultrathin SiO2 layers using different growth methods and various substrates. The structures consist of tetrahedral [SiO4] building blocks in two mirror symmetrical planes, connected via oxygen bridges. This arrangement is called a silica bilayer as it is the thinnest 2D arrangement with the stoichiometry SiO2 known today. With all bonds saturated within the nano-sheet, the interaction with the substrate is based on van der Waals forces. Complex ring networks are observed, including hexagonal honeycomb lattices, point defects and domain boundaries, as well as amorphous domains. The network structures are highly tuneable through variation of the substrate, deposition parameters, cooling procedure, introducing dopants or intercalating small species. The amorphous networks and structural defects were resolved with atomic resolution microscopy and modeled with density functional theory and molecular dynamics. Such data contribute to our understanding of the formation and characteristic motifs of glassy systems. Growth studies and doping with other chemical elements reveal ways to tune ring sizes and defects as well as chemical reactivities. The pristine films have been utilized as molecular sieves and for confining molecules in nanocatalysis. Post growth hydroxylation can be used to tweak the reactivity as well. The electronic properties of silica bilayers are favourable for using silica as insulators in 2D material stacks. Due to the fully saturated atomic structure, the bilayer interacts weakly with the substrate and can be described as quasi-freestanding. Recently, a mm-scale film transfer under structure retention has been demonstrated. The chemical and mechanical stability of silica bilayers is very promising for technological applications in 2D heterostacks. Due to the impact of this bilayer system for glass science, catalysis and the field of 2D materials, a large number of theoretical and experimental studies on silica bilayers have been reported in the last years. This review aims to provide an overview on the insights gained on this material and to point out opportunities for further discovery in various fields.
Mixed biogenic and hydrothermal quartz in Permian lacustrine shale of Santanghu Basin, NW China: implications for penecontemporaneous transformation of silica minerals

NASA Astrophysics Data System (ADS)

Jiao, Xin; Liu, Yiqun; Yang, Wan; Zhou, Dingwu; Wang, Shuangshuang; Jin, Mengqi; Sun, Bin; Fan, Tingting

2018-01-01

The cycling of various isomorphs of authigenic silica minerals is a complex and long-term process. A special type of composite quartz (Qc) grains in tuffaceous shale of Permian Lucaogou Formation in the sediment-starved volcanically and hydrothermally active intracontinental lacustrine Santanghu rift basin (NW China) is studied in detail to demonstrate such processes. Samples from one well in the central basin were subject to petrographic, elemental chemical, and fluid inclusion analyses. About 200 Qc-bearing laminae are 0.1-2 mm and mainly 1 mm thick and intercalated within tuffaceous shale laminae. The Qc grains occur as framework grains and are dispersed in igneous feldspar-dominated matrix, suggesting episodic accumulation. The Qc grains are bedding-parallel, uniform in size (100 s µm), elongate, and radial in crystal pattern, suggesting a biogenic origin. Qc grains are composed of a core of anhedral microcrystalline quartz and an outer part of subhedral mega-quartz grains, whose edges are composed of small euhedral quartz crystals, indicating multiple episodic processes of recrystallization and overgrowth. Abundance of Al and Ti in quartz crystals and estimated temperature from fluid inclusions in Qc grains indicate that processes are related to hydrothermal fluids. Finally, the Qc grains are interpreted as original silica precipitation in microorganism (algae?) cysts, which were reworked by bottom currents and altered by hydrothermal fluids to recrystalize and overgrow during penecontemporaneous shallow burial. It is postulated that episodic volcanic and hydrothermal activities had changed lake water chemistry, temperature, and nutrient supply, resulting in variations in microorganic productivities and silica cycling. The transformation of authigenic silica from amorphous to well crystallized had occurred in a short time span during shallow burial.

Formation and characterization of high surface area thermally stabilized titania/silica composite materials via hydrolysis of titanium(IV) tetra-isopropoxide in sols of spherical silica particles.

PubMed

Khalil, Kamal M S; Elsamahy, Ahmed A; Elanany, Mohamed S

2002-05-15

A direct synthetic route leading to titania particles dispersed on nonporous spherical silica particles has been investigated; 5, 10, and 20% (w/w) titania/silica sols mixtures were achieved via hydrolyzation of titanium tetra-isopropxide solution in the mother liquor of a freshly prepared sol of spherical silica particles (Stöber particles). Titania/silica materials were produced by subsequent drying and calcination of the xerogels so obtained for 3 h at 400 and 600 degrees C. The materials were investigated by means of thermal analyses (TGA and DSC), FT-IR, N(2) gas adsorption-desorption, powder X-ray diffraction (XRD), and transmission electron microscopy (TEM). In spite of the low surface area (13.1 m(2)/g) of the pure spherical silica particles calcined at 400 degrees C, high surface area and mesoporous texture titania/silica materials were obtained (e.g., S(BET) ca. 293 m(2)/g for the 10% titania/silica calcined at 400 degrees C). Moreover, the materials were shown to be amorphous toward XRD up to 600 degrees C, while reasonable surface areas were preserved. It has been concluded that dispersion of titania particles onto the surface of the nonporous spherical silica particles increase their roughness, therefore leading to composite materials of less firm packing and mesoporosity.
Shocked Quartz Aggregates of the Cretaceous-Tertiary Boundary at Colorado, USA

NASA Astrophysics Data System (ADS)

Miura, Y.; Okamoto, M.; Iancu, O. G.

1993-07-01

Shock-metamorphosed quartz (i.e., shocked quartz) at the Cretaceous-Tertiary boundary (K/T) at Colorado [1,2] reveals the following mineralogical data by X-ray diffractometry and high-resolution electron micrograph with energy- dispersive spectrometry. 1. Shocked quartz is not normal (perfect crystalline) quartz mineral but various quartz aggregates that show relatively low X-ray intensity (i.e., imperfect crystalline) and shock lamellae with crystalline quartz and amorphous glass [3]. 2. Analytical electron micrographs indicate that crystalline quartz silica with spotty dislocation features is included in dendritic amorphous glasses of potassium (K) feldspar composition. Various compositions of glassy materials are found in shocked quartz aggregates as matrix or alternate shock lamellae, which is important to estimate the target rock of impact. The composition of glassy matrix is dendritic K-feldspar in the K/T boundary at Clear Creak North (CCN), Colorado, whereas that in the Barringer Crater is quartz-rich composition from the target rock of sandstone (or some mixture with iron meteorite), and that in artificial impact rock [3] is dendritic silica composition. It is found in this study that shocked quartz aggregates from the CCN K/T boundary samples are supplied from quartz and K-feldspar-bearing target rock at impact event (Table 1). Table 1, which appears here in the hard copy, shows the compositions, texture, and origin of shocked quartz aggregates. References: [1] Alvarez L. W. et al. (1980) Science, 208, 1095-1107. [2] Izett G. (1989) GSA Spec. Pap. 249, 1-194. [3] Miura Y. (1991) Shock Waves, 1, 35-41, Springer-Verlag.
Synthesis of amino-functionalized silica nanoparticles for preparation of new laboratory standards

NASA Astrophysics Data System (ADS)

Alvarez-Toral, Aitor; Fernández, Beatriz; Malherbe, Julien; Claverie, Fanny; Pecheyran, Christophe; Pereiro, Rosario

2017-12-01

Platinum group elements (PGEs) are particularly interesting analytes in different fields, including environmental samples as well as high cost materials that contain them, such as for example automotive catalysts. This type of solid samples could be analysed by laser ablation (LA) coupled to ICP-MS, which allow to significantly reducing the analysis time since the time-consuming processes for sample preparation are not required. There is a considerable demand of standards with high PGEs concentration for quantification purposes, which cannot be carried out easily using LA-ICP-MS because the available standards (i.e. NIST SRM 61 × series) do not have such analytes in the same concentration range. In this paper, a new strategy is proposed for the synthesis of homogeneous laboratory standards with Pt, Pd and Rh concentrations that range from 77 μg/g of Pd up to 2035 μg/g of Rh. The proposed strategy is based on the synthesis of monodisperse amino-functionalized amorphous silica nanoparticles, which can retain metal ions. In addition to Pt, Pd and Rh, three lanthanides were also added to the nanoparticles (La, Ce, Nd). Sturdy pressed pellets can be made from the resulting nanopowder without the use of any binder. Elemental composition of standards made of nanoparticles was analysed by conventional nebulization ICP-MS and their homogeneity was successfully evaluated by LA-ICP-MS.
Nanoporous silica-based protocells at multiple scales for designs of life and nanomedicine

DOE PAGES

Sun, Jie; Jakobsson, Eric; Wang, Yingxiao; ...

2015-01-19

In this study, various protocell models have been constructed de novo with the bottom-up approach. Here we describe a silica-based protocell composed of a nanoporous amorphous silica core encapsulated within a lipid bilayer built by self-assembly that provides for independent definition of cell interior and the surface membrane. In this review, we will first describe the essential features of this architecture and then summarize the current development of silica-based protocells at both micro- and nanoscale with diverse functionalities. As the structure of the silica is relatively static, silica-core protocells do not have the ability to change shape, but their interiormore » structure provides a highly crowded and, in some cases, authentic scaffold upon which biomolecular components and systems could be reconstituted. In basic research, the larger protocells based on precise silica replicas of cells could be developed into geometrically realistic bioreactor platforms to enable cellular functions like coupled biochemical reactions, while in translational research smaller protocells based on mesoporous silica nanoparticles are being developed for targeted nanomedicine. Ultimately we see two different motivations for protocell research and development: (1) to emulate life in order to understand it; and (2) to use biomimicry to engineer desired cellular interactions.« less
Nanoporous silica-based protocells at multiple scales for designs of life and nanomedicine

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

Sun, Jie; Jakobsson, Eric; Wang, Yingxiao

In this study, various protocell models have been constructed de novo with the bottom-up approach. Here we describe a silica-based protocell composed of a nanoporous amorphous silica core encapsulated within a lipid bilayer built by self-assembly that provides for independent definition of cell interior and the surface membrane. In this review, we will first describe the essential features of this architecture and then summarize the current development of silica-based protocells at both micro- and nanoscale with diverse functionalities. As the structure of the silica is relatively static, silica-core protocells do not have the ability to change shape, but their interiormore » structure provides a highly crowded and, in some cases, authentic scaffold upon which biomolecular components and systems could be reconstituted. In basic research, the larger protocells based on precise silica replicas of cells could be developed into geometrically realistic bioreactor platforms to enable cellular functions like coupled biochemical reactions, while in translational research smaller protocells based on mesoporous silica nanoparticles are being developed for targeted nanomedicine. Ultimately we see two different motivations for protocell research and development: (1) to emulate life in order to understand it; and (2) to use biomimicry to engineer desired cellular interactions.« less
Structure and Properties of Silica Glass Densified in Cold Compression and Hot Compression

NASA Astrophysics Data System (ADS)

Guerette, Michael; Ackerson, Michael R.; Thomas, Jay; Yuan, Fenglin; Bruce Watson, E.; Walker, David; Huang, Liping

2015-10-01

Silica glass has been shown in numerous studies to possess significant capacity for permanent densification under pressure at different temperatures to form high density amorphous (HDA) silica. However, it is unknown to what extent the processes leading to irreversible densification of silica glass in cold-compression at room temperature and in hot-compression (e.g., near glass transition temperature) are common in nature. In this work, a hot-compression technique was used to quench silica glass from high temperature (1100 °C) and high pressure (up to 8 GPa) conditions, which leads to density increase of ~25% and Young’s modulus increase of ~71% relative to that of pristine silica glass at ambient conditions. Our experiments and molecular dynamics (MD) simulations provide solid evidences that the intermediate-range order of the hot-compressed HDA silica is distinct from that of the counterpart cold-compressed at room temperature. This explains the much higher thermal and mechanical stability of the former than the latter upon heating and compression as revealed in our in-situ Brillouin light scattering (BLS) experiments. Our studies demonstrate the limitation of the resulting density as a structural indicator of polyamorphism, and point out the importance of temperature during compression in order to fundamentally understand HDA silica.
Experimental and numerical simulation of dissolution and precipitation: implications for fracture sealing at Yucca Mountain, Nevada

NASA Astrophysics Data System (ADS)

Dobson, Patrick F.; Kneafsey, Timothy J.; Sonnenthal, Eric L.; Spycher, Nicolas; Apps, John A.

2003-05-01

Plugging of flow paths caused by mineral precipitation in fractures above the potential repository at Yucca Mountain, Nevada could reduce the probability of water seeping into the repository. As part of an ongoing effort to evaluate thermal-hydrological-chemical (THC) effects on flow in fractured media, we performed a laboratory experiment and numerical simulations to investigate mineral dissolution and precipitation under anticipated temperature and pressure conditions in the repository. To replicate mineral dissolution by vapor condensate in fractured tuff, water was flowed through crushed Yucca Mountain tuff at 94 °C. The resulting steady-state fluid composition had a total dissolved solids content of about 140 mg/l; silica was the dominant dissolved constituent. A portion of the steady-state mineralized water was flowed into a vertically oriented planar fracture in a block of welded Topopah Spring Tuff that was maintained at 80 °C at the top and 130 °C at the bottom. The fracture began to seal with amorphous silica within 5 days. A 1-D plug-flow numerical model was used to simulate mineral dissolution, and a similar model was developed to simulate the flow of mineralized water through a planar fracture, where boiling conditions led to mineral precipitation. Predicted concentrations of the major dissolved constituents for the tuff dissolution were within a factor of 2 of the measured average steady-state compositions. The mineral precipitation simulations predicted the precipitation of amorphous silica at the base of the boiling front, leading to a greater than 50-fold decrease in fracture permeability in 5 days, consistent with the laboratory experiment. These results help validate the use of a numerical model to simulate THC processes at Yucca Mountain. The experiment and simulations indicated that boiling and concomitant precipitation of amorphous silica could cause significant reductions in fracture porosity and permeability on a local scale. However, differences in fluid flow rates and thermal gradients between the experimental setup and anticipated conditions at Yucca Mountain need to be factored into scaling the results of the dissolution/precipitation experiments and associated simulations to THC models for the potential Yucca Mountain repository.
Solid-state {sup 27}Al and {sup 29}Si NMR characterization of hydrates formed in calcium aluminate-silica fume mixtures

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

Pena, P.; Rivas Mercury, J.M.; Aza, A.H. de

2008-08-15

Partially deuterated Ca{sub 3}Al{sub 2}(SiO{sub 4}){sub y}(OH){sub 12-4y}-Al(OH){sub 3} mixtures, prepared by hydration of Ca{sub 3}Al{sub 2}O{sub 6} (C{sub 3}A), Ca{sub 12}Al{sub 14}O{sub 33} (C{sub 12}A{sub 7}) and CaAl{sub 2}O{sub 4} (CA) phases in the presence of silica fume, have been characterized by {sup 29}Si and {sup 27}Al magic-angle spinning-nuclear magnetic resonance (MAS-NMR) spectroscopies. NMR spectroscopy was used to characterize anhydrous and fully hydrated samples. In hydrated compounds, Ca{sub 3}Al{sub 2}(OH){sub 12} and Al(OH){sub 3} phases were detected. From the quantitative analysis of {sup 27}Al NMR signals, the Al(OH){sub 3}/Ca{sub 3}Al{sub 2}(OH){sub 12} ratio was deduced. The incorporation of Simore » into the katoite structure, Ca{sub 3}Al{sub 2}(SiO{sub 4}){sub 3-x}(OH){sub 4x}, was followed by {sup 27}Al and {sup 29}Si NMR spectroscopies. Si/OH ratios were determined from the quantitative analysis of {sup 27}Al MAS-NMR components associated with Al(OH){sub 6} and Al(OSi)(OH){sub 5} environments. The {sup 29}Si NMR spectroscopy was also used to quantify the unreacted silica and amorphous calcium aluminosilicate hydrates formed, C-S-H and C-A-S-H for short. From {sup 29}Si NMR spectra, the amount of Si incorporated into different phases was estimated. Si and Al concentrations, deduced by NMR, transmission electron microscopy, energy dispersive spectrometry, and Rietveld analysis of both X-ray and neutron data, indicate that only a part of available Si is incorporated in katoite structures. - Graphical abstract: Transmission electron micrograph of CaAl{sub 2}O{sub 4}-microsilica mixture hydrated at 90 deg. C for 31 days showing a cubic Ca{sub 3}Al{sub 2.0{+-}}{sub 0.2}(SiO{sub 4}){sub 0.9{+-}}{sub 0.2}(OH){sub 1.8} crystal surrounded by unreacted amorphous silica spheres.« less
Interactions of Plutonium and Lanthanides with Ordered Mesoporous Materials

NASA Astrophysics Data System (ADS)

Parsons-Moss, Tashi

Ordered mesoporous materials are porous solids with a regular, patterned structure composed of pores between 2 and 50 nm wide. Such materials have attracted much attention in the past twenty years because the chemistry of their synthesis allows control of their unique physicochemical properties, which can be tuned for a variety of applications. Generally, ordered mesoporous materials have very high specific surface areas and pore volumes, and offer unique structures that are neither crystalline nor amorphous. The large tunable interface provided by ordered mesoporous solids may be advantageous in applications involving sequestration, separation, or detection of actinides and lanthanides in solution. However, the fundamental chemical interactions of actinides and lanthanides must be understood before applications can be implemented. This dissertation focuses primarily on the fundamental interactions of plutonium with organically modified mesoporous silica, as well as several different porous carbon materials, both untreated and chemically oxidized. A method for functionalizing mesoporous silica by self assembly and molecular grafting of functional organosilane ligands was optimized for the 2D-hexagonal ordered mesoporous silica known as SBA-15 (Santa Barbara amorphous silica). Four different organically-modified silica materials were synthesized and characterized with several techniques. To confirm that covalent bonds were formed between the silane anchor of the ligand and the silica substrate, functionalized silica samples were analyzed with 29Si nuclear magnetic resonance spectroscopy. Infrared spectroscopy was used in combination with 13C and 31P nuclear magnetic resonance spectroscopy to verify the molecular structures of the ligands after they were synthesized and grafted to the silica. The densities of the functional silane ligands on the silica surface were estimated using thermogravimetric analysis. Batch sorption experiments were conducted with solutions of Pu(IV), Pu(VI), Eu(III), Ce(III), and Zr(IV). The acetamide phosphonate functionalized silica called Ac-Phos-SBA-15 required more extensive synthesis than the other three functionalized silica materials. Development of functionalized mesoporous silica extractants for actinides is contingent on their synthesis and hydrolytic stability, and these two aspects of the Ac-Phos-SBA-15 material are discussed. This material showed the highest binding affinity for all of the target ions, and the sorption and desorption of Pu(VI) to Ac-Phos-SBA-15 was extensively investigated. Ordered mesoporous carbons are attractive as sorbents because of their extremely high surface areas and large pore volumes, and could be suitable substrates for the development of actinide sensors based on their electrochemical properties. Three different mesoporous carbon materials were synthesized by collaborators to test their application as radionuclide sorbent materials. The first is called CMK (carbons mesostructured by Korea Advanced Institute of Science and Technology), and was synthesized using a hard silica template with 3D-bicontinuous ordered mesostructure. Highly ordered body-centered cubic mesoporous carbon was synthesized by self-assembly of a phenol resin around a soft polymer template, and this material is known as FDU-16 (Fudan University). Etching of the silica portion of mesoporous carbon-silica composites created the 2D-hexagonal mesoporous carbon called C-CS (carbon from carbon-silica nanocomposites) with a bimodal pore size distribution. The as-synthesized nanocast mesoporous carbon in this work is called UN CMK, and the same material after oxidation treatment with nitric acid is called OX CMK. A portion of both FDU-16-type and C-CS-type ordered mesoporous carbons were oxidized with acidic ammonium persulfate, which created the oxidized carbon materials called FDU-16-COOH and C-CS-COOH, respectively. The mesoporous carbons were characterized by scanning electron microscopy to view their particle sizes and morphologies. Their porosities and structures on the meso-scale were analyzed using transmission electron microscopy, nitrogen adsorption isotherms, and small-angle X-ray scattering. The identity and density of functional groups on the different carbon surfaces were investigated using infrared spectroscopy, elemental analysis, thermogravimetric analysis, and determination of the point-of-zero-charge with the powder addition technique. The porous carbon materials studied present a wide range of particle morphologies, mesostructures, surface areas, pore volumes, and surface chemistries. (Abstract shortened by UMI.)
Paleozoic and Mesozoic silica-rich seawater: Evidence from hematitic chert (jasper) deposits

USGS Publications Warehouse

Grenne, Tor; Slack, J.F.

2003-01-01

Laterally extensive beds of highly siliceous, hematitic chert (jasper) are associated with many volcanogenic massive sulfide (VMS) deposits of Late Cambrian to Early Cretaceous age, yet are unknown in analogous younger (including modern) settings. Textural studies suggest that VMS-related jaspers in the Ordovician Løkken ophiolite of Norway were originally deposited as Si- and Fe-rich gels that precipitated from hydrothermal plumes as colloidal silica and iron-oxyhydroxide particles. Rare earth element patterns and Ge/Si ratios of the jaspers reflect precipitation from plumes having seawater dilution factors of 103 to 104, similar to modern examples. We propose that silica in the ancient jaspers is not derived from submarine hydrothermal fluids-as suggested by previous workers-but instead was deposited from silic-rich sea-water. Flocculation and precipitation of the silica were triggered inorganically by the bridging effect of positively charged iron oxyhydroxides in the hydrothermal plume. A model involving amorphous silica (opal-A) precursors to the jaspers suggests that silica contents of Cambrian-Early Cretaceous oceans were at least 110 mg/L SiO2, compared to values of 40-60 mg/L SiO2 estimated in other studies. The evolution of ancient silica-rich to modern Fe-rich precipitates in submarine-hydrothermal plumes reflects a changeover from silica-saturated to silica-depleted seawater through Phanerozoic time, due mainly to ocean-wide emergence of diatoms in the Cretaceous.
Influence Of Carboxymethyl Cellulose For The Transport Of Titanium Dioxide Nanoparticles In Clean Silica And Mineral-Coated Sands

EPA Science Inventory

The transport properties of titanium dioxide (anatase polymorph) nanoparticles encapsulated by carboxymethyl cellulose (CMC) were evaluated as a function of changes in the solute chemical properties in clean quartz, amorphous aluminum and iron hydroxide-coated sands. While prist...
Graphene as a transparent electrode for amorphous silicon-based solar cells

NASA Astrophysics Data System (ADS)

Vaianella, F.; Rosolen, G.; Maes, B.

2015-06-01

The properties of graphene in terms of transparency and conductivity make it an ideal candidate to replace indium tin oxide (ITO) in a transparent conducting electrode. However, graphene is not always as good as ITO for some applications, due to a non-negligible absorption. For amorphous silicon photovoltaics, we have identified a useful case with a graphene-silica front electrode that improves upon ITO. For both electrode technologies, we simulate the weighted absorption in the active layer of planar amorphous silicon-based solar cells with a silver back-reflector. The graphene device shows a significantly increased absorbance compared to ITO-based cells for a large range of silicon thicknesses (34.4% versus 30.9% for a 300 nm thick silicon layer), and this result persists over a wide range of incidence angles.
A novel strategy to design sustained-release poorly water-soluble drug mesoporous silica microparticles based on supercritical fluid technique.

PubMed

Li-Hong, Wang; Xin, Che; Hui, Xu; Li-Li, Zhou; Jing, Han; Mei-Juan, Zou; Jie, Liu; Yi, Liu; Jin-Wen, Liu; Wei, Zhang; Gang, Cheng

2013-09-15

The organic solvent solution immersion method was often used to achieve the loading of the drugs into mesoporous silica, but the drugs that have loaded into the pores of the mesoporous silica would inevitable migrate from the inside to the external surface or near the outside surface during the process of drying. Hence, it often leads to the pores of mesoporous materials not be fully utilized, and results in a low drug loading efficiency and a fast releasing rate. The purpose of this study was to develop a novel drug loading strategy to avoid soluble component migration during the process of drying, then, to prepare poorly water-soluble drug mesoporous silica microparticles with higher drug loading efficiency and longer sustained-release time. Ibuprofen was used as model drug. The microparticles were prepared by a novel method based on mesoporous silica and supercritical fluid (SCF) technique. The drug-loaded mesoporous silica microparticles prepared by SCF technique were analyzed by thermogravimetric analysis (TGA), N2 adsorption/desorption, scanning electron microscopy (SEM), powder X-ray diffraction (XRD) and differential scanning calorimetry (DSC). In vitro releasing study was used to evaluate the sustained-release effect of the drug-loaded microparticles. By virtue of the high diffusibility and the high dissolving capacity of the supercritical carbon dioxide (SCF-CO2), the poorly water-soluble drugs, ibuprofen, entered the pores of the mesoporous silica. The amount and the depth of ibuprofen entered the pores of the mesoporous silica by SCF technique were both larger than those by the solution immersion method. It was found that ibuprofen loaded into the mesoporous silica by SCF technique was amorphous and the largest amount of the ibuprofen loaded into the mesoporous silica by SCF technique could reach 386 mg/g (w/w, ibuprofen/SiO2), it was more than that by the solution immersion method. In vitro releasing study showed that the sustained-release effect of ibuprofen in the samples prepared by SCF technique was 50% in 15 min and 90% in 60 min. It was longer than that prepared by the solution immersion method. Present study showed that sustained-release poorly water-soluble drug mesoporous silica microparticle based on SCF technique has twofold advantages. One is the larger drug loading amount in internal pores of the mesoporous silica, the other is the longer drug releasing time. Copyright © 2013 Elsevier B.V. All rights reserved.
High-pressure-induced structural changes, amorphization and molecule penetration in MFI microporous materials: a review.

PubMed

Vezzalini, Giovanna; Arletti, Rossella; Quartieri, Simona

2014-06-01

This is a comparative study on the high-pressure behavior of microporous materials with an MFI framework type (i.e. natural mutinaite, ZSM-5 and the all-silica phase silicalite-1), based on in-situ experiments in which penetrating and non-penetrating pressure-transmitting media were used. Different pressure-induced phenomena and deformation mechanisms (e.g. pressure-induced over-hydration, pressure-induced amorphization) are discussed. The influence of framework and extra-framework composition and of the presence of silanol defects on the response to the high pressure of MFI-type zeolites is discussed.
Correlated evolution of structure and mechanical loss of a sputtered silica film

NASA Astrophysics Data System (ADS)

Granata, Massimo; Coillet, Elodie; Martinez, Valérie; Dolique, Vincent; Amato, Alex; Canepa, Maurizio; Margueritat, Jérémie; Martinet, Christine; Mermet, Alain; Michel, Christophe; Pinard, Laurent; Sassolas, Benoît; Cagnoli, Gianpietro

2018-05-01

Energy dissipation in amorphous coatings severely affects high-precision optical and quantum transducers. In order to isolate the source of coating loss, we performed an extensive study of Raman scattering and mechanical loss of a thermally treated sputtered silica coating. Our results show that loss is correlated with the population of three-membered rings of Si-O4 tetrahedral units and support the evidence that thermal treatment reduces the density of metastable states separated by a characteristic energy of about 0.5 eV in favor of an increase of the density of states separated by smaller activation energies.
Experimental Study of Cement - Sandstone/Shale - Brine - CO2 Interactions

PubMed Central

2011-01-01

Background Reactive-transport simulation is a tool that is being used to estimate long-term trapping of CO2, and wellbore and cap rock integrity for geologic CO2 storage. We reacted end member components of a heterolithic sandstone and shale unit that forms the upper section of the In Salah Gas Project carbon storage reservoir in Krechba, Algeria with supercritical CO2, brine, and with/without cement at reservoir conditions to develop experimentally constrained geochemical models for use in reactive transport simulations. Results We observe marked changes in solution composition when CO2 reacted with cement, sandstone, and shale components at reservoir conditions. The geochemical model for the reaction of sandstone and shale with CO2 and brine is a simple one in which albite, chlorite, illite and carbonate minerals partially dissolve and boehmite, smectite, and amorphous silica precipitate. The geochemical model for the wellbore environment is also fairly simple, in which alkaline cements and rock react with CO2-rich brines to form an Fe containing calcite, amorphous silica, smectite and boehmite or amorphous Al(OH)3. Conclusions Our research shows that relatively simple geochemical models can describe the dominant reactions that are likely to occur when CO2 is stored in deep saline aquifers sealed with overlying shale cap rocks, as well as the dominant reactions for cement carbonation at the wellbore interface. PMID:22078161
Designing of luminescent GdPO4:Eu@LaPO4@SiO2 core/shell nanorods: Synthesis, structural and luminescence properties

NASA Astrophysics Data System (ADS)

Ansari, Anees A.; Labis, Joselito P.; Aslam Manthrammel, M.

2017-09-01

GdPO4:Eu3+ (core) and GdPO4:Eu@LaPO4 (core/shell) nanorods (NRs) were successfully prepared by urea based co-precipitation process at ambient conditions which was followed by coating with amorphous silica shell via the sol-gel chemical route. The role of surface coating on the crystal structure, crystallinity, morphology, solubility, surface chemistry and luminescence properties were well investigated by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive X-ray (EDX) analysis, Fourier Transform Infrared (FTIR), UV-Vis, and photoluminescence spectroscopy. XRD pattern revealed highly purified, well-crystalline, single phase-hexagonal-rhabdophane structure of GdPO4 crystal. The TEM micrographs exhibited highly crystalline and narrow size distributed rod-shaped GdPO4:Eu3+ nanostructures with average width 14-16 nm and typical length 190-220 nm. FTIR spectra revealed characteristic infrared absorption bands of amorphous silica. High absorbance in a visible region of silica modified core/shell/Si NRs in aqueous environment suggests the high solubility along with colloidal stability. The photoluminescence properties were remarkably enhanced after growth of undoped LaPO4 layers due to the reduction of nonradiative transition rate. The advantages of presented high emission intensity and high solubility of core/shell and core/shell/Si NRs indicated the potential applications in monitoring biological events.
Escaping the Tyranny of Carbothermal Reduction: Fumed Silica from Sustainable, Green Sources without First Having to Make SiCl4.

PubMed

Yi, Eongyu; Hyde, Clare E; Sun, Kai; Laine, Richard M

2016-02-12

Fumed silica is produced in 1000 tons per year quantities by combusting SiCl4 in H2 /O2 flames. Given that both SiCl4 and combustion byproduct HCl are corrosive, toxic and polluting, this route to fumed silica requires extensive safeguards that may be obviated if an alternate route were found. Silica, including rice hull ash (RHA) can be directly depolymerized using hindered diols to generate distillable spirocyclic alkoxysilanes or Si(OEt)4 . We report here the use of liquid-feed flame spray pyrolysis (LF-FSP) to combust the aforementioned precursors to produce fumed silica very similar to SiCl4 -derived products. The resulting powders are amorphous, necked, <50 nm average particle sizes, with specific surface areas (SSAs) of 140-230 m(2) g(-1) . The LF-FSP approach does not require the containment constraints of the SiCl4 process and given that the RHA silica source is produced in million ton per year quantities worldwide, the reported approach represents a sustainable, green and potentially lower-cost alternative. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Increased dissolution rate and oral bioavailability of hydrophobic drug glyburide tablets produced using supercritical CO₂ silica dispersion technology.

PubMed

Guan, Jibin; Han, Jihong; Zhang, Dong; Chu, Chunxia; Liu, Hongzhuo; Sun, Jin; He, Zhonggui; Zhang, Tianhong

2014-04-01

The aim of this study was to design a silica-supported solid dispersion of a water-insoluble drug, glyburide, to increase its dissolution rate and oral absorption using supercritical fluid (SCF) technology. DSC and PXRD results indicated that the encapsulated drug in the optimal solid dispersion was in an amorphous state and the product was stable for 6 months. Glyburide was adsorbed onto the porous silica, as confirmed by the SEM images and BET analysis. Furthermore, FT-IR spectroscopy confirmed that there was no change in the chemical structure of glyburide after the application of SCF. The glyburide silica-based dispersion could also be compressed into tablet form. In vitro drug release analysis of the silica solid dispersion tablets demonstrated faster release of glyburide compared with the commercial micronized tablet. In an in vivo test, the AUC of the tablets composed of the new glyburide silica-based solid dispersion was 2.01 times greater than that of the commercial micronized glyburide tablets. In conclusion, SCF technology presents a promising approach to prepare silica-based solid dispersions of hydrophobic drugs because of its ability to increase their release and oral bioavailability. Copyright © 2013 Elsevier B.V. All rights reserved.
Stabilization and Amorphization of Lovastatin Using Different Types of Silica.

PubMed

Khanfar, Mai; Al-Nimry, Suhair

2017-08-01

Lovastatin (LOV), an antihyperlipidimic agent, is characterized by low solubility/poor dissolution and, thus, low bioavailability (<5%). A beneficial effect on its bioavailability could result from improving its dissolution. One of the most common methods used to enhance dissolution is the preparation of solid dispersions. Solid dispersions of LOV and silica with different surface areas were prepared. The effects of the type of silica, ratio of drug/silica, incubation period with silica, and the effect of surface area were all studied. Characterization of the prepared formulae for possible interaction between drug and polymer was carried out using differential scanning calorimetery, Fourier transform infrared spectroscopy, powder X-ray diffraction, surface area determination, and scanning electron microscopy. The dissolution profiles of all prepared formulae were constructed and evaluated. It was found that the formula made of LOV and Sylysia 350 FCP in a ratio of 1:5 after an incubation period of 48 h resulted in the best release, and it was stable after 3 months storage at 75% RH and 40°C.

Towards Luminescence Dating Of Mosaic Glass

NASA Astrophysics Data System (ADS)

Galli, A.; Martini, M.; Sibila, E.; Villa, I.

The possibility of dating archaeological glass by means of luminescent techniques has been investigated in recent years, despite the difficulties of this application, mainly linked to the amorphous structure of the material. We focused in particular on mosaic glass, after the encouraging results obtained on byzantine and medieval samples. Further studies were devoted to the comprehension of the luminescent mechanisms in silica glasses, and to the investigation of the relationships between luminescence, colouring or opacifier ions and crystalline phase of the vitreous matrix. The results of a study on the dosimetric characteristics of thermoluminescence (TL) and Optically Stimulated Luminescence (OSL) of a few medieval blue-green mosaic glasses from the San Lorenzo church (Milan) are presented, and the experimental protocols established to identify their suitability for dating are discussed.
Performance of dielectric nanocomposites: matrix-free, hairy nanoparticle assemblies and amorphous polymer-nanoparticle blends.

PubMed

Grabowski, Christopher A; Koerner, Hilmar; Meth, Jeffrey S; Dang, Alei; Hui, Chin Ming; Matyjaszewski, Krzysztof; Bockstaller, Michael R; Durstock, Michael F; Vaia, Richard A

2014-12-10

Demands to increase the stored energy density of electrostatic capacitors have spurred the development of materials with enhanced dielectric breakdown, improved permittivity, and reduced dielectric loss. Polymer nanocomposites (PNCs), consisting of a blend of amorphous polymer and dielectric nanofillers, have been studied intensely to satisfy these goals; however, nanoparticle aggregates, field localization due to dielectric mismatch between particle and matrix, and the poorly understood role of interface compatibilization have challenged progress. To expand the understanding of the inter-relation between these factors and, thus, enable rational optimization of low and high contrast PNC dielectrics, we compare the dielectric performance of matrix-free hairy nanoparticle assemblies (aHNPs) to blended PNCs in the regime of low dielectric contrast to establish how morphology and interface impact energy storage and breakdown across different polymer matrices (polystyrene, PS, and poly(methyl methacrylate), PMMA) and nanoparticle loadings (0-50% (v/v) silica). The findings indicate that the route (aHNP versus blending) to well-dispersed morphology has, at most, a minor impact on breakdown strength trends with nanoparticle volume fraction; the only exception being at intermediate loadings of silica in PMMA (15% (v/v)). Conversely, aHNPs show substantial improvements in reducing dielectric loss and maintaining charge/discharge efficiency. For example, low-frequency dielectric loss (1 Hz-1 kHz) of PS and PMMA aHNP films was essentially unchanged up to a silica content of 50% (v/v), whereas traditional blends showed a monotonically increasing loss with silica loading. Similar benefits are seen via high-field polarization loop measurements where energy storage for ∼15% (v/v) silica loaded PMMA and PS aHNPs were 50% and 200% greater than respective comparable PNC blends. Overall, these findings on low dielectric contrast PNCs clearly point to the performance benefits of functionalizing the nanoparticle surface with high-molecular-weight polymers for polymer nanostructured dielectrics.
Effets non-lineaires de second ordre dans les verres de silice

NASA Astrophysics Data System (ADS)

Godbout, Nicolas

Materials possessing inversion symmetry can not have a non-zero second-order susceptibility tensor. Since silica glasses are amorphous and isotropic, they possess this symmetry and therefore do not exhibit second-order nonlinear optical effects. However, the symmetry can be broken by several processes. The central question of this thesis is the determination of the mechanisms responsible for the second-order susceptibility in silica glasses after thermal poling. The presence of this nonlinearity arises through one of these mechanisms: the orientation of dipolar moieties possessing a second-order hyperpolarisability, or the build-up of a permanent electric field by charge motion which creates an apparent χ(2) through the already present χ (3). The dipole orientation model has a bigger potential of generating high optical nonlinearities than the built-in field model. This conclusion is based on a study of the crystalline structures of silica. The measurement of Maker fringes is the most informative technique for characterization of the optical properties of bulk poled samples. Measurements on Infrasil™ and Suprasil™ samples show an optically active layer of approximately 9 and 23 microns, with χ(2) susceptibilities of approximately 0.07 pm/V and 0.02 pm/V respectively. The analysis of Maker fringes in a similar sample suggests that the sign of the surface and bulk χ (2)-s is different, supporting the built-in field model as the origin of χ(2). Based on the results analyzed in this thesis, the second- order susceptibility of silica glasses after thermal poling results from the creation of a permanent built-in electric field caused by the movement of cations coupled to the pre-existing third-order nonlinearity. This claim is based on: the observed pump polarization dependence of Maker fringes, predictions of a steady-state ion migration model about the resulting optical properties and their confirmation by optical measurements; the presence of a bulk nonlinearity and its apparent opposite sign to the one of the surface; polarization and depolarization currents showing only signs of ion migration. (Abstract shortened by UMI.)
Physical characteristics of chitosan-silica composite of rice husk ash

NASA Astrophysics Data System (ADS)

Sumarni, Woro; Sri Iswari, Retno; Marwoto, Putut; Rahayu, Endah F.

2016-02-01

Some previous studies showed that the characteristics of chitosan membranes have a very rigid and non-porous structure so that its utilization is not maximized, particularly in the filtration process. Hence, it needs modification to improve the quality of the chitosan membranes. Adding the silica into the chitosan membranes is one of the offered solutions to overcome the problems of physical and mechanical properties of chitosan. This study aims to investigate the effect of variations in the silica composition to the physical characteristics of the chitosan-silica membranes of rice husk ash that were synthesized. The chitosan used is derived from the chitin of Vannamei shrimps’ shell with 82% degree of de-acetylation, while the silica was synthesized from rice husk ash with rendering of silica (SiO2) by 5% and the results of XRD analysis showed an amorphous phase. Membrane synthesis was performed using the phase inversion method with chitosan-silica mass ratios of rice husk ash, which were 1:0.0; 1:0.5; 1:1.0; 1:1.5 and 1:2.0. The results showed that the addition of silica increases the swelling index and the membrane permeability. The results of the analysis, FTIR spectra, obtained a new functional group after the addition of silica, they are Si-OH, Si-O-Si, and CO- NH2. The morphology test using CCD Microscope MS-804 results in the very tight chitosan membranes without the silica surface, it has no pores, smooth and homogeneous, while the chitosan-silica composite membrane of rice husk ash obviously has cracks and small cavities that seemed to spread out.
Characterisation of silica derived from rice husk (Muar, Johor, Malaysia) decomposition at different temperatures

NASA Astrophysics Data System (ADS)

Azmi, M. A.; Ismail, N. A. A.; Rizamarhaiza, M.; W. M. Hasif. A. A., K.; Taib, H.

2016-07-01

Rice husk was thermally decomposed to yield powder composed of silica (SiO2). Temperatures of 700°C and 1000°C were chosen as the decomposition temperatures. X-Ray Diffraction (XRD), X-Ray Florescence (XRF), Fourier Transform Infrared (FTIR), and Field Emission Scanning Electron Microscope (FESEM) analyses were conducted on a synthetic silica powder (SS-SiO2) and the rice husk ash as for the comparative characterisation study. XRD analyses clearly indicated that the decomposed rice husk yielded silica of different nature which are Crystalline Rice Husk Silica (C-RHSiO2) and Amorphous Rice Husk Silica (A-RHSiO2). Moreover, it was found that SS-SiO2 was of Quartz phase, C-RHSiO2 was of Trydimite and Cristobalite. Through XRF detection, the highest SiO2 purity was detected in SS-SiO2 followed by C-RHSiO2 and A-RHSiO2 with purity percentages of 99.60%, 82.30% and 86.30% respectively. FTIR results clearly indicated silica (SiO2) bonding 1056, 1064, 1047, 777, 790 and 798 cm-1) increased as the crystallinity silica increased. The Cristobalite phase was detected in C-RH SiO2 at the wavelength of 620 cm-1. Morphological features as observed by FESEM analyses confirmed that, SS-SiO2 and C-RH SiO2 showed prominent coarse granular morphology.
Adsorption of Amorphous Silica Nanoparticles onto Hydroxyapatite Surfaces Differentially Alters Surfaces Properties and Adhesion of Human Osteoblast Cells

PubMed Central

Kalia, Priya; Brooks, Roger A.; Kinrade, Stephen D.; Morgan, David J.; Brown, Andrew P.; Rushton, Neil; Jugdaohsingh, Ravin

2016-01-01

Silicon (Si) is suggested to be an important/essential nutrient for bone and connective tissue health. Silicon-substituted hydroxyapatite (Si-HA) has silicate ions incorporated into its lattice structure and was developed to improve attachment to bone and increase new bone formation. Here we investigated the direct adsorption of silicate species onto an HA coated surface as a cost effective method of incorporating silicon on to HA surfaces for improved implant osseointegration, and determined changes in surface characteristics and osteoblast cell adhesion. Plasma-sprayed HA-coated stainless steel discs were incubated in silica dispersions of different concentrations (0–42 mM Si), at neutral pH for 12 h. Adsorbed Si was confirmed by XPS analysis and quantified by ICP-OES analysis following release from the HA surface. Changes in surface characteristics were determined by AFM and measurement of surface wettability. Osteoblast cell adhesion was determined by vinculin plaque staining. Maximum Si adsorption to the HA coated disc occurred after incubation in the 6 mM silica dispersion and decreased progressively with higher silica concentrations, while no adsorption was observed with dispersions below 6 mM Si. Comparison of the Si dispersions that produced the highest and lowest Si adsorption to the HA surface, by TEM-based analysis, revealed an abundance of small amorphous nanosilica species (NSP) of ~1.5 nm in diameter in the 6 mM Si dispersion, with much fewer and larger NSP in the 42 mM Si dispersions. 29Si-NMR confirmed that the NSPs in the 6 mM silica dispersion were polymeric and similar in composition to the larger NSPs in the 42 mM Si dispersion, suggesting that the latter were aggregates of the former. Amorphous NSP adsorbed from the 6 mM dispersion on to a HA-coated disc surface increased the surface’s water contact angle by 53°, whereas that adsorbed from the 42 mM dispersion decreased the contact angle by 18°, indicating increased and decreased hydrophobicity, respectively. AFM showed an increase in surface roughness of the 6 mM Si treated surface, which correlated well with an increase in number of vinculin plaques. These findings suggest that NSP of the right size (relative to charge) adsorb readily to the HA surface, changing the surface characteristics and, thus, improving osteoblast cell adhesion. This treatment provides a simple way to modify plasma-coated HA surfaces that may enable improved osseointegration of bone implants. PMID:26863624
Silica-supported, single-site titanium catalysts for olefin epoxidation. A molecular precursor strategy for control of catalyst structure.

PubMed

Jarupatrakorn, Jonggol; Don Tilley, T

2002-07-17

A molecular precursor approach involving simple grafting procedures was used to produce site-isolated titanium-supported epoxidation catalysts of high activity and selectivity. The tris(tert-butoxy)siloxy titanium complexes Ti[OSi(O(t)Bu)(3)](4) (TiSi4), ((i)PrO)Ti[OSi(O(t)Bu)(3)](3) (TiSi3), and ((t)BuO)(3)TiOSi(O(t)Bu)(3) (TiSi) react with the hydroxyl groups of amorphous Aerosil, mesoporous MCM-41, and SBA-15 via loss of HO(t)Bu and/or HOSi(O(t)Bu)(3) and introduction of titanium species onto the silica surface. Powder X-ray diffraction, nitrogen adsorption/desorption, infrared, and diffuse reflectance ultraviolet spectroscopies were used to investigate the structures and chemical natures of the surface-bound titanium species. The titanium species exist mainly in isolated, tetrahedral coordination environments. Increasing the number of siloxide ligands in the molecular precursor decreases the amount of titanium that can be introduced this way, but also enhances the catalytic activity and selectivity for the epoxidation of cyclohexene with cumene hydroperoxide as oxidant. In addition, the high surface area mesoporous silicas (MCM-41 and SBA-15) are more effective than amorphous silica as supports for these catalysts. Supporting TiSi3 on the SBA-15 affords highly active cyclohexene epoxidation catalysts (0.25-1.77 wt % Ti loading) that provide turnover frequencies (TOFs) of 500-1500 h(-1) after 1 h (TOFs are reduced by about half after calcination). These results demonstrate that oxygen-rich siloxide complexes of titanium are useful as precursors to supported epoxidation catalysts.
High Pressure Response of Siliceous Materials

DTIC Science & Technology

2013-02-01

quartz, Starphire soda lime silicate glass, hydrated Starphire, BOROFLOAT borosilicate glass, an iron-containing soda lime silicate glass, opal (a hydrated... Opal (hydrated amorphous silica). .............................................................................. 10 2.7. ROBAX glass ceramic...spectrum as a function of stress for BOROFLOAT borosilicate glass. .......... 29 4.8. Raman spectrum as a function of stress for opal (hydrated
Simultaneous removal of colour, phosphorus and disinfection from treated wastewater using an agent synthesized from amorphous silica and hydrated lime.

PubMed

Yamashita, Takahiro; Aketo, Tsuyoshi; Minowa, Nobutaka; Sugimoto, Kiyomi; Yokoyama, Hiroshi; Ogino, Akifumi; Tanaka, Yasuo

2013-01-01

An agent synthesized from amorphous silica and hydrated lime (CSH-lime) was investigated for its ability to simultaneously remove the colour, phosphorus and disinfection from the effluents from wastewater treatment plants on swine farms. CSH-lime removed the colour and phosphate from the effluents, with the colour-removal effects especially high at pH 12, and phosphorous removal was more effective in strongly alkaline conditions (pH > 10). Colour decreased from 432 +/-111 (mean +/- SD) to 107 +/- 41 colour units and PO4(3-)P was reduced from 45 +/- 39 mg/L to undetectable levels at the CSH-lime dose of 2.0% w/v. Moreover, CSH-lime reduced the total organic carbon from 99.0 to 37.9 mg/L at the dose of 2.0% w/v and was effective at inactivating total heterotrophic and coliform bacteria. However, CSH-lime did not remove nitrogen compounds such as nitrite, nitrate and ammonium. Colour was also removed from dye solutions by CSH-lime, at the same dose.
Reduction of calcium flux from the extracellular region and endoplasmic reticulum by amorphous nano-silica particles owing to carboxy group addition on their surface.

PubMed

Onodera, Akira; Yayama, Katsutoshi; Morosawa, Hideto; Ishii, Yukina; Tsutsumi, Yasuo; Kawai, Yuichi

2017-03-01

Several studies have reported that amorphous nano-silica particles (nano-SPs) modulate calcium flux, although the mechanism remains incompletely understood. We thus analyzed the relationship between calcium flux and particle surface properties and determined the calcium flux route. Treatment of Balb/c 3T3 fibroblasts with nano-SPs with a diameter of 70 nm (nSP70) increased cytosolic calcium concentration, but that with SPs with a diameter of 300 or 1000 nm did not. Surface modification of nSP70 with a carboxy group also did not modulate calcium flux. Pretreatment with a general calcium entry blocker almost completely suppressed calcium flux by nSP70. Preconditioning by emptying the endoplasmic reticulum (ER) calcium stores slightly suppressed calcium flux by nSP70. These results indicate that nSP70 mainly modulates calcium flux across plasma membrane calcium channels, with subsequent activation of the ER calcium pump, and that the potential of calcium flux by nano-SPs is determined by the particle surface charge.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Ji, Xiaoyu; Lei, Shiming; Yu, Shih -Ying

Semiconductor core optical fibers with a silica cladding are of great interest in nonlinear photonics and optoelectronics applications. Laser crystallization has been recently demonstrated for crystallizing amorphous silicon fibers into crystalline form. Here we explore the underlying mechanism by which long single-crystal silicon fibers, which are novel platforms for silicon photonics, can be achieved by this process. Using finite element modeling, we construct a laser processing diagram that reveals a parameter space within which single crystals can be grown. Utilizing this diagram, we illustrate the creation of single-crystal silicon core fibers by laser crystallizing amorphous silicon deposited inside silica capillarymore » fibers by high-pressure chemical vapor deposition. The single-crystal fibers, up to 5.1 mm long, have a very welldefined core/cladding interface and a chemically pure silicon core that leads to very low optical losses down to ~0.47-1dB/cm at the standard telecommunication wavelength (1550 nm). Furthermore, tt also exhibits a photosensitivity that is comparable to bulk silicon. Creating such laser processing diagrams can provide a general framework for developing single-crystal fibers in other materials of technological importance.« less
Insights into Silicate Carbonation Processes in Water-Bearing Supercritical CO2 Fluids

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

Miller, Quin RS; Thompson, Christopher J.; Loring, John S.

2013-07-01

Long-term geologic storage of carbon dioxide (CO2) is considered an integral part to moderating CO2 concentrations in the atmosphere and subsequently minimizing effects of global climate change. Although subsurface injection of CO2 is common place in certain industries, deployment at the scale required for emission reduction is unprecedented and therefore requires a high degree of predictability. Accurately modeling geochemical processes in the subsurface requires experimental derived data for mineral reactions occurring between the CO2, water, and rocks. Most work in this area has focused on aqueous-dominated systems in which dissolved CO2 reacts to form crystalline carbonate minerals. Comparatively little laboratorymore » research has been conducted on reactions occurring between minerals in the host rock and the wet supercritical fluid phase. In this work, we studied the carbonation of wollastonite [CaSiO3] exposed to variably hydrated supercritical CO2 (scCO2) at a range of temperatures (50, 55 and 70 °C) and pressures (90,120 and 160 bar) that simulate conditions in geologic repositories. Mineral transformation reactions were followed by three novel in situ high pressure techniques, including x-ray diffraction that tracked the rate and extents of wollastonite conversion to calcite. Increased dissolved water concentrations in the supercritical CO2 resulted in increased silicate carbonation approaching ~50 wt. %. Development of thin water films on the mineral surface were directly observed with infrared spectroscopy and determined to be critical for facilitating carbonation processes. Even in extreme low water conditions, magic angle spinning nuclear magnetic resonance detected formation of Q3 [Si(OSi)3OH] and Q4 [Si(OSi)4] amorphous silica species. Unlike the thick (<10 μm) passivating silica layers observed in the fully water saturated scCO2 experiments, images obtained from a focused ion beam sectioned sample indicted these coatings were chemically wollastonite but structurally amorphous. In addition, evidence of an intermediate hydrated amorphous calcium carbonate forming under these conditions further emphasize the importance of understanding geochemical processes occurring in water bearing scCO2 fluids.« less
Quantitative Phase Analysis of Plasma-Treated High-Silica Materials

NASA Astrophysics Data System (ADS)

Kosmachev, P. V.; Abzaev, Yu. A.; Vlasov, V. A.

2018-06-01

The paper presents the X-ray diffraction (XRD) analysis of the crystal structure of SiO2 in two modifications, namely quartzite and quartz sand before and after plasma treatment. Plasma treatment enables the raw material to melt and evaporate after which the material quenches and condenses to form nanoparticles. The Rietveld refinement method is used to identify the lattice parameters of SiO2 phases. It is found that after plasma treatment SiO2 oxides are in the amorphous state, which are modeled within the microcanonical ensemble. Experiments show that amorphous phases are stable, and model X-ray reflection intensities approximate the experimental XRD patterns with fine precision. Within the modeling, full information is obtained for SiO2 crystalline and amorphous phases, which includes atom arrangement, structural parameters, atomic population of silicon and oxygen atoms in lattice sites.
Molecular dynamics simulation of potentiometric sensor response: the effect of biomolecules, surface morphology and surface charge.

PubMed

Lowe, B M; Skylaris, C-K; Green, N G; Shibuta, Y; Sakata, T

2018-05-10

The silica-water interface is critical to many modern technologies in chemical engineering and biosensing. One technology used commonly in biosensors, the potentiometric sensor, operates by measuring the changes in electric potential due to changes in the interfacial electric field. Predictive modelling of this response caused by surface binding of biomolecules remains highly challenging. In this work, through the most extensive molecular dynamics simulation of the silica-water interfacial potential and electric field to date, we report a novel prediction and explanation of the effects of nano-morphology on sensor response. Amorphous silica demonstrated a larger potentiometric response than an equivalent crystalline silica model due to increased sodium adsorption, in agreement with experiments showing improved sensor response with nano-texturing. We provide proof-of-concept that molecular dynamics can be used as a complementary tool for potentiometric biosensor response prediction. Effects that are conventionally neglected, such as surface morphology, water polarisation, biomolecule dynamics and finite-size effects, are explicitly modelled.
Preparation and characterization of silica aerogels from diatomite via ambient pressure drying

NASA Astrophysics Data System (ADS)

Wang, Baomin; Ma, Hainan; Song, Kai

2014-07-01

The silica aerogels were successfully fabricated under ambient pressure from diatomite. The influence of different dilution ratios of diatomite filtrate on physical properties of aerogels were studied. The microstructure, surface functional groups, thermal stability, morphology and mechanical properties of silica aerogels based on diatomite were investigated by BET adsorption, FT-IR, DTA-TG, FESEM, TEM, and nanoindentation methods. The results indicate that the filtrate diluted with distilled water in a proportion of 1: 2 could give silica aerogels in the largest size with highest transparency. The obtained aerogels with density of 0.122-0.203 g/m3 and specific surface area of 655.5-790.7 m2/g are crack free amorphous solids and exhibited a sponge-like structure. Moreover, the peak pore size resided at 9 nm. The initial aerogels were hydrophobic, when being heat-treated around 400°C, the aerogels were transformed into hydrophilic ones. The obtained aerogel has good mechanical properties.
Band gap engineering of N-alloyed Ga{sub 2}O{sub 3} thin films

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

Song, Dongyu; Li, Bingsheng, E-mail: libingsheng@hit.edu.cn, E-mail: ashen@ccny.cuny.edu; Sui, Yu

2016-06-15

The authors report the tuning of band gap of GaON ternary alloy in a wide range of 2.75 eV. The samples were prepared by a two-step nitridation method. First, the samples were deposited on 2-inch fused silica substrates by megnetron sputtering with NH{sub 3} and Ar gas for 60 minutes. Then they were annealed in NH{sub 3} ambience at different temperatures. The optical band gap energies are calculated from transmittance measurements. With the increase of nitridation temperature, the band gap gradually decreases from 4.8 eV to 2.05 eV. X-ray diffraction results indicate that as-deposited amorphous samples can crystallize into monoclinicmore » and hexagonal structures after they were annealed in oxygen or ammonia ambience, respectively. The narrowing of the band gap is attributed to the enhanced repulsion of N2p -Ga3d orbits and formation of hexagonal structure.« less
Photoluminescence Study of Gallium Nitride Thin Films Obtained by Infrared Close Space Vapor Transport.

PubMed

Santana, Guillermo; de Melo, Osvaldo; Aguilar-Hernández, Jorge; Mendoza-Pérez, Rogelio; Monroy, B Marel; Escamilla-Esquivel, Adolfo; López-López, Máximo; de Moure, Francisco; Hernández, Luis A; Contreras-Puente, Gerardo

2013-03-15

Photoluminescence (PL) studies in GaN thin films grown by infrared close space vapor transport (CSVT-IR) in vacuum are presented in this work. The growth of GaN thin films was done on a variety of substrates like silicon, sapphire and fused silica. Room temperature PL spectra of all the GaN films show near band-edge emission (NBE) and a broad blue and green luminescence (BL, GL), which can be seen with the naked eye in a bright room. The sample grown by infrared CSVT on the silicon substrate shows several emission peaks from 2.4 to 3.22 eV with a pronounced red shift with respect to the band gap energy. The sample grown on sapphire shows strong and broad ultraviolet emission peaks (UVL) centered at 3.19 eV and it exhibits a red shift of NBE. The PL spectrum of GaN films deposited on fused silica exhibited a unique and strong blue-green emission peak centered at 2.38 eV. The presence of yellow and green luminescence in all samples is related to native defects in the structure such as dislocations in GaN and/or the presence of amorphous phases. We analyze the material quality that can be obtained by CSVT-IR in vacuum, which is a high yield technique with simple equipment set-up, in terms of the PL results obtained in each case.
Photoluminescence Study of Gallium Nitride Thin Films Obtained by Infrared Close Space Vapor Transport

PubMed Central

Santana, Guillermo; de Melo, Osvaldo; Aguilar-Hernández, Jorge; Mendoza-Pérez, Rogelio; Monroy, B. Marel; Escamilla-Esquivel, Adolfo; López-López, Máximo; de Moure, Francisco; Hernández, Luis A.; Contreras-Puente, Gerardo

2013-01-01

Photoluminescence (PL) studies in GaN thin films grown by infrared close space vapor transport (CSVT-IR) in vacuum are presented in this work. The growth of GaN thin films was done on a variety of substrates like silicon, sapphire and fused silica. Room temperature PL spectra of all the GaN films show near band-edge emission (NBE) and a broad blue and green luminescence (BL, GL), which can be seen with the naked eye in a bright room. The sample grown by infrared CSVT on the silicon substrate shows several emission peaks from 2.4 to 3.22 eV with a pronounced red shift with respect to the band gap energy. The sample grown on sapphire shows strong and broad ultraviolet emission peaks (UVL) centered at 3.19 eV and it exhibits a red shift of NBE. The PL spectrum of GaN films deposited on fused silica exhibited a unique and strong blue-green emission peak centered at 2.38 eV. The presence of yellow and green luminescence in all samples is related to native defects in the structure such as dislocations in GaN and/or the presence of amorphous phases. We analyze the material quality that can be obtained by CSVT-IR in vacuum, which is a high yield technique with simple equipment set-up, in terms of the PL results obtained in each case. PMID:28809356
Opaline silica in young deposits on Mars

USGS Publications Warehouse

Milliken, Ralph E.; Swayze, Gregg A.; Arvidson, Raymond E.; Bishop, Janice L; Clark, Roger N.; Ehlmann, Bethany L.; Green, Robert O.; Grotzinger, John P.; Morris, R.V.; Murchie, Scott L.; Mustard, John F.; Weitz, C.

2008-01-01

High spatial and spectral resolution reflectance data acquired by the Mars Reconnaissance Orbiter Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) instrument reveal the presence of H2O- and SiOH-bearing phases on the Martian surface. The spectra are most consistent with opaline silica and glass altered to various degrees, confirming predictions based on geochemical experiments and models that amorphous silica should be a common weathering product of the basaltic Martian crust. These materials are associated with hydrated Fe sulfates, including H3O-bearing jarosite, and are found in finely stratified deposits exposed on the floor of and on the plains surrounding the Valles Marineris canyon system. Stratigraphic relationships place the formation age of these deposits in the late Hesperian or possibly the Amazonian, implying that aqueous alteration continued to be an important and regionally extensive process on Mars during that time.
The potential use of silica sand as nanomaterials for mortar

NASA Astrophysics Data System (ADS)

Setiati, N. Retno

2017-11-01

The development of nanotechnology is currently experiencing rapid growth. The use of the term nanotechnology is widely applied in areas such as healthcare, industrial, pharmaceutical, informatics, or construction. By the nanotechnology in the field of concrete construction, especially the mechanical properties of concrete are expected to be better than conventional concrete. This study aims to determine the effect of the potential of silica sand as a nanomaterial that is added into the concrete mix The methodology used consist of nanomaterial synthesis process of silica sand using Liquid Polishing Milling Technology (PLMT). The XRF and XRD testing were conducted to determine the composition of silica contained in the silica sand and the level of reactivity of the compound when added into the concrete mix. To determine the effect of nano silica on mortar, then made the specimen with size 50 mm x 50 mm x 50 mm. The composition of mortar is made in two variations, ie by the addition of 3% nano silica and without the addition of nanosilica. To know the mechanical properties of mortar, it is done testing of mortar compressive strength at the age of 28 days. Based on the analysis and evaluation, it is shown that compounds of silica sand in Indonesia, especially Papua reached more than 99% SiO2 and so that the amorphous character of silica sand can be used as a nanomaterial for concrete construction. The results of mechanical tests show that there is an increase of 12% compressive strength of mortar that is added with 3% nano silica.

Effect of a core-softened O-O interatomic interaction on the shock compression of fused silica

NASA Astrophysics Data System (ADS)

Izvekov, Sergei; Weingarten, N. Scott; Byrd, Edward F. C.

2018-03-01

Isotropic soft-core potentials have attracted considerable attention due to their ability to reproduce thermodynamic, dynamic, and structural anomalies observed in tetrahedral network-forming compounds such as water and silica. The aim of the present work is to assess the relevance of effective core-softening pertinent to the oxygen-oxygen interaction in silica to the thermodynamics and phase change mechanisms that occur in shock compressed fused silica. We utilize the MD simulation method with a recently published numerical interatomic potential derived from an ab initio MD simulation of liquid silica via force-matching. The resulting potential indicates an effective shoulder-like core-softening of the oxygen-oxygen repulsion. To better understand the role of the core-softening we analyze two derivative force-matching potentials in which the soft-core is replaced with a repulsive core either in the three-body potential term or in all the potential terms. Our analysis is further augmented by a comparison with several popular empirical models for silica that lack an explicit core-softening. The first outstanding feature of shock compressed glass reproduced with the soft-core models but not with the other models is that the shock compression values at pressures above 20 GPa are larger than those observed under hydrostatic compression (an anomalous shock Hugoniot densification). Our calculations indicate the occurrence of a phase transformation along the shock Hugoniot that we link to the O-O repulsion core-softening. The phase transformation is associated with a Hugoniot temperature reversal similar to that observed experimentally. With the soft-core models, the phase change is an isostructural transformation between amorphous polymorphs with no associated melting event. We further examine the nature of the structural transformation by comparing it to the Hugoniot calculations for stishovite. For stishovite, the Hugoniot exhibits temperature reversal and associated phase transformation, which is a transition to a disordered phase (liquid or dense amorphous), regardless of whether or not the model accounts for core-softening. The onset pressures of the transformation predicted by different models show a wide scatter within 60-110 GPa; for potentials without core-softening, the onset pressure is much higher than 110 GPa. Our results show that the core-softening of the interaction in the oxygen subsystem of silica is the key mechanism for the structural transformation and thermodynamics in shock compressed silica. These results may provide an important contribution to a unified picture of anomalous response to shock compression observed in other network-forming oxides and single-component systems with core-softening of effective interactions.
In vitro cytotoxicity and quantitative silica analysis of diatomaceous earth products.

PubMed

Bye, E; Davies, R; Griffiths, D M; Gylseth, B; Moncrieff, C B

1984-05-01

Mouse peritoneal macrophages were used to evaluate the relative cytotoxicity of a series of diatomaceous earth products in vitro. The amorphous and crystalline silica content of the products was determined by a combination of infrared spectroscopy and x ray powder diffraction techniques. The cytotoxicities of the high cristobalite content flux calcined materials were similar to that of the standard cristobalite ; both the natural and straight calcined materials had significantly greater activities than the flux calcined materials. Thus within the limitations of the macrophage cytotoxicity test the hypothesis that crystalline content is the only determinant of fibrogenicity of diatomaceous earth is not supported.
Magnetic stability of oxygen defects on the SiO 2 surface

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

Adelstein, Nicole; Lee, Donghwa; DuBois, Jonathan L.

2017-02-21

The magnetic stability of E' centers and the peroxy radical on the surface of α-quartz is investigated with first-principles calculations to understand their role in magnetic flux noise in superconducting qubits (SQs) and superconducting quantum interference devices (SQUIDs) fabricated on amorphous silica substrates. Paramagnetic E' centers are common in both stoichiometric and oxygen deficient silica and quartz, and we calculate that they are more common on the surface than the bulk. However, we find the surface defects are magnetically stable in their paramagnetic ground state and thus will not contribute to 1/f noise through fluctuation at millikelvin temperatures.
In vitro cytotoxicity and quantitative silica analysis of diatomaceous earth products.

PubMed Central

Bye, E; Davies, R; Griffiths, D M; Gylseth, B; Moncrieff, C B

1984-01-01

Mouse peritoneal macrophages were used to evaluate the relative cytotoxicity of a series of diatomaceous earth products in vitro. The amorphous and crystalline silica content of the products was determined by a combination of infrared spectroscopy and x ray powder diffraction techniques. The cytotoxicities of the high cristobalite content flux calcined materials were similar to that of the standard cristobalite ; both the natural and straight calcined materials had significantly greater activities than the flux calcined materials. Thus within the limitations of the macrophage cytotoxicity test the hypothesis that crystalline content is the only determinant of fibrogenicity of diatomaceous earth is not supported. Images PMID:6326795
Date palm waste-derived biochar composites with silica and zeolite: synthesis, characterization and implication for carbon stability and recalcitrant potential.

PubMed

Ahmad, Munir; Ahmad, Mahtab; Usman, Adel R A; Al-Faraj, Abdullah S; Abduljabbar, Adel; Ok, Yong Sik; Al-Wabel, Mohammad I

2017-03-23

Engineered organo-mineral composites were synthesized from date palm waste biochar and silica or zeolite via mechanochemical treatments. Date palm tree rachis (leaves) waste biomass was pre-treated with silica or zeolite minerals via ball milling and sonication prior to pyrolysis at 600 °C. The resultant organo-mineral composites and pristine materials were characterized using X-ray diffraction, thermogravimetric-differential thermal (TG-DTA), Fourier transform infrared, scanning electron microscope analyses and surface area and porosity analyzer to investigate the variations in physiochemical and structural characteristics. Compared to the resultant composites derived from non-milled date palm biomass, ball milling increased surface area, while decreased crystallinity index and effective particle size of the biochar composites. Silica composited biochars were located near origin in the van Krevelen diagram indicating lowest H/C and O/C molar ratios, thus suggesting higher aromaticity and lower polarity compared to other biochars. TGA thermograms indicated highest thermal stability of silica composited biochars. Ash and moisture corrected TGA thermograms were used to calculate recalcitrance index (R 50 ) of the materials, which speculated high degradability of biomass (R 50 < 0.4), minimal degradability of biochars and zeolite composited biochars (0.5 < R 50 < 0.7) and high recalcitrant nature of silica composited biochars (R 50 > 0.7). Silica composited biochars exhibited highest carbon sequestration potential (64.17-95.59%) compared to other biochars. Highest recalcitrance and carbon sequestration potential of silica composited biochars may be attributed to changes in structural arrangements in the silica-biochar complex. Encapsulations of biochar particles with amorphous silica via Si-C bonding may have prevented thermal degradation, subsequently increasing recalcitrance potential of silica composited biochars.
Enhanced stab resistance of armor composites with functionalized silica nanoparticles

NASA Astrophysics Data System (ADS)

Mahfuz, Hassan; Clements, Floria; Rangari, Vijaya; Dhanak, Vinod; Beamson, Graham

2009-03-01

Traditionally shear thickening fluid (STF) reinforced with Kevlar has been used to develop flexible armor. At the core of the STF-Kevlar composites is a mixture of polyethylene glycol (PEG) and silica particles. This mixture is often known as STF and is consisted of approximately 45 wt % PEG and 55 wt % silica. During rheological tests, STF shows instantaneous spike in viscosity above a critical shear rate. Fabrication of STF-Kevlar composites requires preparation of STF, dilution with ethanol, and then impregnation with Kevlar. In the current approach, nanoscale silica particles were dispersed directly into a mixture of PEG and ethanol through a sonic cavitation process. Two types of silica nanoparticles were used in the investigation: 30 nm crystalline silica and 7 nm amorphous silica. The admixture was then reinforced with Kevlar fabric to produce flexible armor composites. In the next step, silica particles are functionalized with a silane coupling agent to enhance bonding between silica and PEG. The performance of the resulting armor composites improved significantly. As evidenced by National Institute of Justice spike tests, the energy required for zero-layer penetration (i.e., no penetration) jumped twofold: from 12 to 25 J cm2/g. The source of this improvement has been traced to the formation of siloxane (Si-O-Si) bonds between silica and PEG and superior coating of Kevlar filaments with particles. Fourier transform infrared, x-ray photoemission spectroscopy, and scanning electron microscopy studies were performed to examine chemical bonds, elemental composition, and particle dispersion responsible for such improvement. In summary, our experiments have demonstrated that functionalization of silica particles followed by direct dispersion into PEG resulted in superior Kevlar composites having much higher spike resistance.
SERS active Ag encapsulated Fe@SiO2 nanorods in electromagnetic wave absorption and crystal violet detection.

PubMed

Senapati, Samarpita; Srivastava, Suneel Kumar; Singh, Shiv Brat; Kulkarni, Ajit R

2014-11-01

The present work is focused on the preparation of Fe nanorods by the chemical reduction of FeCl3 (aq) using NaBH4 in the presence of glycerol as template followed by annealing of the product at 500°C in the presence of H2 gas flow. Subsequently, its surface has been modified by silica followed by silver nanoparticles to form silica coated Fe (Fe@SiO2) and Ag encapsulated Fe@SiO2 nanostructure employing the Stöber method and silver mirror reaction respectively. XRD pattern of the products confirmed the formation of bcc phase of iron and fcc phase of silver, though silica remained amorphous. FESEM images established the growth of iron nanorods from the annealed product and also formation of silica and silver coating on its surface. The appearance of the characteristics bands in FTIR confirmed the presence of SiO2 on the Fe surface. Magnetic measurements at room temperature indicated the ferromagnetic behavior of as prepared iron nanorods, Fe@SiO2 and silver encapsulated Fe@SiO2 nanostructures. All the samples exhibited strong microwave absorption property in the high frequency range (10GHz), though it is superior for Ag encapsulated Fe@SiO2 (-14.7dB) compared with Fe@SiO2 (-9.7dB) nanostructures of the same thickness. The synthesized Ag encapsulated Fe@SiO2 nanostructure also exhibited the SERS phenomena, which is useful in the detection of the carcinogenic dye crystal violet (CV) upto the concentration of 10(-10)M. All these findings clearly demonstrate that the Ag encapsulated Fe@SiO2 nanostructure could efficiently be used in the environmental remediation. Copyright © 2014 Elsevier Inc. All rights reserved.
Effects of surface structural disorder and surface coverage on isotopic fractionation during Zn(II) adsorption onto quartz and amorphous silica surfaces

DOE PAGES

Nelson, Joey; Wasylenki, Laura; Bargar, John R.; ...

2017-08-05

Metal ion-mineral surface interactions and the attendant isotopic fractionation depend on the properties of the mineral surface and the local atomic-level chemical environment. Furthermore, these factors have not been systematically examined for phases of the same composition with different levels of surface disorder.
Effects of surface structural disorder and surface coverage on isotopic fractionation during Zn(II) adsorption onto quartz and amorphous silica surfaces

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

Nelson, Joey; Wasylenki, Laura; Bargar, John R.

Metal ion-mineral surface interactions and the attendant isotopic fractionation depend on the properties of the mineral surface and the local atomic-level chemical environment. Furthermore, these factors have not been systematically examined for phases of the same composition with different levels of surface disorder.
In Situ Measurement of the Infrared Spectral Extinction for Various Chemical, Biological, and Background Aerosols

DTIC Science & Technology

2003-09-01

silicon dioxide that is composed of fine sub- micron SiO2 particles. Used commercially as a thickening agent for food and cosmetics, this silica ... aerogel ” is extremely amorphous (94% of its volume is air) and is sometimes used as a fluidizer to improve aerosol dissemination efficiencies. As a
Gusev Crater on Mars: Wet and Dry

NASA Technical Reports Server (NTRS)

Yen, Albert; Gellert, Ralf; Morris, Richard

2008-01-01

The Mars Exploration Rover Spirit has traversed over 7.5 km in 1470 sols of operations at the Gusev Crater landing site. Chemical and mineralogical evidence from approximately 200 in-situ samples indicate various degrees of exposure to liquid water, from wet and saturated to dry and unaltered. (1) Six samples with concentrations of amorphous silica between 60 and 95 wt% were discovered in a small valley less than 50 meters in length. Associated enrichments in titanium oxide, relatively insoluble at low pH, suggest that these silica deposits formed as a result of acidic leaching processes. Liquid water interactions with these surface materials were necessary to remove cations solubilized in the low pH environment or to concentrate silica in solution prior to precipitation. (2) Hydrated ferric sulfates are found in subsurface deposits which have the unmistakable chemical signatures of nearby rocks. The movement of hydrothermal fluids and/or fumarolic vapors through local rocks prior to precipitation of these materials is suggested by these observations. (3) Goethite (alpha-FeOOH), a mineral phase which requires water to form, represents 20% to 35% of the iron in numerous rock samples (Clovis Class) on the West Spur of the Columbia Hills. Alteration of iron under aqueous conditions is clearly indicated by this presence of goethite. (4) Nearly isochemical signatures are found in elemental analyses of over ten distinct samples (Wishstone/Watchtower class rocks), yet the ratio of ferric iron to total iron varies from 0.4 to 0.95. Small quantities of water, insufficient to flush cations from the samples, were likely responsible for this weathering. (5) Bromine, a trace element readily mobilized by water, is found in high concentrations in certain rock interiors and is enhanced in subsurface soils, consistent with transport to localized cold traps by water thin-films. (6) Also relevant to the characterizing the role of liquid water is the discovery of an areally extensive ultramafic sequence of rocks where over 70% of the iron is in unaltered olivine and the ferric to total iron ratio is 0.1. This result indicates that certain materials at the martian surface have been protected from aqueous alteration.
Silicification in Grasses: Variation between Different Cell Types

PubMed Central

Kumar, Santosh; Soukup, Milan; Elbaum, Rivka

2017-01-01

Plants take up silicon as mono-silicic acid, which is released to soil by the weathering of silicate minerals. Silicic acid can be taken up by plant roots passively or actively, and later it is deposited in its polymerized form as amorphous hydrated silica. Major silica depositions in grasses occur in root endodermis, leaf epidermal cells, and outer epidermal cells of inflorescence bracts. Debates are rife about the mechanism of silica deposition, and two contrasting scenarios are often proposed to explain it. According to the passive mode of silicification, silica deposition is a result of silicic acid condensation due to dehydration, such as during transpirational loss of water from the aboveground organs. In general, silicification and transpiration are positively correlated, and continued silicification is sometimes observed after cell and tissue maturity. The other mode of silicification proposes the involvement of some biological factors, and is based on observations that silicification is not necessarily coupled with transpiration. Here, we review evidence for both mechanisms of silicification, and propose that the deposition mechanism is specific to the cell type. Considering all the cell types together, our conclusion is that grass silica deposition can be divided into three modes: spontaneous cell wall silicification, directed cell wall silicification, and directed paramural silicification in silica cells. PMID:28400787
Crystal-chemistry of alteration products of vitrified wastes: Implications on the retention of polluting elements

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

Sterpenich, Jerome

2008-07-01

Alteration products of vitrified wastes coming from the incineration of household refuse (MSW) are described. Two vitrified wastes containing 50% and 70% of fly ash and a synthetic stained-glass with a composition close to that of an ancient glass (medieval stained-glass) were altered under different pH conditions (1, 5.5 corresponding to demineralized water and 10) during 181 days. Under acidic condition, the alteration layer is made of an amorphous hydrated silica gel impoverished in most of the initial elements. A minor phase MPO{sub 4} . nH{sub 2}O, where M represents Fe, Ti, Al, Ca and K cations, also constitutes themore » altered layer of the synthetic stained-glass. Under neutral and basic conditions, the altered layer is made of an amorphous hydrated silica gel and a crystallized calcium phosphate phase. The silica gel is depleted in alkalis and alkali-earth elements but contains significant amounts of aluminium, magnesium and transition elements, whereas the calcium phosphate is a hydroxylapatite-like phase with P-Si substitutions and a Ca/P ratio depending on the pH of the solution. This study shows: (i) the strong influence of pH conditions on the crystal-chemistry of alteration products and thus on the mechanisms of weathering resulting in different trapping of polluting elements, and (ii) that glass alteration does not necessary produce thermodynamically stable phases which has to be taken into account for the prediction of the long-term behavior.« less
Quantifying Silica Reactivity in Subsurface Environments: Reaction Affinity and Solute Matrix Controls on Quartz and SiO2 Glass Dissolution Kinetics

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

Patricia M. Dove

2000-12-13

During the three years of this project, Professor Dove's laboratory made tremendous progress in understanding controls on amorphous silica dissolution kinetics in aqueous solutions. Our findings have already received considerable attention. In hydrothermal and low temperature studies, the work focused on determining quantitative and mechanistic controls on the most abundant silica polymorphs in Earth environments--quartz and amorphous silica. Our studies achieved goals set forth in the original proposal to establish a new quantitative understanding of amorphous silica dissolution. This support has resulted in 10 journal, 12 abstracts and 2 thesis publications. The PI and students were also recognized with 6more » awards during this period. The 1998 EMSP conference in Chicago was an important meeting for our project. The symposium, enabled P.I. Dove to establish valuable contacts with ''users'' having specific needs for the findings of our EMSP project related to the urgency of problems in the Tanks Focus Area (TFA). Since that time, our working relations developed as Dove interacted with TFA scientists and engineers on the problems of waste glass properties. These interactions refined our experimental objectives to better meet their needs. Dove presented the results of EMSP research findings to a TFA subgroup at a Product Acceptance Workshop held in Salt Lake City during December 1998. The travel costs to attend this unanticipated opportunity were paid from EMSP project funds. In January 2000, Dove also attended a similar meeting in Atlanta with PNNL, SRL and BNF scientists/engineers to discuss new issues and make another level of decisions on the Product Acceptance goals. Our EMSP-funded research interfaced very well with the ongoing studies of Dr. Pete McGrail and colleagues in the Applied Geochemistry Group at PNNL. The value of our work to ''users'' was further demonstrated when Dove's EMSP-funded Postdoc, Dr. Jonathan Icenhower was hired by the same PNNL group. With the Icenhower move from postdoc in the Dove lab to a senior scientist position at PNNL, we directly facilitated information transfer from the ''university to user'' environment. Icenhower brought experience in silica-water reactivity and the experimental expertise in high-quality methods of mineral-water reaction kinetics to the PNNL waste clean-up effort. In a further interaction, M.S. student Troy Lorier was hired at the Savannah River Laboratory for a staff position with the Bill Holtzcheiter glass group. His research meshed well with on-going efforts at SRL. In short, our EMSP project went well beyond the academic goals of producing high quality scientific knowledge to establish connections with on-site users to solve problems in TFA. This project also produced new talent for the waste immobilization effort. This EMSP project was highly successful and we thank our sponsors for the opportunity to advance scientific knowledge in this important area of research.« less
Synthesis and characterization of LTA nanozeolite using barley husk silica: Mercury removal from standard and real solutions

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

Azizi, Seyed Naser, E-mail: azizi@umz.ac.ir; Dehnavi, Ahmad Roozbehani, E-mail: Roozbehanisulfur@yahoo.com; Joorabdoozha, Amir

2013-05-15

Highlights: ► Silica extraction from barley husk with high purity for the synthesis of A nanozeolite. ► Free template A nanozeolite synthesized via new source of silica at low temperature. ► Optimization of SiO{sub 2}/Al{sub 2}O{sub 3}, Na{sub 2}O/SiO{sub 2} ratios, temperature and time of the synthesis. ► Utilizing of synthesized A nanozeolite for mercury removal from aqueous solutions. ► Mercury removal at optimized pH, contact time and adsorbent dose from real solution. - Abstract: In this study, synthesized Lined Type A (LTA) nanozeolite from barley husk silica (BHS) was used for mercury removal from standard and real aqueous solutions.more » The BHS in amorphous phase with 80% purity was extracted from barley husk ash (BHA), and used effectively as a new source of silica for the synthesis of NaA nanozeolite. The NaA nanocrystal in pure phase has been synthesized at low temperature, without adding any organic additives. The effects of heating time, reaction temperature, SiO{sub 2}/Al{sub 2}O{sub 3}, and Na{sub 2}O/SiO{sub 2} mole ratios on the crystallization of NaA nanozeolite were studied. The adsorption capacity of mercury (II) was studied as a function of pH, contact time, and amount of adsorbent. The crystallization of NaA nanozeolite from BHS was characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), Brunauer–Emmett–Teller (BET), and FTIR techniques. Moreover, concentration of Hg{sup 2+} ions in the aqueous solutions was analyzed by hydride generation atomic absorption spectroscopy method (HG-AAS). The standard and real samples analysis showed that NaA nanozeolite is capable of Hg{sup 2+} ions removal from the aqueous solutions. Efficiency of mercury (II) adsorption from real solutions onto the nano-sized NaA zeolite was 98%.« less
Titania-coated manganite nanoparticles: Synthesis of the shell, characterization and MRI properties

NASA Astrophysics Data System (ADS)

Jirák, Zdeněk; Kuličková, Jarmila; Herynek, Vít; Maryško, Miroslav; Koktan, Jakub; Kaman, Ondřej

2017-04-01

Novel procedure for coating of oxide nanoparticles with titania, employing hydrolysis and polycondensation of titanium alkoxides under high-dilution conditions and cationic surfactants, is developed and applied to magnetic cores of perovskite manganite. Bare particles of the ferromagnetic La0.65Sr0.35MnO3 phase, possessing high magnetization, M10 kOe(4.5 K) = 63.5 emu g-1, and Curie temperature, TC = 355 K, are synthesized by sol-gel procedure and subsequently coated with titania. Further, a comparative silica-coated product is prepared. In order to analyse the morphology, colloidal stability, and surface properties of these two types of coated particles, a detailed study by means of transmission electron microscopy, dynamic light scattering, zeta-potential measurements, and IR spectroscopy is carried out. The experiments on the titania-coated sample reveal a continuous though porous character of the TiO2 shell, the nature of which is amorphous but can be transformed to anatase at higher temperatures. Finally, the relaxometric study at the magnetic field of 0.5 T, performed to quantity the transverse relaxivity and its temperature dependence, reveals important differences between the titania-coated and silica-coated nanoparticles.
Composition of weathering crusts on sandstones from natural outcrops and architectonic elements in an urban environment.

PubMed

Marszałek, Mariola; Alexandrowicz, Zofia; Rzepa, Grzegorz

2014-12-01

This work presents mineralogical and chemical characteristics of weathering crusts developed on sandstones exposed to various air pollution conditions. The samples have been collected from sandstone tors in the Carpathian Foothill and from buildings in Kraków. It has been stated that these crusts differ in both fabric and composition. The sandstone black crust from tors is rich in organic matter and composed of amorphous silica. Sulphate incrustations accompanied by dust particles have been only sometimes observed. Beneath the black crust, a zone coloured by iron (oxyhydr)oxides occurs. The enrichment of the surface crust in silica and iron compounds protects the rock interior from atmospheric impact. The sandstones from architectonic details are also covered by a thin carbon-rich black crust, but they are visibly loosened. Numerous salts, mainly gypsum and halite, crystallise here, thus enhancing deterioration of the rock. Moreover, spherical particles originated from industrial emissions are much more common. Gypsum in natural outcrops, forms isolated and well-developed crystals, whilst these found on the architectonic details are finer and densely cover the surface. Such diversity reflects various concentrations of acid air pollutants in solutions.
CYTOTOXIC EFFECTS OF SOME MINERAL DUSTS ON SYRIAN HAMSTER PERITONEAL MACROPHAGES

PubMed Central

Bey, Elke; Harington, J. S.

1971-01-01

Hamster peritoneal macrophages were grown in cell culture and their response to various conditions was examined. The cultures responded favorably to high concentrations of serum and to medium which had been preconditioned by contact with tumor cells. After 2–3 days of adaptation, they entered into a period of stability which lasted from the 4th to the 9th day. Macrophage cultures in this stable phase were treated with various samples of mineral dusts and their response determined by counting the number of viable macrophages/cm2 at intervals over a period of 72 hr. Crystalline silica Snowit was found to be nontoxic. Amorphous silica Fransil caused a characteristic cytotoxic effect and a rapid decline in cell population at doses less than 150 µg/5 x 105 cells. Of the three different kinds of asbestos used, chrysotile was toxic and amosite and crocidolite nontoxic at equivalent concentrations. A comparison of two preparations of chrysotile which differed in surface area showed that weight rather than surface area determines toxicity. Pretreatment of chrysotile with tryptose phosphate broth under drastic conditions accelerated but did not increase the final intensity of the cytotoxic effect. PMID:4101804
Phase Composition, Crystallite Size and Physical Properties of B2O3-added Forsterite Nano-ceramics

NASA Astrophysics Data System (ADS)

Pratapa, S.; Chairunnisa, A.; Nurbaiti, U.; Handoko, W. D.

2018-05-01

This study was aimed to know the effect of B2O3 addition on the phase composition, crystallite size and dielectric properties of forsterite (Mg2SiO4) nano-ceramics. It utilized a purified silica sand from Tanah Laut, South Kalimantan as the source of (amorphous) silica and a magnesium oxide (MgO) powder. They were thoroughly mixed and milled prior to calcination. The addition of 1, 2, 3, and 4 wt% B2O3 to the calcined powder was done before uniaxial pressing and then sintering at 950 °C for 4 h. The phase composition and forsterite crystallite size, the microstructure and the dielectric constant of the sintered samples were characterized using X-ray diffractometer (XRD), Scanning Electron Microscope (SEM) and Vector Network Analyzer (VNA), respectively. Results showed that all samples contained forsterite, periclase (MgO) and proto enstatite (MgSiO3) with different weight fractions and forsterite crystallite size. In general, the weight fraction and crystallite size of forsterite increased with increasing B2O3 addition. The weight fraction and crystallite size of forsterite in the 4%-added sample reached 99% wt and 164 nm. Furthermore, the SEM images showed that the average grain size became slightly larger and the ceramics also became slightly denser as more B2O3 was added. The results are in accordance with density measurements using the Archimedes method which showed that the 4% ceramic exhibited 1.845 g/cm3 apparent density, while the 1% ceramic 1.681 g/cm3. We also found that the higher the density, the higher the average dielectric constant, i.e. it was 4.6 for the 1%-added sample and 6.4 for the 4%-added sample.
Preparation and characterization of new photoluminescent nano-powder based on Eu3+:La2Ti2O7 and dispersed into silica matrix for latent fingerprint detection

NASA Astrophysics Data System (ADS)

Saif, M.; Alsayed, N.; Mbarek, A.; El-Kemary, M.; Abdel-Mottaleb, M. S. A.

2016-12-01

Pure lanthanum titanate doped with europium metal ions (La2Ti2O7:Eu3+) and dispersed in silica matrix phosphor powder was prepared by sol-gel process followed by thermal treatment. The prepared nanophosphors were characterized by powder X-ray Diffraction (XRD), Fourier Transform Infrared (FT-IR), Transmission Electron Microscope (TEM), Energy Dispersive Spectroscopy (EDX), and Photoluminescence Spectroscopy (PL). The effects of silica, thermal treatment, Eu3+ ion, and surfactant (CTAB) concentrations on the crystal, morphology, and photoluminescence properties were investigated. The present work found that dispersion of La2Ti2O7:Eu3+ into silica matrix significantly altered the morphology of La2Ti2O7:Eu3+ from high crystalline micro-plate like shape into amorphous aggregated Nano-spherical shape. The high separated spherical shape with intense red PL emission and long lifetime was obtained from 10 mol% Eu3+:La2Ti2O7:Eu3+, dispersed into silica matrix, and prepared in the presence of CTAB. The high PL Nano-phosphor has been successfully used in developing latent fingerprint from various forensic relevant materials.

A hydrogen leak-tight, transparent cryogenic sample container for ultracold-neutron transmission measurements

NASA Astrophysics Data System (ADS)

Döge, Stefan; Hingerl, Jürgen

2018-03-01

The improvement of the number of extractable ultracold neutrons (UCNs) from converters based on solid deuterium (sD2) crystals requires a good understanding of the UCN transport and how the crystal's morphology influences its transparency to the UCNs. Measurements of the UCN transmission through cryogenic liquids and solids of interest, such as hydrogen (H2) and deuterium (D2), require sample containers with thin, highly polished and optically transparent windows and a well defined sample thickness. One of the most difficult sealing problems is that of light gases like hydrogen and helium at low temperatures against high vacuum. Here we report on the design of a sample container with two 1 mm thin amorphous silica windows cold-welded to aluminum clamps using indium wire gaskets, in order to form a simple, reusable, and hydrogen-tight cryogenic seal. The container meets the above-mentioned requirements and withstands up to 2 bar hydrogen gas pressure against isolation vacuum in the range of 10-5 to 10-7 mbar at temperatures down to 4.5 K. Additionally, photographs of the crystallization process are shown and discussed.
In Situ Observation of High-Pressure Phase Transitions in SiO2 Under Shock Loading Using Time Resolved X-Ray Diffraction

NASA Astrophysics Data System (ADS)

Tracy, S. J.; Turneaure, S.; Duffy, T. S.

2016-12-01

Quartz is one of the most abundant minerals in Earth's crust and serves as an archetype for silicate minerals generally. The shock metamorphism of silica is important for understanding and interpreting meteorite impact events. Shock compression of quartz is characterized by a phase transition occurring over a broad mixed-phase region ( 10-40 GPa). Despite decades of study, the nature of this transformation and the structure of the high-pressure phase remain poorly understood. In situ x-ray diffraction data on shock-compressed SiO2 was collected at the Dynamic Compression Sector at the Advanced Photon Source. The behavior both single crystal alpha-quartz and fused silica was investigated under dynamic loading through a series real-time synchrotron x-ray diffraction measurements during peak stresses up to 65 GPa. A two-stage light gas gun was used to accelerate LiF flyer plates that impacted the SiO2 samples resulting in a propagating step-like increase in pressure and temperature behind the shock front. Four consecutive x-ray frames, separated by 153 ns, were collected during the transient loading and unloading. These measurements allow for the determination of time-dependent atomic arrangements, demonstrating that both amorphous silica as well as crystalline alpha-quartz transform to stishovite above 36 GPa. These measurements reveal important information about the role of kinetics as well texture development and potential defect structures in the transformed material.
Hydrothermal alteration maps of the central and southern Basin and Range province of the United States compiled from Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) data

USGS Publications Warehouse

Mars, John L.

2013-01-01

Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) data and Interactive Data Language (IDL) logical operator algorithms were used to map hydrothermally altered rocks in the central and southern parts of the Basin and Range province of the United States. The hydrothermally altered rocks mapped in this study include (1) hydrothermal silica-rich rocks (hydrous quartz, chalcedony, opal, and amorphous silica), (2) propylitic rocks (calcite-dolomite and epidote-chlorite mapped as separate mineral groups), (3) argillic rocks (alunite-pyrophyllite-kaolinite), and (4) phyllic rocks (sericite-muscovite). A series of hydrothermal alteration maps, which identify the potential locations of hydrothermal silica-rich, propylitic, argillic, and phyllic rocks on Landsat Thematic Mapper (TM) band 7 orthorectified images, and geographic information systems shape files of hydrothermal alteration units are provided in this study.
Effectiveness of silica based sol-gel microencapsulation method for odorants and flavors leading to sustainable environment

PubMed Central

Ashraf, Muhammad Aqeel; Khan, Aysha Masood; Ahmad, Mushtaq; Sarfraz, Maliha

2015-01-01

Microencapsulation has become a hot topic in chemical research. Technology mainly used for control release and protection purposes. The sol-gel micro encapsulation approach for fragrance and aroma in porous silica-based materials leads to sustainable odorant and flavored materials with novel and unique beneficial properties. Sol-gel encapsulation of silica based micro particles considered economically cheap as capital investment in manufacturing is very low and environmentally friendly. Amorphous sol-gel SiO2 is non-toxic and safe, whereas the sol-gel entrapment of delicate chemicals in its inner pores results in pronounced chemical and physical stabilization of the entrapped active agents, thereby broadening the practical utilization of chemically unstable essential oils (EOs). Reviewing progress in the fabrication of diverse odorant and flavored sol-gels, shows us how different synthetic strategies are appropriate for practical application with important health and environmental benefits. PMID:26322304
Effectiveness of silica based sol-gel microencapsulation method for odorants and flavors leading to sustainable environment.

PubMed

Ashraf, Muhammad Aqeel; Khan, Aysha Masood; Ahmad, Mushtaq; Sarfraz, Maliha

2015-01-01

Microencapsulation has become a hot topic in chemical research. Technology mainly used for control release and protection purposes. The sol-gel micro encapsulation approach for fragrance and aroma in porous silica-based materials leads to sustainable odorant and flavored materials with novel and unique beneficial properties. Sol-gel encapsulation of silica based micro particles considered economically cheap as capital investment in manufacturing is very low and environmentally friendly. Amorphous sol-gel SiO2 is non-toxic and safe, whereas the sol-gel entrapment of delicate chemicals in its inner pores results in pronounced chemical and physical stabilization of the entrapped active agents, thereby broadening the practical utilization of chemically unstable essential oils (EOs). Reviewing progress in the fabrication of diverse odorant and flavored sol-gels, shows us how different synthetic strategies are appropriate for practical application with important health and environmental benefits.
Centrifugation-assisted Assembly of Colloidal Silica into Crack-Free and Transferrable Films with Tunable Crystalline Structures

PubMed Central

Fan, Wen; Chen, Min; Yang, Shu; Wu, Limin

2015-01-01

Self-assembly of colloidal particles into colloidal films has many actual and potential applications. While various strategies have been developed to direct the assembly of colloidal particles, fabrication of crack-free and transferrable colloidal film with controllable crystal structures still remains a major challenge. Here we show a centrifugation-assisted assembly of colloidal silica spheres into free-standing colloidal film by using the liquid/liquid interfaces of three immiscible phases. Through independent control of centrifugal force and interparticle electrostatic repulsion, polycrystalline, single-crystalline and quasi-amorphous structures can be readily obtained. More importantly, by dehydration of silica particles during centrifugation, the spontaneous formation of capillary water bridges between particles enables the binding and pre-shrinkage of the assembled array at the fluid interface. Thus the assembled colloidal films are not only crack-free, but also robust and flexible enough to be easily transferred on various planar and curved substrates. PMID:26159121
Age hardening of 6061/alumina-silica fiber composite

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

Khangaonkar, P.R.; Shamsul, J.B.; Azmi, R.

1994-12-31

Continuous alumina-silica fiber (Altex of Sumitomo) which yields high performance composites with some aluminium alloys was tried for squeeze cast 6061 based composites with volume fractions of 0.5 and 0.32, and the matrix microhardness and resistivity changes during age hardening were studied. The matrix in the composites hardened much more than the unreinforced alloy. Microhardness increases of up to 70 VPN above the solution treated condition at various aging temperatures were observed. The resistivity variation indicated an appreciable state of internal stress which continued to persist even when hardness fell by overaging. Energy dispersive X-ray analysis indicated that the regionsmore » close to the fibers had a higher silicon content than the matrix, and amorphous silica in the fiber may have a role in the formation of an enriched layer which may help the bonding and strength in the composite.« less
Repetitive Dosing of Fumed Silica Leads to Profibrogenic Effects through Unique Structure–Activity Relationships and Biopersistence in the Lung

DOE PAGES

Sun, Bingbing; Wang, Xiang; Liao, Yu-Pei; ...

2016-08-02

Contrary to the notion that the use of fumed silica in consumer products can “generally (be) regarded as safe” (GRAS), the high surface reactivity of pyrogenic silica differs from other forms of synthetic amorphous silica (SAS), including the capacity to induce membrane damage and acute proinflammatory changes in the murine lung. Additionally, the chain-like structure and reactive surface silanols also allow fumed silica to activate the NLRP3 inflammasome, leading to IL-1β production. This pathway is known to be associated with subchronic inflammation and profibrogenic effects in the lung by α-quartz and carbon nanotubes. Different from the latter materials, bolus dosemore » instillation of 21 mg/kg fumed silica did not induce sustained IL-1β production or subchronic pulmonary effects. In contrast, the NLRP3 inflammasome pathway was continuously activated by repetitive-dose administration of 3 × 7 mg/kg fumed silica, 1 week apart. We also found that while single-dose exposure failed to induce profibrotic effects in the lung, repetitive dosing can trigger increased collagen production, even at 3 × 3 mg/kg. The change between bolus and repetitive dosing was due to a change in lung clearance, with recurrent dosing leading to fumed silica biopersistence, sustained macrophage recruitment, and activation of the NLRP3 pathway. These subchronic proinflammatory effects disappeared when less surface-reactive titanium-doped fumed silica was used for recurrent administration. Finally, these data indicate that while fumed silica may be regarded as safe for some applications, we should reconsider the GRAS label during repetitive or chronic inhalation exposure conditions.« less
Tracing the beginning of crystallization of amorphous forsterite thin films using AFM and IR spectroscopy

NASA Astrophysics Data System (ADS)

Oehm, B.; Burchard, M.; Lattard, D.; Dohmen, R.; Chakraborty, S.

2009-12-01

Observations of accretion disks of Young Stellar Objects revealed dust of crystalline Mg-silicates, in particular of forsterite, which is assumed to result from high temperature annealing of amorphous cosmic dust particles. We are performing annealing experiments to obtain kinetic parameters of the crystallization that are necessary for the numerical modeling of accretion disks. We use thin films obtained by Pulsed Laser Deposition (PLD) on Si (111) wafers. The thin films are completely amorphous, chemically homogeneous (on the Mg2SiO4 composition) and with a continuous and flat surface. They are annealed for 1 to 260 h at 1073K in a vertical furnace and drop-quenched. To monitor the progress of crystallization, the samples are characterized by AFM and SEM imaging and IR spectroscopy. After 2.5 h of annealing AFM images reveal elliptical features, below 1 µm in diameter, with a central elevation and surrounded by a lowering of the surface which indicate material transport within the elliptical domains. These elliptical features most probably represent early nucleation sites in an amorphous matrix. The IR spectra still show the broad bands of Si-O stretching modes typical of amorphous silica without clear evidence for crystalline forsterite. After 6 h of annealing, AFM and SEM images show circular and square features both with a central elevation in the range of 80 to 120 nm. IR spectra show a few weak bands that can be assigned to crystalline forsterite (bending and stretching of tetrahedra). After 10 h of annealing planar faces appear in the former pyramidal features and the surrounding matrix evolves into domains with spherolitic appearance. IR spectra of these samples display typical bands of crystalline forsterite. With increasing annealing time AFM images picture the further growth of the planar faces towards idiomorphic crystals. SEM imaging shows surface roughening with increasing annealing time. The quantitative evaluation of the surface roughness of AFM images point to three evolutionary stages during annealing. The quantitative evaluation of IR spectra reveals that the forsterite bands continuously grow with increasing annealing time up to 64 h but that no significant change appears for longer run durations. AFM imaging proves to be a powerful tool to detect the very first signs of crystallization and to trace its further evolution.
Novel nanometer-level uniform amorphous carbon coating for boron powders by direct pyrolysis of coronene without solvent.

PubMed

Ye, ShuJun; Song, MingHui; Kumakura, Hiroaki

2015-01-30

A 3 nm coronene coating and a 4 nm amorphous carbon coating with a uniform shell-core encapsulation structure for nanosized boron (B) powders are formed by a simple process in which coronene is directly mixed with boron particles without a solvent and heated at 520 °C for 1 h or at 630 °C for 3 h in a vacuum-sealed silica tube. Coronene has a melting point lower than its decomposition temperature, which enables liquid coronene to cover B particles by liquid diffusion and penetration without the need for a solvent. The diffusion and penetration of coronene can extend to the boundaries of particles and to inside the agglomerated nanoparticles to form a complete shell-core encapsulated structure. As the temperature is increased, thermal decomposition of coronene on the B particles results in the formation of a uniform amorphous carbon coating layer. This novel and simple nanometer-level uniform amorphous carbon coating method can possibly be applied to many other powders; thus, it has potential applications in many fields at low cost.
Nanostructured Materials

DTIC Science & Technology

2012-08-30

improve oxidation resistance due to a rapidly forming ceramic-like, passivating and self - healing silica layer when exposed to high incident fluxes...have stronger bond dissociation energies (-8.3 eV). The POSS cage is not destroyed by the AO, but forms a passivating self -rigidizing/ self - healing ...polymers (including amorphous, semi-crystalline, crystalline, and rubber , etc.) possess con- siderable amounts of internal and external free volume
Whispering gallery modes in a spherical microcavity with a photoluminescent shell

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

Grudinkin, S. A., E-mail: grudink@gvg.ioffe.ru; Dontsov, A. A.; Feoktistov, N. A.

2015-10-15

Whispering-gallery mode spectra in optical microcavities based on spherical silica particles coated with a thin photoluminescent shell of hydrogenated amorphous silicon carbide are studied. The spectral positions of the whispering-gallery modes for spherical microcavities with a shell are calculated. The dependence of the spectral distance between the TE and TM modes on the shell thickness is examined.
The effects of size and surface modification of amorphous silica particles on biodistribution and liver metabolism in mice

NASA Astrophysics Data System (ADS)

Lu, Xiaoyan; Ji, Cai; Jin, Tingting; Fan, Xiaohui

2015-05-01

Engineered nanoparticles, with unconventional properties, are promising platforms for biomedical applications. Since they may interact with a wide variety of biomolecules, it is critical to understand the impact of the physicochemical properties of engineered nanoparticles on biological systems. In this study, the effects of particle size and surface modification alone or in combination of amorphous silica particles (SPs) on biological responses were determined using a suite of general toxicological assessments and metabonomics analysis in mice model. Our results suggested that amino or carboxyl surface modification mitigated the liver toxicity of plain-surface SPs. 30 nm SPs with amino surface modification were found to be the most toxic SPs among all the surface-modified SP treatments at the same dosage. When treatment dose was increased, submicro-sized SPs with amino or carboxyl surface modification also induced liver toxicity. Biodistribution studies suggested that 70 nm SPs were mainly accumulated in liver and spleen regardless of surface modifications. Interestingly, these two organs exhibited different uptake trends. Furthermore, metabonomics studies indicated that surface modification plays a more dominant role to affect the liver metabolism than particle size.
Advanced treatment technique for swine wastewater using two agents: Thermally polymerized amorphous silica and hydrated lime for color and phosphorus removal and sulfur for nitrogen removal.

PubMed

Hasegawa, Teruaki; Kurose, Yohei; Tanaka, Yasuo

2017-10-01

The efficacy of advanced treatment of swine wastewater using thermally polymerized, modified amorphous silica and hydrated lime (M-CSH-lime) for color and phosphorus removal and sulfur for nitrogen removal was examined with a demonstration-scale treatment plant. The color removal rate was approximately 78% at M-CSH-lime addition rates of > 0.055 wt/v%. The PO43--P removal rate exceeded 99.9% with > 0.023 wt/v%. pH of the effluent from the M-CSH-lime reactor increased with the addition rate till a maximum value of 12.7, which was effective in disinfection. The recovered M-CSH-lime would be suitable as a phosphorus fertilizer because the total P 2 O 5 content was approximately 10%. The nitrogen oxide (NOx-N) removal rate by sulfur denitrification increased to approximately 80% when the NOx-N loading rate was around 0.1 kg-N/ton-S/day. It was suggested that the combination of the two processes would be effective in the advanced treatment of swine wastewater. © 2017 Japanese Society of Animal Science.
Single-crystal silicon optical fiber by direct laser crystallization

DOE PAGES

Ji, Xiaoyu; Lei, Shiming; Yu, Shih -Ying; ...

2016-12-05

Semiconductor core optical fibers with a silica cladding are of great interest in nonlinear photonics and optoelectronics applications. Laser crystallization has been recently demonstrated for crystallizing amorphous silicon fibers into crystalline form. Here we explore the underlying mechanism by which long single-crystal silicon fibers, which are novel platforms for silicon photonics, can be achieved by this process. Using finite element modeling, we construct a laser processing diagram that reveals a parameter space within which single crystals can be grown. Utilizing this diagram, we illustrate the creation of single-crystal silicon core fibers by laser crystallizing amorphous silicon deposited inside silica capillarymore » fibers by high-pressure chemical vapor deposition. The single-crystal fibers, up to 5.1 mm long, have a very welldefined core/cladding interface and a chemically pure silicon core that leads to very low optical losses down to ~0.47-1dB/cm at the standard telecommunication wavelength (1550 nm). Furthermore, tt also exhibits a photosensitivity that is comparable to bulk silicon. Creating such laser processing diagrams can provide a general framework for developing single-crystal fibers in other materials of technological importance.« less
Silica Precipitation and Scaling in Dynamic Geothermal Systems

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

Bohlmann, E.G.; Shor, A.J.; Berlinski, P.

1976-01-01

The authors are modifying an existing 100 gpm titanium loop to provide a facility for studying the formation of silica precipitates, their properties and fates, principally as a function of brine composition, temperature, and flow conditions. This loop demonstrated excellent serviceability over a period of years in saline water corrosion studies (to 275 C and 2 M NaCl), with and without pollutant additives such as H{sub 2}S, NH{sub 3}, and SO{sub 2}, and should be equally useful in this application. Simulated silica saturated geothermal waters are prepared by circulating part of the loop flow ({approx} 1 gpm) through a bypassmore » column filled with amorphous silica powder. Exploratory studies in a Once-Through Development System indicated that porous Vycor (Cornin-Glass Code No.7930, 97% SiO{sub 2}, 3% B{sub 2}O{sub 3}) was a suitable material for loading the column. A recent run at {approx} 220 C confirmed this: the system approached equilibrium in agreement with calculation and with the anticipated 15 psi pressure drop through an 18 in. deep bed of 140-200 mesh Vycor powder.« less
Cathodoluminescence of SiOx under-stoichiometric silica layers

NASA Astrophysics Data System (ADS)

Salh, Roushdey; von Czarnowski, A.; Zamoryanskaya, M. V.; Kolesnikova, E. V.; Fitting, H.-J.

2006-06-01

Under-stoichiometric thin silica layers SiOx with different stoichiometric degree 1 x 2, were prepared by thermal evaporation of silicon monoxide in vacuum and in ambient oxygen atmosphere of various pressure onto crystalline silicon substrates. The chemical composition has been determined by Fourier transform infrared spectroscopy (FTIR). A special formula is derived to correlate the stoichiometric degree x with the wavenumber of the main TO stretching mode (Si-O-Si) in silica, finally to determine the actual composition values x of the layers. Cathodoluminescence (CL) of these layers shows the development of typical amorphous SiO2 luminescence bands at the composition threshold x > 1.5 and then onwards to x = 2. These luminescence bands were observed at 4.3, 2.7, 2.15, and 1.9 eV. The green-yellow luminescence (2.15 eV) is strongly increasing with the annealing temperature up to 1300 °C and is assigned to phase separation of SiOx into Si and SiO2 and formation of hexamer silicon rings in the understoichiometric silica network. Finally we observe Si nanoclusters by means of transmission elec- tron microscopy (TEM) micrographs.
Effects of alteration product precipitation on glass dissolution

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

Strachan, Denis M.; Neeway, James J.

2014-06-01

Understanding the mechanisms that control the durability of nuclear waste glass is paramount if reliable models are to be constructed so that the glass dissolution rate in a given geological repository can be calculated. Presently, it is agreed that (boro)silicate glasses dissolve in water at a rate dependent on the solution concentration of orthosilicic acid (H 4SiO 4) with higher [H 4SiO 4] leading to lower dissolution rates. Once the reaction has slowed as a result of the buildup of H 4SiO 4, another increase in the rate has been observed that corresponds to the precipitation of certain silica-bearing alterationmore » products. However, it has also been observed that the concentration of silica-bearing solution species does not significantly decrease, indicating saturation, while other glass tracer elements concentrations continue to increase, indicating that the glass is still dissolving. In this study, we have used the Geochemist’s Workbench code to investigate the relationship between glass dissolution rates and the precipitation rate of a representative zeolitic silica-bearing alteration product, analcime [Na(AlSi 2O 6)∙H 2O]. To simplify the calculations, we suppressed all alteration products except analcime, gibbsite (Al(OH) 3), and amorphous silica. The pseudo-equilibrium-constant matrix for amorphous silica was substituted for the glass pseudo-equilibrium-constant matrix because it has been shown that silicate glasses act as a silica-only solid with respect to kinetic considerations. In this article, we present the results of our calculations of the glass dissolution rate at different values for the analcime precipitation rate constant and the effects of varying the glass dissolution rate constant at a constant analcime precipitation rate constant. From the simulations we conclude, firstly, that the rate of glass dissolution is dependent on the kinetics of formation of the zeolitic phase. Therefore, the kinetics of secondary phase formation is an important parameter that should be taken into account in future glass dissolution modeling efforts. Secondly, the results indicate that, in the absence of a gel layer, the glass dissolution rate controls the rate of analcime precipitation in the long term. Finally, the meaning of these results pertinent to long-term glass durability is discussed.« less
Effect of interparticle interactions on size determination of zirconia and silica based systems – A comparison of SAXS, DLS, BET, XRD and TEM

PubMed Central

Pabisch, Silvia; Feichtenschlager, Bernhard; Kickelbick, Guido; Peterlik, Herwig

2012-01-01

The aim of this work is a systematic comparison of size characterisation methods for two completely different model systems of oxide nanoparticles, i.e. amorphous spherical silica and anisotropic facet-shaped crystalline zirconia. Size and/or size distribution were determined in a wide range from 5 to 70 nm using small-angle X-ray scattering (SAXS), dynamic light scattering (DLS), nitrogen sorption (BET), X-ray diffraction (XRD) and transmission electron microscopy (TEM). A nearly perfect coincidence was observed only for SAXS and TEM for both types of particles. For zirconia nanoparticles considerable differences between different measurement methods were observed. PMID:22347721
Structure and optical properties of silica-supported Ag-Au nanoparticles.

PubMed

Barreca, Davide; Gasparotto, Alberto; Maragno, Cinzia; Tondello, Eugenio; Gialanella, Stefano

2007-07-01

Bimetallic Ag-Au nanoparticles are synthesized by sequential deposition of Au and Ag on amorphous silica by Radio Frequency (RF)-sputtering under mild conditions. Specimens are thoroughly characterized by a multi-technique approach, aimed at investigating the system properties as a function of the Ag/Au content, as well as the evolution induced by ex-situ annealing under inert (N2) or reducing (4% H2/N2) atmospheres. The obtained results demonstrate the possibility to obtain Ag-Au alloyed nanoparticles with controllable size, shape, structure, and dispersion under mild conditions, so that the optical properties can be finely tuned as a function of the synthesis and thermal treatment conditions.

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

Azmi, M. A.; Ismail, N. A. A.; Rizamarhaiza, M.

Rice husk was thermally decomposed to yield powder composed of silica (SiO{sub 2}). Temperatures of 700°C and 1000°C were chosen as the decomposition temperatures. X-Ray Diffraction (XRD), X-Ray Florescence (XRF), Fourier Transform Infrared (FTIR), and Field Emission Scanning Electron Microscope (FESEM) analyses were conducted on a synthetic silica powder (SS-SiO{sub 2}) and the rice husk ash as for the comparative characterisation study. XRD analyses clearly indicated that the decomposed rice husk yielded silica of different nature which are Crystalline Rice Husk Silica (C-RHSiO{sub 2}) and Amorphous Rice Husk Silica (A-RHSiO{sub 2}). Moreover, it was found that SS-SiO{sub 2} was ofmore » Quartz phase, C-RHSiO{sub 2} was of Trydimite and Cristobalite. Through XRF detection, the highest SiO{sub 2} purity was detected in SS-SiO{sub 2} followed by C-RHSiO{sub 2} and A-RHSiO{sub 2} with purity percentages of 99.60%, 82.30% and 86.30% respectively. FTIR results clearly indicated silica (SiO{sub 2}) bonding 1056, 1064, 1047, 777, 790 and 798 cm{sup −1}) increased as the crystallinity silica increased. The Cristobalite phase was detected in C-RH SiO{sub 2} at the wavelength of 620 cm{sup −1}. Morphological features as observed by FESEM analyses confirmed that, SS-SiO{sub 2} and C-RH SiO{sub 2} showed prominent coarse granular morphology.« less
Influence of polyols on the formation of nanocrystalline nickel ferrite inside silica matrices

NASA Astrophysics Data System (ADS)

Stoia, Marcela; Barvinschi, Paul; Barbu-Tudoran, Lucian; Bunoiu, Mădălin

2017-01-01

We have synthesized nickel ferrite/silica nanocomposites, using a modified sol-gel method that combines the sol-gel processing with the thermal decomposition of metal-organic precursors, leading to a homogenous dispersion of ferrite nanoparticles within the silica matrix and a narrow size distribution. We used as starting materials tetraethyl orthosilicate (TEOS) as source of silica, Fe(III) and Ni(II) nitrates as sources of metal cations, and polyols as reducing agent (polyvinyl alcohol, 1,4-butanediol and their mixture). TG/DTA coupled technique evidenced the redox interaction between the polyol and the mixture of metal nitrates during the heating of the gel, with formation of nickel ferrite precursors in the pores of the silica-gels. FT-IR spectroscopy confirmed the formation of metal carboxylates inside the silica-gels and the interaction of the polyols with the Si-OH groups of the polysiloxane network. X-ray diffractometry evidenced that in case of nanocomposites obtained by using a single polyol, nickel ferrite forms as single crystalline phase inside the amorphous silica matrix, while in case of using a mixture of polyols the nickel oxide appears as a secondary phase. TEM microscopy and elemental mapping evidenced the fine nature of the obtained nickel ferrite nanoparticles that are homogenously dispersed within the silica matrix. The obtained nanocomposites exhibit magnetic behavior very close to superparamagnetism slightly depending on the presence and nature of the organic compounds used in synthesis; the magnetization reached at 5 kOe magnetic field was 7 emu/g for all composites.
Plasma-Functionalized Polytetrafluoroethylene Nanoparticles for Improved Wear in Lubricated Contact

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

Sharma, Vinay; Timmons, Richard; Erdemir, Ali

Plasma-functionalized polytetrafluoroethylene (PTFE) nanoparticles were employed to evaluate their utility in improving the lubrication property of a group III mineral oil with a significantly low amount of zinc dialkyl dithiophosphate (ZDDP). The particles were coated with two consecutive films; the initial coating contained silica to enhance amorphous glassy tribofilm formation, followed by a methacrylate film to protect the silica coating and enhance dispersibility in the oil. The functionalized nanoparticles were evaluated for their tribological performance using a high-frequency reciprocating rig, in a cylinder-on-flat configuration. The oil formulations containing ZDDP (350 ppm phosphorus level) and the functionalized nanoparticles resulted in dramaticmore » reductions in the friction coefficient and overall wear compared to the samples containing nonfunctionalized PTFE nanoparticles, ZDDP (350 ppm P), and samples devoid of nanoparticles but containing ZDDP with a 700 ppm P treat rate. XPS and XANES spectroscopy were employed to characterize the tribological films formed on the test samples. The samples with functionalized particles and ZDDP clearly exhibited tribofilms with Si- and F-doped polyphosphates of Zn coupled with the presence of ZnS at the metal-tribofilm interface. On the other hand, oils without the functionalized nanoparticles have oxides of Fe and to a lesser extent short-chain phosphates of Zn. The overall results suggest that the synergism between plasma-coated PTFE nanoparticles and ZDDP contributed to the development of protective tribofilms even at reduced amount of phosphorus in the oil. This new method of employing nanoparticles to deliver novel antifriction and antiwear chemistries at the tribological interfaces stands out as a promising approach to further reduce P levels in oils without compromising friction and wear performance.« less
Neutral vs zwitterionic glycine forms at the water/silica interface: structure, energies, and vibrational features from B3LYP periodic simulations.

PubMed

Rimola, Albert; Civalleri, Bartolomeo; Ugliengo, Piero

2008-12-16

B3LYP periodic calculations with a triple-xi-polarized Gaussian basis set have been used to study adsorption of glycine on a hydroxylated silica surface (2.2 OH/nm2) model derived from the (001) surface of edingtonite. The simulation envisages glycine adsorbed either as a gas-phase molecule or when microsolvated by up to five H20 molecules. Both neutral and zwitterionic forms of glycine have been considered and their structural, energetic, and spectroscopic vibrational features compared internally and with experiments. As a gas phase glycine sticks in its neutral form at the silica surface, the zwitterion being highly unstable and with transition-state character. When glycine is microsolvated at the silica interface, two H20 molecules render the zwitterion population comparable to that of the neutral form whereas with four H2O molecules the neutral glycine population is wiped out in favor of the zwitterion. With four H20 molecules the most stable structure shows no direct contact between glycine and the silica surface, H20 acting as a mediator via H-bond interactions. The B3LYP energies and structural data were also supported by comparing the scaled harmonic vibrational features with literature FTIR data of glycine adsorbed on an amorphous silica surface either from the gas phase or in water solution.
Organic-Silica Interactions in Saline: Elucidating the Structural Influence of Calcium in Low-Salinity Enhanced Oil Recovery.

PubMed

Desmond, J L; Juhl, K; Hassenkam, T; Stipp, S L S; Walsh, T R; Rodger, P M

2017-09-08

Enhanced oil recovery using low-salinity solutions to sweep sandstone reservoirs is a widely-practiced strategy. The mechanisms governing this remain unresolved. Here, we elucidate the role of Ca 2+ by combining chemical force microscopy (CFM) and molecular dynamics (MD) simulations. We probe the influence of electrolyte composition and concentration on the adsorption of a representative molecule, positively-charged alkylammonium, at the aqueous electrolyte/silica interface, for four electrolytes: NaCl, KCl, MgCl 2 , and CaCl 2 . CFM reveals stronger adhesion on silica in CaCl 2 compared with the other electrolytes, and shows a concentration-dependent adhesion not observed for the other electrolytes. Using MD simulations, we model the electrolytes at a negatively-charged amorphous silica substrate and predict the adsorption of methylammonium. Our simulations reveal four classes of surface adsorption site, where the prevalence of these sites depends only on CaCl 2 concentration. The sites relevant to strong adhesion feature the O - silica site and Ca 2+ in the presence of associated Cl - , which gain prevalence at higher CaCl 2 concentration. Our simulations also predict the adhesion force profile to be distinct for CaCl 2 compared with the other electrolytes. Together, these analyses explain our experimental data. Our findings indicate in general how silica wettability may be manipulated by electrolyte concentration.
Photovoltaic's silica-rich waste sludge as supplementary cementitious material (SCM)

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

Quercia, G., E-mail: g.quercia@tue.nl; Eindhoven University of Technology, Department of the Built Environment, P.O. Box 513, 5600 MB Eindhoven; Putten, J.J.G. van der

2013-12-15

Waste sludge, a solid recovered from wastewater of photovoltaic-industries, composes of agglomerates of nano-particles like SiO{sub 2} and CaCO{sub 3}. This sludge deflocculates in aqueous solutions into nano-particles smaller than 1 μm. Thus, this sludge constitutes a potentially hazardous waste when it is improperly disposed. Due to its high content of amorphous SiO{sub 2}, this sludge has a potential use as supplementary cementitious material (SCM) in concrete. In this study the main properties of three different samples of photovoltaic's silica-rich waste sludge (nSS) were physically and chemically characterized. The characterization techniques included: scanning electron microscopy (SEM), X-ray energy dispersive spectroscopymore » (EDS), X-ray diffraction (XRD), nitrogen physical adsorption isotherm (BET method), density by Helium pycnometry, particle size distribution determined by laser light scattering (LLS) and zeta-potential measurements by dynamic light scattering (DLS). In addition, a dispersability study was performed to design stable slurries to be used as liquid additives for the concrete production on site. The effects on the hydration kinetics of cement pastes by the incorporation of nSS in the designed slurries were determined using an isothermal calorimeter. A compressive strength test of standard mortars with 7% of cement replacement was performed to determine the pozzolanic activity of the waste nano-silica sludge. Finally, the hardened system was fully characterized to determine the phase composition. The results demonstrate that the nSS can be utilized as SCM to replace portion of cement in mortars, thereby decreasing the CO{sub 2} footprint and the environmental impact of concrete. -- Highlights: •Three different samples of PV nano-silica sludge (nSS) were fully characterized. •nSS is composed of agglomerates of nano-particles like SiO{sub 2} and CaCO{sub 3}. •Dispersability studies demonstrated that nSS agglomerates are broken to nano-size. •nSS can be classified as a pozzolanic material with activity index higher than 100. •nSS can be use as a potential SCM to partly replace cement in concrete.« less
A silica-supported solid dispersion of bifendate using supercritical carbon dioxide method with enhanced dissolution rate and oral bioavailability.

PubMed

Cai, Cuifang; Liu, Muhua; Li, Yun; Guo, Bei; Chang, Hui; Zhang, Xiangrong; Yang, Xiaoxu; Zhang, Tianhong

2016-01-01

In this study, to enhance the dissolution rate and oral bioavailability of bifendate, a silica-supported solid dispersion (SD) of bifendate was prepared using supercritical carbon dioxide (ScCO2) technology. The properties of bifendate-silica SD were characterized by differential scanning calorimetry (DSC), X-ray diffraction (X-RD) and scanning electron microscopy. The pharmacokinetic study was carried out in beagle dogs using commercial bifendate dropping pills as a reference which is a conventional SD formulation of bifendate and PEG6000. A novel method of Ultra Performance Convergence Chromatography-tandem mass spectrometry (UPC(2)™-MS/MS) method was applied to determine bifendate concentration in plasma. The amorphous state of bifendate in bifendate-silica SD was revealed in X-RD and DSC when the ratios of bifendate and silica were 1:15 and 1:19, respectively. In vitro dissolution rate was significantly improved with cumulative release of 67% within 20 min relative to 8% for the physical mixture of bifendate and silica, and which was also higher than the commercial dropping pill of 52%. After storage at 75% relative humidity (RH) for 10 d, no recrystallization was found and reduced dissolution rate was obtained due to the absorption of moisture. In pharmacokinetic study, Cmax and AUC0-t for bifendate-silica SD were 153.1 ng/ml and 979.8 ng h/ml, respectively. AUC0-t of bifendate-silica SDs was ∼1.6-fold higher than that of the commercial dropping pills. These results suggest that adsorbing bifendate onto porous silica via ScCO2 technique could be a feasible method to enhance oral bioavailability together with a higher dissolution rate.
Silica coating influences the corona and biokinetics of cerium oxide nanoparticles.

PubMed

Konduru, Nagarjun V; Jimenez, Renato J; Swami, Archana; Friend, Sherri; Castranova, Vincent; Demokritou, Philip; Brain, Joseph D; Molina, Ramon M

2015-10-12

The physicochemical properties of nanoparticles (NPs) influence their biological outcomes. We assessed the effects of an amorphous silica coating on the pharmacokinetics and pulmonary effects of CeO2 NPs following intratracheal (IT) instillation, gavage and intravenous injection in rats. Uncoated and silica-coated CeO2 NPs were generated by flame spray pyrolysis and later neutron-activated. These radioactive NPs were IT-instilled, gavaged, or intravenously (IV) injected in rats. Animals were analyzed over 28 days post-IT, 7 days post-gavage and 2 days post-injection. Our data indicate that silica coating caused more but transient lung inflammation compared to uncoated CeO2. The transient inflammation of silica-coated CeO2 was accompanied by its enhanced clearance. Then, from 7 to 28 days, clearance was similar although significantly more (141)Ce from silica-coated (35%) was cleared than from uncoated (19%) (141)CeO2 in 28 days. The protein coronas of the two NPs were significantly different when they were incubated with alveolar lining fluid. Despite more rapid clearance from the lungs, the extrapulmonary (141)Ce from silica-coated (141)CeO2 was still minimal (<1%) although lower than from uncoated (141)CeO2 NPs. Post-gavage, nearly 100% of both NPs were excreted in the feces consistent with very low gut absorption. Both IV-injected (141)CeO2 NP types were primarily retained in the liver and spleen. The silica coating significantly altered the plasma protein corona composition and enhanced retention of (141)Ce in other organs except the liver. We conclude that silica coating of nanoceria alters the biodistribution of cerium likely due to modifications in protein corona formation after IT and IV administration.
Optical response of thin amorphous films to infrared radiation

NASA Astrophysics Data System (ADS)

Orosco, J.; Coimbra, C. F. M.

2018-03-01

We briefly review the electrical-optical response of materials to radiative forcing within the formalism of the Kramers-Kronig relations. A commensurate set of criteria is described that must be met by any frequency-domain model representing the time-domain response of a real (i.e., physically possible) material. The criteria are applied to the Brendel-Bormann (BB) oscillator, a model that was originally introduced for its fidelity at reproducing the non-Lorentzian peak broadening experimentally observed in the infrared absorption by thin amorphous films but has since been used for many other common materials. We show that the BB model fails to satisfy the established physical criteria. Taking an alternative approach to the model derivation, a physically consistent model is proposed. This model provides the appropriate line-shape broadening for modeling the infrared optical response of thin amorphous films while adhering strictly to the Kramers-Kronig criteria. Experimental data for amorphous alumina (Al2O3 ) and amorphous quartz silica (SiO2) are used to obtain model parametrizations for both the noncausal BB model and the proposed causal model. The proposed model satisfies consistency criteria required by the underlying physics and reproduces the experimental data with better fidelity (and often with fewer parameters) than previously proposed permittivity models.
Oxidative stress, inflammation, and DNA damage in multiple organs of mice acutely exposed to amorphous silica nanoparticles.

PubMed

Nemmar, Abderrahim; Yuvaraju, Priya; Beegam, Sumaya; Yasin, Javed; Kazzam, Elsadig E; Ali, Badreldin H

2016-01-01

The use of amorphous silica (SiO2) in biopharmaceutical and industrial fields can lead to human exposure by injection, skin penetration, ingestion, or inhalation. However, the in vivo acute toxicity of amorphous SiO2 nanoparticles (SiNPs) on multiple organs and the mechanisms underlying these effects are not well understood. Presently, we investigated the acute (24 hours) effects of intraperitoneally administered 50 nm SiNPs (0.25 mg/kg) on systemic toxicity, oxidative stress, inflammation, and DNA damage in the lung, heart, liver, kidney, and brain of mice. Lipid peroxidation was significantly increased by SiNPs in the lung, liver, kidney, and brain, but was not changed in the heart. Similarly, superoxide dismutase and catalase activities were significantly affected by SiNPs in all organs studied. While the concentration of tumor necrosis factor α was insignificantly increased in the liver and brain, its increase was statistically significant in the lung, heart, and kidney. SiNPs induced a significant elevation in pulmonary and renal interleukin 6 and interleukin-1 beta in the lung, liver, and brain. Moreover, SiNPs caused a significant increase in DNA damage, assessed by comet assay, in all the organs studied. SiNPs caused leukocytosis and increased the plasma activities of lactate dehydrogenase, creatine kinase, alanine aminotranferase, and aspartate aminotransferase. These results indicate that acute systemic exposure to SiNPs causes oxidative stress, inflammation, and DNA damage in several major organs, and highlight the need for thorough evaluation of SiNPs before they can be safely used in human beings.
Oral hesperidin-Amorphization and improved dissolution properties by controlled loading onto porous silica.

PubMed

Wei, Qionghua; Keck, Cornelia M; Müller, Rainer H

2017-02-25

The oral bioavailability of poorly soluble drugs can be improved by amorphization generated by loading into the pores of mesoporous particles (pore size 2-50nm). The main mechanisms are increased kinetic saturation solubility and dissolution velocity due to the amorphous drug state and the nano-size of the drug (=increased dissolution pressure). In this study, the maximum achievable drug loading compared to the theoretical drug loading, and the effect of drug loading degree on the dissolution properties (solubility, dissolution velocity) were investigated. Hesperidin was used as the model active (having also practical relevance for e.g. nutraceutical products), loading was performed onto AEROPERL ® 300 Pharma. Degree of successful drug loading could be easily followed by simple light microscopy (=useful tool for formulation optimization), and was in agreement with scanning electron microscopy. Amorphous versus crystalline state was followed by X-ray diffraction and differential scanning calorimetry. Loadings prepared were 28.6wt.%, 54.5wt.% and 60.0wt.%, the maximum theoretical loading was 72.5wt.%. Obviously the maximum drug loading is not achievable, the 54.5wt.% drug loading was the practical maximum with already some minor crystalline hesperidin on the surface. Interestingly, the maximum kinetic saturation solubility was obtained for the 54.5wt.% drug loading (941.74μg/ml in pH 6.8 PBS), versus 408.80μg/ml for the 60.0wt.% drug loading (=overloaded system). The raw drug powder had a thermodynamic solubility of only 18.40μg/ml. The fastest in vitro release was obtained with the 28.6wt.% loaded system, followed by the 54.5wt.% and 60.0wt.% loadings. The dissolution properties (solubility, dissolution velocity) can obviously be influenced by a "controlled loading". This is a simple, cost-effective technological alternative to modulating this property by chemical modification of silica, requiring a new costly regulatory approval of these chemically modified materials. Copyright © 2016. Published by Elsevier B.V.
Photoluminescence of ZnS-SiO2:Ce Thin Films Deposited by Magnetron Sputtering

NASA Astrophysics Data System (ADS)

Mizuno, Masao

2011-12-01

Photoluminescent emissions of zinc sulfide-silica-cerium thin films deposited by magnetron sputtering were observed. The films consisted of ZnS nanocrystals embedded in amorphous SiO2 matrices. ZnS-SiO2:Ce films exhibited photoluminescence even without postannealing. Their emission spectra showed broad patterns in the visible range; the emitted colors depended on film composition.
Infrared Spectra and Binding Energies of Chemical Warfare Nerve Agent Simulants on the Surface of Amorphous Silica

DTIC Science & Technology

2013-06-24

Limited TPD of Water from Zeolite Linde 4A. Thermochim. Acta 1998, 319 (1), 177−184. (43) Palermo, A.; Löffler, D. G. Kinetics of Water Desorption...from Pelletized 4A and 5A Zeolites . Thermochim. Acta 1990, 159, 171−176. (44) Gorte, R. J. Design Parameters for Temperature Programmed Desorption from
Release of mineral-bound water prior to subduction tied to shallow seismogenic slip off Sumatra

NASA Astrophysics Data System (ADS)

Hüpers, Andre; Torres, Marta E.; Owari, Satoko; McNeill, Lisa C.; Dugan, Brandon; Henstock, Timothy J.; Milliken, Kitty L.; Petronotis, Katerina E.; Backman, Jan; Bourlange, Sylvain; Chemale, Farid; Chen, Wenhuang; Colson, Tobias A.; Frederik, Marina C. G.; Guèrin, Gilles; Hamahashi, Mari; House, Brian M.; Jeppson, Tamara N.; Kachovich, Sarah; Kenigsberg, Abby R.; Kuranaga, Mebae; Kutterolf, Steffen; Mitchison, Freya L.; Mukoyoshi, Hideki; Nair, Nisha; Pickering, Kevin T.; Pouderoux, Hugo F. A.; Shan, Yehua; Song, Insun; Vannucchi, Paola; Vrolijk, Peter J.; Yang, Tao; Zhao, Xixi

2017-05-01

Plate-boundary fault rupture during the 2004 Sumatra-Andaman subduction earthquake extended closer to the trench than expected, increasing earthquake and tsunami size. International Ocean Discovery Program Expedition 362 sampled incoming sediments offshore northern Sumatra, revealing recent release of fresh water within the deep sediments. Thermal modeling links this freshening to amorphous silica dehydration driven by rapid burial-induced temperature increases in the past 9 million years. Complete dehydration of silicates is expected before plate subduction, contrasting with prevailing models for subduction seismogenesis calling for fluid production during subduction. Shallow slip offshore Sumatra appears driven by diagenetic strengthening of deeply buried fault-forming sediments, contrasting with weakening proposed for the shallow Tohoku-Oki 2011 rupture, but our results are applicable to other thickly sedimented subduction zones including those with limited earthquake records.
Vitrification of radioactive contaminated soil by means of microwave energy

NASA Astrophysics Data System (ADS)

Yuan, Xun; Qing, Qi; Zhang, Shuai; Lu, Xirui

2017-03-01

Simulated radioactive contaminated soil was successfully vitrified by microwave sintering technology and the solidified body were systematically studied by Raman, XRD and SEM-EDX. The Raman results show that the solidified body transformed to amorphous structure better at higher temperature (1200 °C). The XRD results show that the metamictization has been significantly enhanced by the prolonged holding time at 1200 °C by microwave sintering, while by conventional sintering technology other crystal diffraction peaks, besides of silica at 2θ = 27.830°, still exist after being treated at 1200 °C for much longer time. The SEM-EDX discloses the micro-morphology of the sample and the uniform distribution of Nd element. All the results show that microwave technology performs vitrification better than the conventional sintering method in solidifying radioactive contaminated soil.
New developments using carbon dioxide as a solvent: Monolayers and nanocomposites. 1. Reactions of organosilanes with oxidized silicon surfaces in carbon dioxide. 2. Polymer/polymer nanocomposites synthesized in carbon dioxide

NASA Astrophysics Data System (ADS)

Cao, Chuntao

The aim of this research was to explore new directions for carbon dioxide. The first project emphasized silyl monolayer synthesis. Silylation reactions were performed in both liquid and supercritical carbon dioxide. Different monofunctional organosilanes reacted with silica surfaces, forming covalently attached monolayers. These monolayers were characterized using contact angle measurements, X-ray photoelectron spectroscopy, and ellipsometry. Reaction kinetics were established, and compared with silylations in organic solvents. The reaction rate in CO2 is higher than that in conventional solvents while the final coverage is slightly lower than the optimized conditions for conventional solvents. Other multi-functional silanes were also studied. The silylation of nanoporous silica surfaces showed bonding densities almost as high as the maximum value reported in literature for small-pore substrates. Overall, CO2 is a good solvent for silylations on silica surfaces. The second project was to synthesize polymer/polymer nanocomposites using a CO2-assisted templating method. Semicrystalline polymers are composed of tens-of-nanometer thick crystalline lamellae and an amorphous matrix. CO2 normally swells only the amorphous and interlamellar regions. The goal of this research was to selectively bring monomers to the amorphous and interlamellar regions with the help of CO2. In situ polymerization and precipitation fixes the structure, replicating the nano-structure of the semicrystalline polymer substrate. Ring-opening metathesis polymerization was performed inside of CO2-swollen poly(4-methyl-1-pentene) (PMP) of high crystallinity. Several polymer/polymer nanocomposites were successfully produced using this method. They were characterized by a variety of techniques, such as transmission electron microscopy (TEM), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA) and wide angle X-ray diffraction (WAXD). Infrared studies and TEM indicated that one type of composite, polynorbomene/PMP, had a gradient distribution of polynorbornene inside of the PMP matrix. Another composite, polyoctenamer/PMP prepared by cis-cyclooctene polymerization, exhibited very interesting mechanical properties. The poly(dicyclopentadiene)/PMP composites are unique nanometer-scale blends of a highly crosslinked thermoset with a thermoplastic polymer.
Iron and silicon isotope behaviour accompanying weathering in Icelandic soils, and the implications for iron export from peatlands

NASA Astrophysics Data System (ADS)

Opfergelt, S.; Williams, H. M.; Cornelis, J. T.; Guicharnaud, R. A.; Georg, R. B.; Siebert, C.; Gislason, S. R.; Halliday, A. N.; Burton, K. W.

2017-11-01

Incipient warming of peatlands at high latitudes is expected to modify soil drainage and hence the redox conditions, which has implications for Fe export from soils. This study uses Fe isotopes to assess the processes controlling Fe export in a range of Icelandic soils including peat soils derived from the same parent basalt, where Fe isotope variations principally reflect differences in weathering and drainage. In poorly weathered, well-drained soils (non-peat soils), the limited Fe isotope fractionation in soil solutions relative to the bulk soil (Δ57Fesolution-soil = -0.11 ± 0.12‰) is attributed to proton-promoted mineral dissolution. In the more weathered poorly drained soils (peat soils), the soil solutions are usually lighter than the bulk soil (Δ57Fesolution-soil = -0.41 ± 0.32‰), which indicates that Fe has been mobilised by reductive mineral dissolution and/or ligand-controlled dissolution. The results highlight the presence of Fe-organic complexes in solution in anoxic conditions. An additional constraint on soil weathering is provided by Si isotopes. The Si isotope composition of the soil solutions relative to the soil (Δ30Sisolution-soil = 0.92 ± 0.26‰) generally reflects the incorporation of light Si isotopes in secondary aluminosilicates. Under anoxic conditions in peat soils, the largest Si isotope fractionation in soil solutions relative to the bulk soil is observed (Δ30Sisolution-soil = 1.63 ± 0.40‰) and attributed to the cumulative contribution of secondary clay minerals and amorphous silica precipitation. Si supersaturation in solution with respect to amorphous silica is reached upon freezing when Al availability to form aluminosilicates is limited by the affinity of Al for metal-organic complexes. Therefore, the precipitation of amorphous silica in peat soils indirectly supports the formation of metal-organic complexes in poorly drained soils. These observations highlight that in a scenario of decreasing soil drainage with warming high latitude peatlands, Fe export from soils as Fe-organic complexes will increase, which in turn has implications for Fe transport in rivers, and ultimately the delivery of Fe to the oceans.
Can in vitro assays substitute for in vivo studies in assessing the pulmonary hazards of fine and nanoscale materials?

NASA Astrophysics Data System (ADS)

Sayes, Christie M.; Reed, Kenneth L.; Subramoney, Shekhar; Abrams, Lloyd; Warheit, David B.

2009-02-01

Risk evaluations for nanomaterials require the generation of hazard data as well as exposure assessments. Most of the validated nanotoxicity studies have been conducted using in vivo experimental designs. It would be highly desirable to develop in vitro pulmonary hazard tests to assess the toxicity of fine and nanoscale particle-types. However, in vitro evaluations for pulmonary hazards are known to have limited predictive value for identifying in vivo lung toxicity effects. Accordingly, this study investigated the capacity of in vitro screening studies to predict in vivo pulmonary toxicity of several fine or nanoparticle-types following exposures in rats. Initially, complete physicochemical characterization of particulates was conducted, both in the dry and wet states. Second, rats were exposed by intratracheal instillation to 1 or 5 mg/kg of the following particle-types: carbonyl iron, crystalline silica, amorphous silica, nanoscale zinc oxide, or fine zinc oxide. Inflammation and cytotoxicity endpoints were measured at 24 h, 1 week, 1 month and 3 months post-instillation exposure. In addition, histopathological analyses of lung tissues were conducted at 3 months post-exposure. Pulmonary cell in vitro studies consisted of three different culture conditions at 4 different time periods. These included (1) rat L2 lung epithelial cells, (2) primary rat alveolar macrophages, and (3) alveolar macrophage—L2 lung epithelial cell co-cultures which were incubated with the same particles as tested in the in vivo study for 1, 4, 24, or 48 h. Cell culture fluids were evaluated for cytotoxicity endpoints and inflammatory cytokines at the different time periods in an attempt to match the biomarkers assessed in the in vivo study. Results of in vivo pulmonary toxicity studies demonstrated that instilled carbonyl iron particles produced little toxicity. Crystalline silica and amorphous silica particle exposures produced substantial inflammatory and cytotoxic effects initially, but only the crystalline silica variety produced sustained and progressive inflammatory and cytotoxic responses, leading to the development of pulmonary fibrosis. Exposures to nanoscale or fine-sized zinc oxide particles produced potent but typical "metal fume fever"-like reversible inflammation/cytotoxic effects which were resolved by 1-month postinstillation exposure. In contrast to the in vivo results, using cytotoxicity and inflammation endpoints, in vitro effects to the various particle-types were difficult to gauge, owing to the number of variables that were studied (i.e., cell-types, time-course, dose response (including particle overload doses)), and various endpoints (e.g., cytotoxicity = LDH, MTT; inflammation/cytokines = MIP-2). For instance, none of the in vitro endpoints could mimic a transient inflammatory/cytotoxic response—as was measured following exposures to amorphous silica, or fine or nanoscale zinc oxide particles. We conclude that current in vitro cell culture systems do not accurately forecast the pulmonary hazard responses of instilled particle-types. It seems clear that in vitro cellular systems will need to be further developed, standardized, and validated (relative to in vivo effects) in order to provide useful screening data on the relative toxicity of inhaled particles.
1H MAS NMR (magic-angle spinning nuclear magnetic resonance) techniques for the quantitative determination of hydrogen types in solid catalysts and supports.

PubMed

Kennedy, Gordon J; Afeworki, Mobae; Calabro, David C; Chase, Clarence E; Smiley, Randolph J

2004-06-01

Distinct hydrogen species are present in important inorganic solids such as zeolites, silicoaluminophosphates (SAPOs), mesoporous materials, amorphous silicas, and aluminas. These H species include hydrogens associated with acidic sites such as Al(OH)Si, non-framework aluminum sites, silanols, and surface functionalities. Direct and quantitative methodology to identify, measure, and monitor these hydrogen species are key to monitoring catalyst activity, optimizing synthesis conditions, tracking post-synthesis structural modifications, and in the preparation of novel catalytic materials. Many workers have developed several techniques to address these issues, including 1H MAS NMR (magic-angle spinning nuclear magnetic resonance). 1H MAS NMR offers many potential advantages over other techniques, but care is needed in recognizing experimental limitations and developing sample handling and NMR methodology to obtain quantitatively reliable data. A simplified approach is described that permits vacuum dehydration of multiple samples simultaneously and directly in the MAS rotor without the need for epoxy, flame sealing, or extensive glovebox use. We have found that careful optimization of important NMR conditions, such as magnetic field homogeneity and magic angle setting are necessary to acquire quantitative, high-resolution spectra that accurately measure the concentrations of the different hydrogen species present. Details of this 1H MAS NMR methodology with representative applications to zeolites, SAPOs, M41S, and silicas as a function of synthesis conditions and post-synthesis treatments (i.e., steaming, thermal dehydroxylation, and functionalization) are presented.
Strain-modulated electronic and thermal transport properties of two-dimensional O-silica

NASA Astrophysics Data System (ADS)

Han, Yang; Qin, Guangzhao; Jungemann, Christoph; Hu, Ming

2016-07-01

Silica is one of the most abundant materials in the Earth’s crust and is a remarkably versatile and important engineering material in various modern science and technology. Recently, freestanding and well-ordered two-dimensional (2D) silica monolayers with octahedral (O-silica) building blocks were found to be theoretically stable by (Wang G et al 2015 J. Phys. Chem. C 119 15654-60). In this paper, by performing first-principles calculations, we systematically investigated the electronic and thermal transport properties of 2D O-silica and also studied how these properties can be tuned by simple mechanical stretching. Unstrained 2D O-silica is an insulator with an indirect band gap of 6.536 eV. The band gap decreases considerably with bilateral strain up to 29%, at which point a semiconductor-metal transition occurs. More importantly, the in-plane thermal conductivity of freestanding 2D O-silica is found to be unusually high, which is around 40 to 50 times higher than that of bulk α-quartz and more than two orders of magnitude higher than that of amorphous silica. The thermal conductivity of O-silica decreases by almost two orders of magnitude when the bilateral stretching strain reaches 10%. By analyzing the mode-dependent phonon properties and phonon-scattering channel, the phonon lifetime is found to be the dominant factor that leads to the dramatic decrease of the lattice thermal conductivity under strain. The very sensitive response of both band gap and phonon transport properties to the external mechanical strain will enable 2D O-silica to easily adapt to the different environment of realistic applications. Our study is expected to stimulate experimental exploration of further physical and chemical properties of 2D silica systems, and offers perspectives on modulating the electronic and thermal properties of related low-dimensional structures for applications such as thermoelectric, photovoltaic, and optoelectronic devices.

Strain-modulated electronic and thermal transport properties of two-dimensional O-silica.

PubMed

Han, Yang; Qin, Guangzhao; Jungemann, Christoph; Hu, Ming

2016-07-01

Silica is one of the most abundant materials in the Earth's crust and is a remarkably versatile and important engineering material in various modern science and technology. Recently, freestanding and well-ordered two-dimensional (2D) silica monolayers with octahedral (O-silica) building blocks were found to be theoretically stable by (Wang G et al 2015 J. Phys. Chem. C 119 15654-60). In this paper, by performing first-principles calculations, we systematically investigated the electronic and thermal transport properties of 2D O-silica and also studied how these properties can be tuned by simple mechanical stretching. Unstrained 2D O-silica is an insulator with an indirect band gap of 6.536 eV. The band gap decreases considerably with bilateral strain up to 29%, at which point a semiconductor-metal transition occurs. More importantly, the in-plane thermal conductivity of freestanding 2D O-silica is found to be unusually high, which is around 40 to 50 times higher than that of bulk α-quartz and more than two orders of magnitude higher than that of amorphous silica. The thermal conductivity of O-silica decreases by almost two orders of magnitude when the bilateral stretching strain reaches 10%. By analyzing the mode-dependent phonon properties and phonon-scattering channel, the phonon lifetime is found to be the dominant factor that leads to the dramatic decrease of the lattice thermal conductivity under strain. The very sensitive response of both band gap and phonon transport properties to the external mechanical strain will enable 2D O-silica to easily adapt to the different environment of realistic applications. Our study is expected to stimulate experimental exploration of further physical and chemical properties of 2D silica systems, and offers perspectives on modulating the electronic and thermal properties of related low-dimensional structures for applications such as thermoelectric, photovoltaic, and optoelectronic devices.
Synthesis of lithium superionic conductor by growth of a nanoglass within mesoporous silica SBA-15 template

NASA Astrophysics Data System (ADS)

Chatterjee, Soumi; Miah, Milon; Saha, Shyamal Kumar; Chakravorty, Dipankar

2018-04-01

Nanodimensional silica based glasses containing alkali ions have recently been grown using suitable templates. These have shown electrical properties drastically different from those of their bulk counterpart. We have synthesized silicophosphate glasses having lithium ions with concentrations of 15-35 mole% Li2O within mesoporous silica SBA-15 (Santa Barbara amorphous-15) comprising of pores of diameter ~5 nm. The nanoglasses are characterized by electrical conductivities 5-6 orders of magnitude higher than those of the corresponding bulk glasses. These properties are attributed to the presence of a larger free volume in the nanoglasses as compared to their bulk states. The nanocomposites with 35 mole% Li2O exhibit an electrical conductivity of ~3 × 10-4 S · cm-1 at around room temperature. The activation energy for Li+ ion migration has been estimated from the conductivity-temperature variation to be 0.078 eV. These nanocomposites are believed to be ideally suited for the fabrication of solid state lithium ion batteries. We have also explored the efficiency of silicophosphate glass powders as possible electrode materials. Glass of composition 70SiO2/30P2O5 was prepared by using Pluronic P-123 tri-block copolymer along with suitable precursor sols. Cyclic voltammetric and galvanostatic charge/discharge measurements were carried out on the samples prepared in combination with suitable conductive fillers using a two-electrode system. These exhibited a high specific capacitance of 356 F g-1 making them ideally suitable as electrode materials for making a lithium ion solid state battery system.
Ultrapermeable, reverse-selective nanocomposite membranes.

PubMed

Merkel, T C; Freeman, B D; Spontak, R J; He, Z; Pinnau, I; Meakin, P; Hill, A J

2002-04-19

Polymer nanocomposites continue to receive tremendous attention for application in areas such as microelectronics, organic batteries, optics, and catalysis. We have discovered that physical dispersion of nonporous, nanoscale, fumed silica particles in glassy amorphous poly(4-methyl-2-pentyne) simultaneously and surprisingly enhances both membrane permeability and selectivity for large organic molecules over small permanent gases. These highly unusual property enhancements, in contrast to results obtained in conventional filled polymer systems, reflect fumed silica-induced disruption of polymer chain packing and an accompanying subtle increase in the size of free volume elements through which molecular transport occurs, as discerned by positron annihilation lifetime spectroscopy. Such nanoscale hybridization represents an innovative means to tune the separation properties of glassy polymeric media through systematic manipulation of molecular packing.
Sample Desorption/Onization From Mesoporous Silica

DOEpatents

Iyer, Srinivas; Dattelbaum, Andrew M.

2005-10-25

Mesoporous silica is shown to be a sample holder for laser desorption/ionization of mass spectrometry. Supported mesoporous silica was prepared by coating an ethanolic silicate solution having a removable surfactant onto a substrate to produce a self-assembled, ordered, nanocomposite silica thin film. The surfactant was chosen to provide a desired pore size between about 1 nanometer diameter and 50 nanometers diameter. Removal of the surfactant resulted in a mesoporous silica thin film on the substrate. Samples having a molecular weight below 1000, such as C.sub.60 and tryptophan, were adsorbed onto and into the mesoporous silica thin film sample holder and analyzed using laser desorption/ionization mass spectrometry.
Modeling the self-assembly of ordered nanoporous materials

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

Monson, Peter; Auerbach, Scott

This report describes progress on a collaborative project on the multiscale modeling of the assembly processes in the synthesis of nanoporous materials. Such materials are of enormous importance in modern technology with application in the chemical process industries, biomedicine and biotechnology as well as microelectronics. The project focuses on two important classes of materials: i) microporous crystalline materials, such as zeolites, and ii) ordered mesoporous materials. In the first case the pores are part of the crystalline structure, while in the second the structures are amorphous on the atomistic length scale but where surfactant templating gives rise to order onmore » the length scale of 2 - 20 nm. We have developed a modeling framework that encompasses both these kinds of materials. Our models focus on the assembly of corner sharing silica tetrahedra in the presence of structure directing agents. We emphasize a balance between sufficient realism in the models and computational tractibility given the complex many-body phenomena. We use both on-lattice and off-lattice models and the primary computational tools are Monte Carlo simulations with sampling techniques and ensembles appropriate to specific situations. Our modeling approach is the first to capture silica polymerization, nanopore crystallization, and mesopore formation through computer-simulated self assembly.« less
Anthropic changes to the biotic factor of soil formation from forests to managed grasslands along summits of the western Pyrenees Mountains, France

NASA Astrophysics Data System (ADS)

Leigh, David; Gragson, Theodore

2017-04-01

Mounting evidence indicates that highland pastures of the humid-temperate western Pyrenees were converted from mixed forests to managed grasslands thousands of years ago, as early as during the late Neolithic and Bronze age by human actions including use of fire. We observe pronounced differences between soil profiles of ancient pastures and old-growth forests in otherwise similar landscape positions. In order to test physical and chemical differences, we collected paired samples of forest versus grassland soils at four separate hillslope sites where there was a clear boundary between the two vegetation types. Animal trails were excluded from sampling. Factors of climate, topography, parent material, and time of soil formation were essentially identical in the forests and pastures of each site, but the time of soil under grassland vegetation may have varied. Each paired hillslope site included five core samples (7.6 cm diameter) from the upper 7.6 cm of the mineral soil within each vegetation type, and the A horizon thickness was recorded at each core hole site. In addition, one complete soil profile was sampled in each vegetation type at each site, making a total of 20 core samples and 4 complete profiles from each respective vegetation type. In addition, we measured the magnetic susceptibility of the mineral soil surface on two transects crossing the vegetation boundary. Core samples have been measured for bulk density, pH, plant-available nutrients, and organic matter; and tests for total carbon and nitrogen, amorphous silica, charcoal, and other forms of black carbon are ongoing. Preliminary results indicate pastured A horizons are about three times as thick as forested soils, contain more organic matter, have lower soil bulk densities, have much finer and stronger structural development of soil aggregates. These traits favor much greater infiltration and water holding capacities of the pastured soils, which we have validated with saturated hydraulic conductivity tests. Pedogenically, the pastured soils indicate that melanization processes have been much more pronounced than in the forested soils. Distinct changes in soil materials result from conversion to pasture. Significantly more black carbon (including macro-charcoal) appears to be present in the pastured soils, indicating that it plays an important role in melanization, in addition to long-term sequestration of carbon. Pastured soils contain greater contents of amorphous silica due to more rapid phytolith production from grasses as opposed to trees. Pastures register significantly higher soil magnetic susceptibility than forests, presumably from past use of fire. In essence, anthropic manipulation of the biotic factor of pedogenesis has created new soil materials, processes, and functions. Our current research involves radiocarbon and chronostratigraphy to establish rates of this anthropisation of the biotic factor.
Spectroscopic study on the role of TiO{sub 2} in the adsorption of Eu(III) and U(VI) on silica surfaces in aqueous solutions

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

Im, Hee-Jung, E-mail: imhj@kaeri.re.kr; Park, Kyoung Kyun; Jung, Euo Chang

2014-10-15

Highlights: • Enhanced adsorption of Eu(III) and U(VI) onto TiO{sub 2}-coated silica. • Enhanced Eu(III) luminescence and lifetime on TiO{sub 2}-coated silica. • Energy transfer from TiO{sub 2} of TiO{sub 2}-coated silica to Eu(III) in solutions. - Abstract: To determine the effects of TiO{sub 2} on the adsorption of actinides onto mineral surfaces in groundwater, silica was partially coated with TiO{sub 2}, and Eu(III) and U(VI) were individually adsorbed from separate 0.1 mM concentration solutions. The TiO{sub 2}-coated silica showed higher Eu(III) and U(VI) adsorption capacities for increasing amounts of TiO{sub 2} coated on the silica surfaces, and thus themore » existence of TiO{sub 2} can decrease the mobility of Eu(III) and U(VI) contaminants. In luminescence studies, it was found that TiO{sub 2} considerably enhanced the luminescence of the adsorbed Eu(III) indicating that TiO{sub 2}–Eu(III) forms surface complexes which may decrease the number of water molecules at the inner sphere of Eu(III), but this was not observed for U(VI). An energy transfer from the TiO{sub 2} to the Eu(III) was confirmed in this case of amorphous TiO{sub 2}-coated silica in Eu(III) solutions, and an increase of the luminescence lifetime of Eu(III) for increasing concentrations of coated TiO{sub 2} was also observed.« less
Reduction of Acute Inflammatory Effects of Fumed Silica Nanoparticles in the Lung by Adjusting Silanol Display through Calcination and Metal Doping

PubMed Central

Sun, Bingbing; Pokhrel, Suman; Dunphy, Darren R.; Zhang, Haiyuan; Ji, Zhaoxia; Wang, Xiang; Wang, Meiying; Liao, Yu-Pei; Chang, Chong Hyun; Dong, Juyao; Li, Ruibin; Mädler, Lutz; Brinker, C. Jeffrey; Nel, André E.; Xia, Tian

2015-01-01

The production of pyrogenic (fumed) silica is increasing worldwide at a 7% annual growth rate, including expanded use in food, pharmaceuticals and other industrial products. Synthetic amorphous silica, including fumed silica, has been generally recognized as safe (GRAS) for use in food products by the Food and Drug Administration (FDA). However, emerging evidence from experimental studies now suggests that fumed silica could be hazardous due to its siloxane ring structure, high silanol density, and “string-of-pearl-like” aggregate structure, which could combine to cause membrane disruption, generation of reactive oxygen species, pro-inflammatory effects, and liver fibrosis. Based on this structure-activity analysis (SAA), we investigated whether calcination and rehydration of fumed silica changes its hazard potential in the lung due to an effect on silanol density display. This analysis demonstrated that the accompanying change in surface reactivity could indeed impact cytokine production in macrophages and acute inflammation in the lung, in a manner that is dependent on siloxane ring reconstruction. Confirmation of this SAA in vivo, prompted us to consider safer design of fumed silica properties by titanium (Ti) and aluminum (Al) doping (0–7%), using flame spray pyrolysis (FSP). Detailed characterization revealed that increased Ti and Al doping could reduce surface silanol density and expression of three-membered siloxane rings, leading to dose-dependent reduction in hydroxyl radical generation, membrane perturbation, potassium efflux, NLRP3 inflammasome activation and cytotoxicity in THP-1 cells. The reduction of NLRP3 inflammasome activation was also confirmed in bone marrow-derived macrophages (BMDMs). Ti- and to a lesser extent Al-doping, also ameliorated acute pulmonary inflammation, demonstrating the possibility of a safer design approach for fumed silica, should that be required for specific use circumstances. PMID:26200133
Evaluation of rice husk ash as filler in tread compounds

NASA Astrophysics Data System (ADS)

Fernandes, M. R. S.; Furtado, C. R. G.; de Sousa, A. M. F.

2014-05-01

Rice which is one of the largest agriculture crops produces around 22% of rice rusk during its milling process. This material is mainly used as fuel for energy generation, which results in an ash, which disposal represents an environmental issue. The rice husk ash (RHA) contains over than 70% of silica in an amorphous form and a lot of applications is being developed for it all over the world. The use of silica as a filler in the tire industry is growing since it contributes significantly to the reduction of fuel consumption of the automobiles, allowing at the same time better traction (safety). This paper presents an evaluation of the use of RHA as filler in rubber tread compounds prepared in lab scale and compares its performance with compounds prepared with commercial silica and carbon black, the fillers normally used in tire industry. Mechanical and rheological properties are evaluated, with emphasis for tan delta as an indicator of tread performance related with rolling resistance (fuel consumption) and wet grip/traction (safety).
Knowledge gaps in risk assessment of nanosilica in food: evaluation of the dissolution and toxicity of different forms of silica.

PubMed

Dekkers, Susan; Bouwmeester, Hans; Bos, Peter M J; Peters, Ruud J B; Rietveld, Anton G; Oomen, Agnes G

2013-06-01

This manuscript describes the follow-up study of our previous publication on the presence and risks of nanosilica in food. New information on the presence of nanosilica in the gastrointestinal tract is evaluated and information on nanosilica and synthetic amorphous silica (SAS) is compared to assess its relevance for risk assessment of nanosilica in food. Irrespective of whether SAS should be regarded as a nanomaterial or a non-nanoform of silica, a comparison to nanosilica is relevant to determine whether there are differences in physicochemical properties, which may lead to differences in toxicity. Based on this comparison, knowledge gaps are identified and recommendations for a targeted approach to facilitate risk assessment of nanosilica in food are given. Considering the discussion to which extent nanomaterials with (slightly) different physicochemical characteristics can be grouped for risk assessment--the sameness issue--actual exercises as presented in this manuscript are highly relevant for bringing this discussion forward.
Biogeochemistry and limnology in Antarctic subglacial weathering: molecular evidence of the linkage between subglacial silica input and primary producers in a perennially ice-covered lake

NASA Astrophysics Data System (ADS)

Takano, Yoshinori; Kojima, Hisaya; Takeda, Eriko; Yokoyama, Yusuke; Fukui, Manabu

2015-12-01

We report a 6,000 years record of subglacial weathering and biogeochemical processes in two perennially ice-covered glacial lakes at Rundvågshetta, on the Soya Coast of Lützow-Holm Bay, East Antarctica. The two lakes, Lake Maruwan Oike and Lake Maruwan-minami, are located in a channel that drains subglacial water from the base of the East Antarctic ice sheet. Greenish-grayish organic-rich laminations in sediment cores from the lakes indicate continuous primary production affected by the inflow of subglacial meltwater containing relict carbon, nitrogen, sulfur, and other essential nutrients. Biogenic silica, amorphous hydrated silica, and DNA-based molecular signatures of sedimentary facies indicate that diatom assemblages are the dominant primary producers, supported by the input of inorganic silicon (Si) from the subglacial inflow. This study highlights the significance of subglacial water-rock interactions during physical and chemical weathering processes and the importance of such interactions for the supply of bioavailable nutrients.
Mechanisms of anomalous compressibility of vitreous silica

NASA Astrophysics Data System (ADS)

Clark, Alisha N.; Lesher, Charles E.; Jacobsen, Steven D.; Sen, Sabyasachi

2014-11-01

The anomalous compressibility of vitreous silica has been known for nearly a century, but the mechanisms responsible for it remain poorly understood. Using GHz-ultrasonic interferometry, we measured longitudinal and transverse acoustic wave travel times at pressures up to 5 GPa in vitreous silica with fictive temperatures (Tf) ranging between 985 °C and 1500 °C. The maximum in ultrasonic wave travel times-corresponding to a minimum in acoustic velocities-shifts to higher pressure with increasing Tf for both acoustic waves, with complete reversibility below 5 GPa. These relationships reflect polyamorphism in the supercooled liquid, which results in a glassy state possessing different proportions of domains of high- and low-density amorphous phases (HDA and LDA, respectively). The relative proportion of HDA and LDA is set at Tf and remains fixed on compression below the permanent densification pressure. The bulk material exhibits compression behavior systematically dependent on synthesis conditions that arise from the presence of floppy modes in a mixture of HDA and LDA domains.
Investigation of the interface in silica-encapsulated liposomes by combining solid state NMR and first principles calculations.

PubMed

Folliet, Nicolas; Roiland, Claire; Bégu, Sylvie; Aubert, Anne; Mineva, Tzonka; Goursot, Annick; Selvaraj, Kaliaperumal; Duma, Luminita; Tielens, Frederik; Mauri, Francesco; Laurent, Guillaume; Bonhomme, Christian; Gervais, Christel; Babonneau, Florence; Azaïs, Thierry

2011-10-26

In the context of nanomedicine, liposils (liposomes and silica) have a strong potential for drug storage and release schemes: such materials combine the intrinsic properties of liposome (encapsulation) and silica (increased rigidity, protective coating, pH degradability). In this work, an original approach combining solid state NMR, molecular dynamics, first principles geometry optimization, and NMR parameters calculation allows the building of a precise representation of the organic/inorganic interface in liposils. {(1)H-(29)Si}(1)H and {(1)H-(31)P}(1)H Double Cross-Polarization (CP) MAS NMR experiments were implemented in order to explore the proton chemical environments around the silica and the phospholipids, respectively. Using VASP (Vienna Ab Initio Simulation Package), DFT calculations including molecular dynamics, and geometry optimization lead to the determination of energetically favorable configurations of a DPPC (dipalmitoylphosphatidylcholine) headgroup adsorbed onto a hydroxylated silica surface that corresponds to a realistic model of an amorphous silica slab. These data combined with first principles NMR parameters calculations by GIPAW (Gauge Included Projected Augmented Wave) show that the phosphate moieties are not directly interacting with silanols. The stabilization of the interface is achieved through the presence of water molecules located in-between the head groups of the phospholipids and the silica surface forming an interfacial H-bonded water layer. A detailed study of the (31)P chemical shift anisotropy (CSA) parameters allows us to interpret the local dynamics of DPPC in liposils. Finally, the VASP/solid state NMR/GIPAW combined approach can be extended to a large variety of organic-inorganic hybrid interfaces.
Experimental investigation on high performance RC column with manufactured sand and silica fume

NASA Astrophysics Data System (ADS)

Shanmuga Priya, T.

2017-11-01

In recent years, the use High Performance Concrete (HPC) has increased in construction industry. The ingredients of HPC depend on the availability and characteristics of suitable alternative materials. Those alternative materials are silica fume and manufactured sand, a by products from ferro silicon and quarry industries respectively. HPC made with silica fume as partial replacement of cement and manufactured sand as replacement of natural sand is considered as sustainable high performance concrete. In this present study the concrete was designed to get target strength of 60 MPa as per guide lines given by ACI 211- 4R (2008). The laboratory study was carried out experimentally to analyse the axial behavior of reinforced cement HPC column of size 100×100×1000mm and square in cross section. 10% of silica fume was preferred over ordinary portland cement. The natural sand was replaced by 0, 20, 40, 60, 80 and 100% with Manufactured Sand (M-Sand). In this investigation, totally 6 column specimens were cast for mixes M1 to M6 and were tested in 1000kN loading frame at 28 days. From this, Load-Mid height deflection curves were drawn and compared. Maximum ultimate load carrying capacity and the least deflection is obtained for the mix prepared by partial replacement of cement with 10% silica fume & natural sand by 100% M-Sand. The fine, amorphous and pozzalonic nature of silica fume and fine mineral particles in M- Sand increased the stiffness of HPC column. The test results revealed that HPC can be produced by using M-Sand with silica fume.
Free energy of adhesion of lipid bilayers on silica surfaces

NASA Astrophysics Data System (ADS)

Schneemilch, M.; Quirke, N.

2018-05-01

The free energy of adhesion per unit area (hereafter referred to as the adhesion strength) of lipid arrays on surfaces is a key parameter that determines the nature of the interaction between materials and biological systems. Here we report classical molecular simulations of water and 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) lipid bilayers at model silica surfaces with a range of silanol densities and structures. We employ a novel technique that enables us to estimate the adhesion strength of supported lipid bilayers in the presence of water. We find that silanols on the silica surface form hydrogen bonds with water molecules and that the water immersion enthalpy for all surfaces varies linearly with the surface density of these hydrogen bonds. The adhesion strength of lipid bilayers is a linear function of the surface density of hydrogen bonds formed between silanols and the lipid molecules on crystalline surfaces. Approximately 20% of isolated silanols form such bonds but more than 99% of mutually interacting geminal silanols do not engage in hydrogen bonding with water. On amorphous silica, the bilayer displays much stronger adhesion than expected from the crystalline surface data. We discuss the implications of these results for nanoparticle toxicity.
Fossilization of Iron-Oxidizing Bacteria at Hydrothermal Vents: a Useful Biosignature on Mars?

NASA Astrophysics Data System (ADS)

Leveille, R. J.; Lui, S.

2009-05-01

Iron oxidizing bacteria are ubiquitous in marine and terrestrial environments on Earth, where they often display distinctive cell morphologies and are commonly encrusted by minerals, especially bacteriogenic iron oxides and silica. Putative microfossils of iron oxidizing bacteria have been found in jaspers as old as 490Ma and microbial iron oxidation may be an ancient metabolic pathway. In order to investigate the usefulness of mineralized iron oxidizing bacteria as a biosignature, we have examined mineral samples collected from relict hydrothermal systems along Explorer Ridge, NE Pacific Ocean. In addition, microaerophilic, neutrophilic iron oxidizing bacteria, isolated from Pacific hydrothermal vents, were grown in a Fe-enriched seawater medium at constant pH (6.5) and oxygen concentration (5 percent) in a controlled bioreactor system. Both natural samples and experimental products were examined with a combination of variable pressure scanning electron microscopy (SEM), field emission gun SEM, and in some cases by preparing samples with a focused ion beam (FIB) milling system. Natural seafloor samples display abundant filamentous forms often resembling, in both size and shape, the twisted stalks of Gallionella and the elongated filaments of Leptothrix. Generally, these filamentous features are 1-5 microns in diameter and up to several microns in length. Some samples consist entirely of low- density, porous masses of silica encrusted filamentous forms. Presumably, these masses were formed by a rapid precipitation by the influx of silica-rich fluids into a microbial mat dominated by bacteria with filamentous morphologies. The presence of rare, amorphous (unmineralized) filamentous matter rich in C and Fe suggests that these bacteria were iron oxidizers. There is no evidence that sulfur oxidizers were present. Filamentous features sectioned by FIB milling show internal material within semi-hollow tubular-like features. Silica encrustations also show pseudo-concentric growth bands. In the bioreactor cultures, constant conditions led to abundant microbial growth and formation of an iron oxyhydroxide precipitate, either in direct association with the cells or within the growth medium. This suggests that not all of the iron precipitation is biogenic in origin. Cells typically show a filamentous morphology reminiscent of the mineral-encrusted forms observed in the natural samples. Continuing work includes high-resolution TEM observations of cultured organisms, examination of 2-year long in situ seafloor incubation experiments, and bioreactor silicification experiments in order to better understand the roles of iron and silica in the fossilization process. Microaerophilic iron oxidation could have existed on the early Earth in environments containing small amounts of oxygen produced either by locally concentrated photosynthetic microorganisms (e.g., cyanobacteria) or abiotically, as proposed for the subsurface of the Fe-dominated Rio Tinto (Spain) basin system. By analogy, similar subsurface or near-surface microaerophilic environments could have existed on Mars in the past. The distinctive morphologies and mineralization patterns of iron oxidizing bacteria could be a useful biosignature to search for on Mars. Deposits and biogenic features similar to those described here could theoretically be identified on Mars with existing imaging and analytical technologies. Therefore, future missions to Mars should target ancient hydrothermal systems, some of which have been putatively identified already.
Electromagnetic mixed waste processing system for asbestos decontamination

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

Kasevich, R.S.; Vaux, W.; Ulerich, N.

The overall objective of this three-phase program is to develop an integrated process for treating asbestos-containing material that is contaminated with radioactive and hazardous constituents. The integrated process will attempt to minimize processing and disposal costs. The objectives of Phase 1 were to establish the technical feasibility of asbestos decomposition, inorganic radionuclide nd heavy metal removal, and organic volatilization. Phase 1 resulted in the successful bench-scale demonstration of the elements required to develop a mixed waste treatment process for asbestos-containing material (ACM) contaminated with radioactive metals, heavy metals, and organics. Using the Phase 1 data, a conceptual process was developed.more » The Phase 2 program, currently in progress, is developing an integrated system design for ACM waste processing. The Phase 3 program will target demonstration of the mixed waste processing system at a DOE facility. The electromagnetic mixed waste processing system employs patented technologies to convert DOE asbestos to a non-hazardous, radionuclide-free, stable waste. The dry, contaminated asbestos is initially heated with radiofrequency energy to remove organic volatiles. Second,the radionuclides are removed by solvent extraction coupled with ion exchange solution treatment. Third, the ABCOV method converts the asbestos to an amorphous silica suspension at low temperature (100{degrees}C). Finally the amorphous silica is solidified for disposal.« less
Effects of milling media on the fabrication of melt-derived bioactive glass powder for biomaterial application

NASA Astrophysics Data System (ADS)

Ibrahim, Nurul Farhana; Mohamad, Hasmaliza; Noor, Siti Noor Fazliah Mohd

2016-12-01

The present work aims to study the effects of using different milling media on bioactive glass produced through melt-derived method for biomaterial application. The bioactive glass powder based on SiO2-CaO-Na2O-P2O5 system was fabricated using two different types of milling media which are tungsten carbide (WC) and zirconia (ZrO2) balls. However, in this work, no P2O5 was added in the new composition. XRF analysis indicated that tungsten trioxide (WO3) was observed in glass powder milled using WC balls whereas ZrO2 was observed in glass powder milled using ZrO2 balls. Amorphous structure was detected with no crystalline peak observed through XRD analysis for both glass powders. FTIR analysis confirmed the formation of silica network with the existence of functional groups Si-O-Si (bend), Si-O-Si (tetrahedral) and Si-O-Si (stretch) for both glass powders. The results revealed that there was no significant effect of milling media on amorphous silica network glass structure which shows that WC and zirconia can be used as milling media for bioactive glass fabrication without any contamination. Therefore, the fabricated BG can be tested safely for bioactivity assessment in biological fluids environment.
In Vitro and In Vivo Investigation of the Potential of Amorphous Microporous Silica as a Protein Delivery Vehicle

PubMed Central

Vanmellaert, Lieve; Vermaelen, Peter; Deroose, Christophe M.; Naert, Ignace; Cardoso, Marcio Vivan; Martens, Johan A.

2013-01-01

Delivering growth factors (GFs) at bone/implant interface needs to be optimized to achieve faster osseointegration. Amorphous microporous silica (AMS) has a potential to be used as a carrier and delivery platform for GFs. In this work, adsorption (loading) and release (delivery) mechanism of a model protein, bovine serum albumin (BSA), from AMS was investigated in vitro as well as in vivo. In general, strong BSA adsorption to AMS was observed. The interaction was stronger at lower pH owing to favorable electrostatic interaction. In vitro evaluation of BSA release revealed a peculiar release profile, involving a burst release followed by a 6 h period without appreciable BSA release and a further slower release later. Experimental data supporting this observation are discussed. Apart from understanding protein/biomaterial (BSA/AMS) interaction, determination of in vivo protein release is an essential aspect of the evaluation of a protein delivery system. In this regard micropositron emission tomography (μ-PET) was used in an exploratory experiment to determine in vivo BSA release profile from AMS. Results suggest stronger in vivo retention of BSA when adsorbed on AMS. This study highlights the possible use of AMS as a controlled protein delivery platform which may facilitate osseointegration. PMID:23991413
The role of the surfaces in the photon absorption in Ge nanoclusters embedded in silica.

PubMed

Cosentino, Salvatore; Mirabella, Salvatore; Miritello, Maria; Nicotra, Giuseppe; Lo Savio, Roberto; Simone, Francesca; Spinella, Corrado; Terrasi, Antonio

2011-02-11

The usage of semiconductor nanostructures is highly promising for boosting the energy conversion efficiency in photovoltaics technology, but still some of the underlying mechanisms are not well understood at the nanoscale length. Ge quantum dots (QDs) should have a larger absorption and a more efficient quantum confinement effect than Si ones, thus they are good candidate for third-generation solar cells. In this work, Ge QDs embedded in silica matrix have been synthesized through magnetron sputtering deposition and annealing up to 800°C. The thermal evolution of the QD size (2 to 10 nm) has been followed by transmission electron microscopy and X-ray diffraction techniques, evidencing an Ostwald ripening mechanism with a concomitant amorphous-crystalline transition. The optical absorption of Ge nanoclusters has been measured by spectrophotometry analyses, evidencing an optical bandgap of 1.6 eV, unexpectedly independent of the QDs size or of the solid phase (amorphous or crystalline). A simple modeling, based on the Tauc law, shows that the photon absorption has a much larger extent in smaller Ge QDs, being related to the surface extent rather than to the volume. These data are presented and discussed also considering the outcomes for application of Ge nanostructures in photovoltaics.PACS: 81.07.Ta; 78.67.Hc; 68.65.-k.

Acute Toxicity of Amorphous Silica Nanoparticles in Intravenously Exposed ICR Mice

PubMed Central

Wang, Wen; Jin, Minghua; Du, Zhongjun; Li, Yanbo; Duan, Junchao; Yu, Yongbo; Sun, Zhiwei

2013-01-01

This study aimed to evaluate the acute toxicity of intravenously administrated amorphous silica nanoparticles (SNPs) in mice. The lethal dose, 50 (LD50), of intravenously administrated SNPs was calculated in mice using Dixon's up-and-down method (262.45±33.78 mg/kg). The acute toxicity was evaluated at 14 d after intravenous injection of SNPs at 29.5, 103.5 and 177.5 mg/kg in mice. A silicon content analysis using ICP-OES found that SNPs mainly distributed in the resident macrophages of the liver (10.24%ID/g), spleen (34.78%ID/g) and lung (1.96%ID/g). TEM imaging showed only a small amount in the hepatocytes of the liver and in the capillary endothelial cells of the lung and kidney. The levels of serum LDH, AST and ALT were all elevated in the SNP treated groups. A histological examination showed lymphocytic infiltration, granuloma formation, and hydropic degeneration in liver hepatocytes; megakaryocyte hyperplasia in the spleen; and pneumonemia and pulmonary interstitial thickening in the lung of the SNP treated groups. A CD68 immunohistochemistry stain indicated SNPs induced macrophage proliferation in the liver and spleen. The results suggest injuries induced by the SNPs in the liver, spleen and lungs. Mononuclear phagocytic cells played an important role in the injury process. PMID:23593469
Constructing first-principles phase diagrams of amorphous LixSi using machine-learning-assisted sampling with an evolutionary algorithm

NASA Astrophysics Data System (ADS)

Artrith, Nongnuch; Urban, Alexander; Ceder, Gerbrand

2018-06-01

The atomistic modeling of amorphous materials requires structure sizes and sampling statistics that are challenging to achieve with first-principles methods. Here, we propose a methodology to speed up the sampling of amorphous and disordered materials using a combination of a genetic algorithm and a specialized machine-learning potential based on artificial neural networks (ANNs). We show for the example of the amorphous LiSi alloy that around 1000 first-principles calculations are sufficient for the ANN-potential assisted sampling of low-energy atomic configurations in the entire amorphous LixSi phase space. The obtained phase diagram is validated by comparison with the results from an extensive sampling of LixSi configurations using molecular dynamics simulations and a general ANN potential trained to ˜45 000 first-principles calculations. This demonstrates the utility of the approach for the first-principles modeling of amorphous materials.
Silicon Biomineralization on the Earth

NASA Astrophysics Data System (ADS)

Mitra, D.; Das, S.

2010-12-01

Silicon biomineralization in nature occurs as either ‘biologically controlled biomineralization’; where silicon is precipitated to serve some physiological purpose; or as ‘biologically induced biomineralization’; where mineralization occurs as a byproduct of cell’s metabolic activity or through its interactions with the environment. In biologically controlled mineralization, there is an overwhelming control of the microorganism on nucleation and mineral growth stage. There is delineation of space (as intracellular silica deposition vesicle (SDV)) for the locus of mineralization, which is sealed off from the external environment. Then silicate is sequestered and transferred to the mineralization site by energy driven (energy may be derived from photosynthesis or from glucose metabolism) pump mechanism in presence of specific transporter protein. In biologically induced biomineralization, first, there is silicon nucleation, which leads to the spontaneous growth of some critical nuclei which are resistant to rapid dissolution. Then growth of these silicon nuclei (if the ions are same) or precipitation over the nuclei (if the ions are different) occurs. Ultimately the initial amorphous phase is converted into a crystalline phase. Silicon deposition may also occur due to Ostwald ripening. If silica concentration is more than the solubility of amorphous silica (at 100oC ~ 380 mg L-1), monomeric silica [Si(OH)4] is formed which is converted into oligomers (dimers, trimers and tetramers) by polymerization. Ultimately large polymers of silanol (-Si-OH-) and siloxane (-Si-O-Si-) are formed. Silicification then occurs by hydrogen bonding with neutrally charged polysaccharides, by cation bridging with the cell wall or by direct electrostatic interactions with cationic amino groups present in protein-rich biofilms. Diatoms are the world’s largest contributor to biomineralization of silicon. Diatom silicon transporters (SITs) are membrane associated proteins that directly transport silicic acid. Specific transport enzymes then promote silicification in a supersaturated state of silicon, thus increasing the rate of silicification within diatoms to about 106 times the abiological formation rate. There are five SIT genes - cfSIT1-5 having 10 transmembrane segments, one intracellular N terminus, and one intracellular C-terminal coiled-coil motif in Cylindrotheca fusiformis. SIT genes of other diatoms are very similar, although the coiled-coil motif may be absent. Slicon transporter gene of rice has also been described recently. SDV membrane or the Silicalemma contains different proteins and when external silica is low they are increased in amount. Different types of polypeptides known as silaffins and long-chain polyamines (LCPA) are found in embedded proteins of silica matrix after dissolving it with hydrofluoric acid from purified frustules of diatoms. Silaffins 1A, 1B, 2, 1H, 1L, and LCPA can promote rapid precipitation of silica. Some native silaffins (Nat Sil-1A and 2), which are regulatory molecules of LCPA, are also obtained after treatment of frustules with ammonium fluoride. It is very difficult to explain the exact reasons for this silicification. Probably it was developed in a more silica rich hydrosphere during the Cambrian period.
THE EFFECT OF TEMPERATURE AND UNIAXIAL PRESSURE ON THE DENSIFICATION BEHAVIOR OF SILICA AEROGEL GRANULES

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

Matyas, Josef; Robinson, Matthew J.; Fryxell, Glen E.

Materials are being developed in U.S. for the removal and immobilization of iodine from gaseous products of nuclear fuel reprocessing in support of the Fuel Cycle Technology Separations and Waste Forms Campaign. The silver-functionalized silica aerogel proved to be an excellent candidate for this treatment because of its high selectivity and sorption capacity for radioiodine and its possible conversion to a durable silica-based waste form. The present study investigated with nitrogen sorption and helium pycnometry the effect of pressureless isothermal sintering at temperatures of 900-1400°C for 2.5-90 min or isothermal hot-pressing at 1200°C for 2.5 min on densification of rawmore » and silver-functionalized silica aerogel granules. Rapid sintering was observed at 1050 and 1200°C. Only 15 min of pressureless sintering at 1200°C resulted in almost complete densification. The macropores disappeared, surface area decreased from 1114 m2/g to 25 m2/g, pore volume from 7.41 cm3/g to 0.09 cm3/g, and adsorption pore size from 18.7 to 7 nm. The skeletal density of sintered granules was similar to the bulk density of amorphous silica (2.2 g/cm3). The hot-pressing accelerated the sintering process, decreasing significantly the pore size and volume.« less
Ultraviolet radiation and nanoparticle induced intracellular free radicals generation measured in human keratinocytes by electron paramagnetic resonance spectroscopy.

PubMed

Rancan, F; Nazemi, B; Rautenberg, S; Ryll, M; Hadam, S; Gao, Q; Hackbarth, S; Haag, S F; Graf, C; Rühl, E; Blume-Peytavi, U; Lademann, J; Vogt, A; Meinke, M C

2014-05-01

Several nanoparticle-based formulations used in cosmetics and dermatology are exposed to sunlight once applied to the skin. Therefore, it is important to study possible synergistic effects of nanoparticles and ultraviolet radiation. Electron paramagnetic resonance spectroscopy (EPR) was used to detect intracellular free radicals induced by ultraviolet B (UVB) radiation and amorphous silica nanoparticle and to evaluate the influence of nanoparticle surface chemistry on particle cytotoxicity toward HaCaT cells. Uncoated titanium dioxide nanoparticles served as positive control. In addition, particle intracellular uptake, viability, and induction of interleukin-6 were measured. We found that photo-activated titanium dioxide particles induced a significant amount of intracellular free radicals. On the contrary, no intracellular free radicals were generated by the investigated silica nanoparticles in the dark as well as under UVB radiation. However, under UVB exposure, the non-functionalized silica nanoparticles altered the release of IL-6. At the same concentrations, the amino-functionalized silica nanoparticles had no influence on UVB-induced IL-6 release. EPR spectroscopy is a useful technique to measure nanoparticle-induced intracellular free radicals. Non-toxic concentrations of silica particles enhanced the toxicity of UVB radiation. This synergistic effect was not mediated by particle-generated free radicals and correlated with particle surface charge and intracellular distribution. © 2013 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.
Flame Retardant Effect of Aerogel and Nanosilica on Engineered Polymers

NASA Technical Reports Server (NTRS)

Williams, Martha K.; Smith, Trent M.; Roberson, Luke B.; Yang, Feng; Nelson, Gordon L.

2010-01-01

Aerogels are typically manufactured vIa high temperature and pressure-critical-point drying of a colloidal metal oxide gel filled with solvents. Aerogel materials derived from silica materials represent a structural morphology (amorphous, open-celled nanofoams) rather than a particular chemical constituency. Aerogel is not like conventional foams in that it is a porous material with extreme microporosity and composed of individual features only a few nanometers in length with a highly porous dendriticlike structure. This unique substance has unusual properties such as low thermal conductivity, refractive index and sound suppression; in addition to its exceptional ability to capture fast moving dust. The highly porous nature of the aerogel's structure provides large amounts of surface area per unit weight. For instance, a silica aerogel material with a density of 100 kilograms per cubic meters can have surface areas of around 800 to 1500 square meters per gram depending on the precursors and process utilized to produce it. To take advantage of the unique properties of silica aerogels, especially the ultra light weight and low thermal conductivity, their composites with various engineering polymers were prepared and their flammability was investigated by Cone Calorimetry. The flammability of various polystyrene/silica aerogel nanocomposites were measured. The combination of these nanocomposites with a NASA patented flame retardant SINK were also studied. The results were compared with the base polymer to show the differences between composites with different forms of silica.
Limits of metastability in amorphous ices: the neutron scattering Debye-Waller factor.

PubMed

Amann-Winkel, Katrin; Löw, Florian; Handle, Philip H; Knoll, Wiebke; Peters, Judith; Geil, Burkhard; Fujara, Franz; Loerting, Thomas

2012-12-21

Recently, it became clear that relaxation effects in amorphous ices play a very important role that has previously been overlooked. The thermodynamic history of amorphous samples strongly affects their transition behavior. In particular, well-relaxed samples show higher thermal stability, thereby providing a larger window to investigate their glass transitions. We here present neutron scattering experiments using fixed elastic window scans on relaxed forms of amorphous ice, namely expanded high density amorphous ice (eHDA), a variant of low density amorphous ice (LDA-II) and hyperquenched glassy water (HGW). These amorphous ices are expected to be true glassy counterparts of deeply supercooled liquid water, therefore fast precursor dynamics of structural relaxation are expected to appear below the calorimetric glass transition temperature. The Debye-Waller factor shows a very weak sub-T(g) anomaly in some of the samples, which might be the signature of such fast precursor dynamics. However, we cannot find this behavior consistently in all samples at all reciprocal length scales of momentum transfer.
Size-Dependent Brittle-to-Ductile Transition in Silica Glass Nanofibers.

PubMed

Luo, Junhang; Wang, Jiangwei; Bitzek, Erik; Huang, Jian Yu; Zheng, He; Tong, Limin; Yang, Qing; Li, Ju; Mao, Scott X

2016-01-13

Silica (SiO2) glass, an essential material in human civilization, possesses excellent formability near its glass-transition temperature (Tg > 1100 °C). However, bulk SiO2 glass is very brittle at room temperature. Here we show a surprising brittle-to-ductile transition of SiO2 glass nanofibers at room temperature as its diameter reduces below 18 nm, accompanied by ultrahigh fracture strength. Large tensile plastic elongation up to 18% can be achieved at low strain rate. The unexpected ductility is due to a free surface affected zone in the nanofibers, with enhanced ionic mobility compared to the bulk that improves ductility by producing more bond-switching events per irreversible bond loss under tensile stress. Our discovery is fundamentally important for understanding the damage tolerance of small-scale amorphous structures.
Mesoporous Silica Matrix as a Tool for Minimizing Dipolar Interactions in NiFe2O4 and ZnFe2O4 Nanoparticles

PubMed Central

Virumbrales, Maider; Saez-Puche, Regino; Torralvo, María José; Blanco-Gutierrez, Veronica

2017-01-01

NiFe2O4 and ZnFe2O4 nanoparticles have been prepared encased in the MCM (Mobile Composition of Matter) type matrix. Their magnetic behavior has been studied and compared with that corresponding to particles of the same composition and of a similar size (prepared and embedded in amorphous silica or as bare particles). This study has allowed elucidation of the role exerted by the matrix and interparticle interactions in the magnetic behavior of each ferrite system. Thus, very different superparamagnetic behavior has been found in ferrite particles of similar size depending on the surrounding media. Also, the obtained results clearly provide evidence of the vastly different magnetic behavior for each ferrite system. PMID:28640197
Spectroscopic and magnetic studies of highly dispersible superparamagnetic silica coated magnetite nanoparticles

NASA Astrophysics Data System (ADS)

Tadyszak, Krzysztof; Kertmen, Ahmet; Coy, Emerson; Andruszkiewicz, Ryszard; Milewski, Sławomir; Kardava, Irakli; Scheibe, Błażej; Jurga, Stefan; Chybczyńska, Katarzyna

2017-07-01

Superparamagnetic behavior in aqueously well dispersible magnetite core-shell Fe3O4@SiO2 nanoparticles is presented. The magnetic properties of core-shell nanoparticles were measured with use of the DC, AC magnetometry and EPR spectroscopy. Particles where characterized by HR-TEM and Raman spectroscopy, showing a crystalline magnetic core of 11.5 ± 0.12 nm and an amorphous silica shell of 22 ± 1.5 nm in thickness. The DC, AC magnetic measurements confirmed the superparamagnetic nature of nanoparticles, additionally the EPR studies performed at much higher frequency than DC, AC magnetometry (9 GHz) have confirmed the paramagnetic nature of the nanoparticles. Our results show the excellent magnetic behavior of the particles with a clear magnetite structure, which are desirable properties for environmental remediation and biomedical applications.
Switchable vanadium oxide films by a sol-gel process

NASA Astrophysics Data System (ADS)

Partlow, D. P.; Gurkovich, S. R.; Radford, K. C.; Denes, L. J.

1991-07-01

Thin polycrystalline films of VO2 and V2O3 were deposited on a variety of substrates using a sol-gel process. The orientation, microstructure, optical constants, and optical and electrical switching behavior are presented. These films exhibited sharp optical switching behavior even on an amorphous substrate such as fused silica. The method yields reproducible results and is amenable to the coating of large substrates and curved surfaces such as mirrors and lenses.
Fabrication and Characterization of Dense Zirconia and Zirconia-Silica Ceramic Nanofibers

PubMed Central

Guo, Guangqing; Fan, Yuwei

2011-01-01

The objective of this study was to prepare dense zirconia-yttria (ZY), zirconia-silica (ZS) and zirconia-yttria-silica (ZYS) nanofibers as reinforcing elements for dental composites. Zirconium (IV) propoxide, yttrium nitrate hexahydrate, and tetraethyl orthosilicate (TEOS) were used as precursors for the preparation of zirconia, yttria, and silica sols. A small amount (1–1.5 wt%) of polyethylene oxide (PEO) was used as a carry polymer. The sols were preheated at 70 °C before electrospinning and their viscosity was measured with a viscometer at different heating time. The gel point was determined by viscosity–time (η–t) curve. The ZY, ZS and ZYS gel nanofibers were prepared using a special reactive electrospinning device under the conditions near the gel point. The as-prepared gel nanofibers had diameters between 200 and 400 nm. Dense (nonporous) ceramic nanofibers of zirconia-yttria (96/4), zirconia-silica (80/20) and zirconia-yttria-silica (76.8/3.2/20) with diameter of 100–300 nm were obtained by subsequent calcinations at different temperatures. The gel and ceramic nanofibers obtained were characterized by scanning electron microscope (SEM), high-resolution field-emission scanning electron microscope (FE-SEM), thermogravimetric analyzer (TGA), differential scanning calorimeter (DSC), Fourier transform infrared spectrometer (FT-IR), and X-ray diffraction (XRD). SEM micrograph revealed that ceramic ZY nanofibers had grained structure, while ceramic ZS and ZYS nanofibers had smooth surfaces, both showing no visible porosity under FE-SEM. Complete removal of the polymer PEO was confirmed by TGA/DSC and FT-IR. The formation of tetragonal phase of zirconia and amorphous silica was proved by XRD. In conclusion, dense zirconia-based ceramic nanofibers can be fabricated using the new reactive sol–gel electrospinning technology with minimum organic polymer additives. PMID:21133090
Presence of nanosilica (E551) in commercial food products: TNF-mediated oxidative stress and altered cell cycle progression in human lung fibroblast cells.

PubMed

Athinarayanan, Jegan; Periasamy, Vaiyapuri Subbarayan; Alsaif, Mohammed A; Al-Warthan, Abdulrahman A; Alshatwi, Ali A

2014-04-01

Silica (E551) is commonly used as an anti-caking agent in food products. The morphology and the dimension of the added silica particles are not, however, usually stated on the food product label. The food industry has adapted nanotechnology using engineered nanoparticles to improve the quality of their products. However, there has been increased debate regarding the health and safety concerns related to the use of engineered nanoparticles in consumer products. In this study, we investigated the morphology and dimensions of silica (E551) particles in food. The silica content of commercial food products was determined using inductively coupled plasma optical emission spectrometry. The result indicates that 2.74-14. 45 μg/g silica was found in commercial food products; however, the daily dietary intake in increase causes adverse effects on human health. E551 was isolated from food products and the morphology, particle size, crystalline nature, and purity of the silica particles were analyzed using XRD, FTIR, TEM, EDX and DLS. The results of these analyses confirmed the presence of spherical silica nanoparticles (of amorphous nature) in food, approximately 10-50 nm in size. The effects of E551 on human lung fibroblast cell viability, intracellular ROS levels, cell cycle phase, and the expression levels of metabolic stress-responsive genes (CAT, GSTA4, TNF, CYP1A, POR, SOD1, GSTM3, GPX1, and GSR1) were studied. The results suggest that E551 induces a dose-dependent cytotoxicity and changes in ROS levels and alters the gene expression and cell cycle. Treatment with a high concentration of E551 caused significant cytotoxic effects on WI-38 cells. These findings have implications for the use of these nanoparticles in the food industry.
A co-culture system with an organotypic lung slice and an immortal alveolar macrophage cell line to quantify silica-induced inflammation.

PubMed

Hofmann, Falk; Bläsche, Robert; Kasper, Michael; Barth, Kathrin

2015-01-01

There is growing evidence that amorphous silica nanoparticles cause toxic effects on lung cells in vivo as well as in vitro and induce inflammatory processes. The phagocytosis of silica by alveolar macrophages potentiates these effects. To understand the underlying molecular mechanisms of silica toxicity, we applied a co-culture system including the immortal alveolar epithelial mouse cell line E10 and the macrophage cell line AMJ2-C11. In parallel we exposed precision-cut lung slices (lacking any blood cells as well as residual alveolar macrophages) of wild type and P2rx7-/- mice with or without AMJ2-C11 cells to silica nanoparticles. Exposure of E10 cells as well as slices of wild type mice resulted in an increase of typical alveolar epithelial type 1 cell proteins like T1α, caveolin-1 and -2 and PKC-β1, whereas the co-culture with AMJ2-C11 showed mostly a slightly lesser increase of these proteins. In P2rx7-/- mice most of these proteins were slightly decreased. ELISA analysis of the supernatant of wild type and P2rx7-/- mice precision-cut lung slices showed decreased amounts of IL-6 and TNF-α when incubated with nano-silica. Our findings indicate that alveolar macrophages influence the early inflammation of the lung and also that cell damaging reagents e.g. silica have a smaller impact on P2rx7-/- mice than on wild type mice. The co-culture system with an organotypic lung slice is a useful tool to study the role of alveolar macrophages during lung injury at the organoid level.
Quantitative determination of amorphous cyclosporine in crystalline cyclosporine samples by Fourier transform infrared spectroscopy.

PubMed

Bertacche, Vittorio; Pini, Elena; Stradi, Riccardo; Stratta, Fabio

2006-01-01

The purpose of this study is the development of a quantification method to detect the amount of amorphous cyclosporine using Fourier transform infrared (FTIR) spectroscopy. The mixing of different percentages of crystalline cyclosporine with amorphous cyclosporine was used to obtain a set of standards, composed of cyclosporine samples characterized by different percentages of amorphous cyclosporine. Using a wavelength range of 450-4,000 cm(-1), FTIR spectra were obtained from samples in potassium bromide pellets and then a partial least squares (PLS) model was exploited to correlate the features of the FTIR spectra with the percentage of amorphous cyclosporine in the samples. This model gave a standard error of estimate (SEE) of 0.3562, with an r value of 0.9971 and a standard error of prediction (SEP) of 0.4168, which derives from the cross validation function used to check the precision of the model. Statistical values reveal the applicability of the method to the quantitative determination of amorphous cyclosporine in crystalline cyclosporine samples.
The simulated silicification of bacteria--new clues to the modes and timing of bacterial preservation and implications for the search for extraterrestrial microfossils.

PubMed

Toporski, Jan K W; Steele, Andrew; Westall, Frances; Thomas-Keprta, Kathie L; McKay, David S

2002-01-01

Evidence of microbial life on Earth has been found in siliceous rock formations throughout the geological and fossil record. To understand the mechanisms of silicification and thus improve our search patterns for evidence of fossil microbial life in rocks, a series of controlled laboratory experiments were designed to simulate the silicification of microorganisms. The bacterial strains Pseudomonas fluorescens and Desulphovibrio indonensis were exposed to silicifying media. The experiments were designed to determine how exposure time to silicifying solutions and to silicifying solutions of different Si concentration affect the fossilization of microbial biofilms. The silicified biofilms were analyzed using transmission electron microscopy (TEM) in combination with energy-dispersive spectroscopy. Both bacterial species showed evidence of silicification after 24 h in 1,000 ppm silica solution, although D. indonensis was less prone to silicification. The degree of silicification of individual cells of the same sample varied, though such variations decreased with increasing exposure time. High Si concentration resulted in better preservation of cellular detail; the Si concentration was more important than the duration in Si solution. Even though no evidence of amorphous silica precipitation was observed, bacterial cells became permineralized. High-resolution TEM analysis revealed nanometer-sized crystallites characterized by lattice fringe-spacings that match the (10-11) d-spacing of quartz formed within bacterial cell walls after 1 week in 5,000 ppm silica solution. The mechanisms of silicification under controlled laboratory conditions and the implication for silicification in natural environments are discussed, along with the relevance of our findings in the search for early life on Earth and extraterrestrial life.
Amorphous Phase Characterization Through X-Ray Diffraction Profile Modeling: Implications for Amorphous Phases in Gale Crater Rocks and Soils

NASA Technical Reports Server (NTRS)

Achilles, C. N.; Downs, G. W.; Downs, R. T.; Morris, R. V.; Rampe, E. B.; Ming, D. W.; Chipera, S. J.; Blake, D. F.; Vaniman, D. T.; Bristow, T. F.;

2018-01-01

The CheMin X-ray diffraction instrument on the Mars Science Laboratory rover has analyzed 18 rock and soil samples in Gale crater. Diffraction data allow for the identification of major crystalline phases based on the positions and intensities of well-defined peaks and also provides information regarding amorphous and poorly-ordered materials based on the shape and positions of broad scattering humps. The combination of diffraction data, elemental chemistry from APXS (Alpha Particle X-ray Spectrometer) and evolved gas analyses (EGA) from SAM (Sample Analysis at Mars) help constrain possible amorphous materials present in each sample (e.g., glass, opal, iron oxides, sulfates) but are model dependent. We present a novel method to characterize amorphous material in diffraction data and, through this approach, aim to characterize the phases collectively producing the amorphous profiles in CheMin diffraction data. This method may be applied to any diffraction data from samples containing X-ray amorphous materials, not just CheMin datasets, but we re-strict our discussion to Martian-relevant amorphous phases and diffraction data measured by CheMin or CheMin-like instruments.

Silica biogeochemical cycle in temperate ecosystems of the Pampean Plain, Argentina

NASA Astrophysics Data System (ADS)

Osterrieth, Margarita; Borrelli, Natalia; Alvarez, María Fernanda; Fernández Honaine, Mariana

2015-11-01

Silicophytoliths were produced in the plant communities of the Pampean Plain during the Quaternary. The biogeochemistry of silicon is scarcely known in continental environments of Argentina. The aim of this work is to present a synthesis of: the plant production and the presence of silicophytoliths in soils with grasses, and its relationship with silica content in soil solution, soil matrix and groundwaters in temperate ecosystems of the Pampean Plain, Argentina. We quantified the content of silicophytoliths in representative grasses and soils of the area. Mineralochemical determinations of the soils' matrix were made. The concentration of silica was determined in soil solution and groundwaters. The silicophytoliths assemblages in plants let to differenciate subfamilies within Poaceae. In soils, silicophytoliths represent 40-5% of the total components, conforming a stock of 59-72 × 103 kg/ha in A horizons. The concentration of SiO2 in soil solution increases with depth (453-1243 μmol/L) in relation with plant communities, their nutritional requirements and root development. The average concentration of silica in groundwaters is 840 umol/L. In the studied soils, inorganic minerals and volcanic shards show no features of weathering. About 10-40% of silicophytoliths were taxonomically unidentified because of their weathering degrees. The matrix of the aggregates is made up by microaggregates composed of carbon and silicon. The weathering of silicophytoliths is a process that contributes to the formation of amorphous silica-rich matrix of the aggregates. So, silicophytoliths could play an important role in the silica cycle being a sink and source of Si in soils and enriching soil solutions and groundwaters.
Amorphous surface layer versus transient amorphous precursor phase in bone - A case study investigated by solid-state NMR spectroscopy.

PubMed

Von Euw, Stanislas; Ajili, Widad; Chan-Chang, Tsou-Hsi-Camille; Delices, Annette; Laurent, Guillaume; Babonneau, Florence; Nassif, Nadine; Azaïs, Thierry

2017-09-01

The presence of an amorphous surface layer that coats a crystalline core has been proposed for many biominerals, including bone mineral. In parallel, transient amorphous precursor phases have been proposed in various biomineralization processes, including bone biomineralization. Here we propose a methodology to investigate the origin of these amorphous environments taking the bone tissue as a key example. This study relies on the investigation of a bone tissue sample and its comparison with synthetic calcium phosphate samples, including a stoichiometric apatite, an amorphous calcium phosphate sample, and two different biomimetic apatites. To reveal if the amorphous environments in bone originate from an amorphous surface layer or a transient amorphous precursor phase, a combined solid-state nuclear magnetic resonance (NMR) experiment has been used. The latter consists of a double cross polarization 1 H→ 31 P→ 1 H pulse sequence followed by a 1 H magnetization exchange pulse sequence. The presence of an amorphous surface layer has been investigated through the study of the biomimetic apatites; while the presence of a transient amorphous precursor phase in the form of amorphous calcium phosphate particles has been mimicked with the help of a physical mixture of stoichiometric apatite and amorphous calcium phosphate. The NMR results show that the amorphous and the crystalline environments detected in our bone tissue sample belong to the same particle. The presence of an amorphous surface layer that coats the apatitic core of bone apatite particles has been unambiguously confirmed, and it is certain that this amorphous surface layer has strong implication on bone tissue biogenesis and regeneration. Questions still persist on the structural organization of bone and biomimetic apatites. The existing model proposes a core/shell structure, with an amorphous surface layer coating a crystalline bulk. The accuracy of this model is still debated because amorphous calcium phosphate (ACP) environments could also arise from a transient amorphous precursor phase of apatite. Here, we provide an NMR spectroscopy methodology to reveal the origin of these ACP environments in bone mineral or in biomimetic apatite. The 1 H magnetization exchange between protons arising from amorphous and crystalline domains shows unambiguously that an ACP layer coats the apatitic crystalline core of bone et biomimetic apatite platelets. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Synthesis and characterization of titanium oxide supported silica materials

NASA Astrophysics Data System (ADS)

Schrijnemakers, Koen

2002-01-01

Titania-silica materials are interesting materials for use in catalysis, both as a catalyst support as well as a catalyst itself. Titania-silica materials combine the excellent support and photocatalytic properties of titania with the high thermal and mechanical stability of silica. Moreover, the interaction of titania with silica leads to new active sites, such as acid and redox sites, that are not found on the single oxides. In this Ph.D. two recently developed deposition methods were studied and evaluated for their use to create titanium oxide supported silica materials, the Chemical Surface Coating (CSC) and the Molecular Designed Dispersion (MDD). These methods were applied to two structurally different silica supports, an amorphous silica gel and the highly ordered MCM-48. Both methods are based on the specific interaction between a titanium source and the functional groups on the silica surface. With the CSC method high amounts of titanium can be obtained. However, clustering of the titania phase is observed in most cases. The MDD method allows much lower titanium amounts to be deposited without the formation of crystallites. Only at the highest Ti loading very small crystallites are formed after calcination. MCM-48 and silica gel are both pure SiO2 materials and therefore chemically similar to each other. However, they possess a different morphology and are synthesized in a different way. As such, some authors have reported that the MCM-48 surface would be more reactive than the surface of silica gel. In our experiments however no differences could be observed that confirmed this hypothesis. In the CSC method, the same reactions were observed and similar amounts of Ti and Cl were deposited. In the case of the MDD method, no difference in the reaction mechanism was observed. However, due to the lower thermal and hydrothermal stability of the MCM-48 structure compared to silica gel, partial incorporation of Ti atoms in the pore walls of MCM-48 took place. This incorporation manifested itself in both pore size as well as unit cell size increase and had a stabilizing effect on the titanium oxide coating prepared by the CSC method. Due to the incorporation of Ti in MCM-48, the coating was more firmly bound to the surface and no clustering was observed during the calcination in contrast to the silica gel support where no incorporation has taken place.

A new photoluminescence emission peak of ZnO SiO2 nanocomposites and its energy transfer to Eu3+ ions

NASA Astrophysics Data System (ADS)

Hong, Jian-He; Cong, Chang-Jie; Zhang, Zhi-Guo; Zhang, Ke-Li

2007-07-01

This work reports a new photoluminescence (PL) emission peak at about 402 nm from amorphous ZnO nanoparticles in a silica matrix, and the energy transfer from it to Eu3+ ions. The amorphous ZnO SiO2 nanocomposites were prepared by the sol gel method, which is verified by X-ray diffraction (XRD) profiles and FT IR spectra. The luminescence emission spectra are fitted by four Gauss profiles, two of which at longer wavelength are due to the defects of the material and the others to amorphous ZnO nanoparticles and the Zn O Si interface state. With the reduction of Zn/Si ratio and diethanolamine, the relative intensities of visible emission decrease. The weak visible emission is due to the reduction of defects after calcined at high temperature. The new energy state at the Zn O Si interface results in strong emission at about 402 nm. When Eu3+ ions are co-doped, weak energy transfer from ZnO SiO2 nanocomposites to Eu3+ emission are observed in the excitation spectra.
Framboidal iron oxide: Chondrite-like material from the black mat, Murray Springs, Arizona

NASA Astrophysics Data System (ADS)

Fayek, Mostafa; Anovitz, Lawrence M.; Allard, Lawrence F.; Hull, Sharon

2012-02-01

At the end of the Pleistocene a Younger Dryas "black mat" was deposited on top of the Pleistocene sediments in many parts of North America. A study of the magnetic fraction (~ 10,900 ± 50 B.P.) from the basal section of the black mat at Murray Springs, AZ revealed the presence of amorphous iron oxide framboids in a glassy iron-silica matrix. These framboids are very similar in appearance and chemistry to those reported from several types of carbonaceous chondrites. The glass contains iron, silicon, oxygen, vanadium and minor titanium, while the framboidal particles contain calcium as well. The major element chemistry of both the spherules and the glass matrix are consistent with the chemistry of material associated with meteorite impact sites and meteorites. Electron microscopy confirms that the glassy material is indeed amorphous, and also shows that what appear to be individual oxide particles are amorphous as well. The latter appears consistent with their overall morphology that, while euhedral, typically shows significant fracture. Based on these data, we argue that these particles are the product of a hypervelocity impact.
Elemental properties of coal slag and measured airborne exposures at two coal slag processing facilities

PubMed Central

Mugford, Christopher; Boylstein, Randy; Gibbs, Jenna L

2017-01-01

In 1974, the National Institute for Occupational Safety and Health recommended a ban on the use of silica sand abrasives containing >1% silica due to the risk of silicosis. This gave rise to substitutes including coal slag. An Occupational Safety and Health Administration investigation in 2010 uncovered a case cluster of suspected pneumoconiosis in four former workers at a coal slag processing facility in Illinois, possibly attributable to occupational exposure to coal slag dust. This article presents the results from a National Institute for Occupational Safety and Health industrial hygiene survey at the same coal slag processing facility and a second facility. The industrial hygiene survey consisted of the collection of: a) bulk samples of unprocessed coal slag, finished granule product, and settled dust for metals and silica; b) full-shift area air samples for dust, metals, and crystalline silica; and c) full-shift personal air samples for dust, metals, and crystalline silica. Bulk samples consisted mainly of iron, manganese, titanium, and vanadium. Some samples had detectable levels of arsenic, beryllium, cadmium, and cobalt. Unprocessed coal slags from Illinois and Kentucky contained 0.43–0.48% (4,300–4,800 mg/kg) silica. Full-shift area air samples identified elevated total dust levels in the screen (2–38 mg/m3) and bag house (21 mg/m3) areas. Full-shift area air samples identified beryllium, chromium, cobalt, copper, iron, nickel, manganese, and vanadium. Overall, personal air samples for total and respirable dust (0.1–6.6 mg/m3 total; and 0.1–0.4 mg/m3 respirable) were lower than area air samples. All full-shift personal air samples for metals and silica were below published occupational exposure limits. All bulk samples of finished product granules contained less than 1% silica, supporting the claim coal slag may present less risk for silicosis than silica sand. We note that the results presented here are solely from two coal slag processing facilities, and more in-depth air monitoring is needed to better characterize occupational exposure to coal slag dust, metals, and silica at similar facilities. PMID:27808662
Elemental properties of coal slag and measured airborne exposures at two coal slag processing facilities.

PubMed

Mugford, Christopher; Boylstein, Randy; Gibbs, Jenna L

2017-05-01

In 1974, the National Institute for Occupational Safety and Health recommended a ban on the use of silica sand abrasives containing >1% silica due to the risk of silicosis. This gave rise to substitutes including coal slag. An Occupational Safety and Health Administration investigation in 2010 uncovered a case cluster of suspected pneumoconiosis in four former workers at a coal slag processing facility in Illinois, possibly attributable to occupational exposure to coal slag dust. This article presents the results from a National Institute for Occupational Safety and Health industrial hygiene survey at the same coal slag processing facility and a second facility. The industrial hygiene survey consisted of the collection of: (a) bulk samples of unprocessed coal slag, finished granule product, and settled dust for metals and silica; (b) full-shift area air samples for dust, metals, and crystalline silica; and (c) full-shift personal air samples for dust, metals, and crystalline silica. Bulk samples consisted mainly of iron, manganese, titanium, and vanadium. Some samples had detectable levels of arsenic, beryllium, cadmium, and cobalt. Unprocessed coal slags from Illinois and Kentucky contained 0.43-0.48% (4,300-4,800 mg/kg) silica. Full-shift area air samples identified elevated total dust levels in the screen (2-38 mg/m 3 ) and bag house (21 mg/m 3 ) areas. Full-shift area air samples identified beryllium, chromium, cobalt, copper, iron, nickel, manganese, and vanadium. Overall, personal air samples for total and respirable dust (0.1-6.6 mg/m 3 total; and 0.1-0.4 mg/m 3 respirable) were lower than area air samples. All full-shift personal air samples for metals and silica were below published occupational exposure limits. All bulk samples of finished product granules contained less than 1% silica, supporting the claim coal slag may present less risk for silicosis than silica sand. We note that the results presented here are solely from two coal slag processing facilities, and more in-depth air monitoring is needed to better characterize occupational exposure to coal slag dust, metals, and silica at similar facilities.
The use of inverse phase gas chromatography to study the change of surface energy of amorphous lactose as a function of relative humidity and the processes of collapse and crystallisation.

PubMed

Newell, H E; Buckton, G; Butler, D A; Thielmann, F; Williams, D R

2001-04-17

The purpose of this study was to assess the effect of relative humidity (RH) on the surface energy of amorphous lactose. Two samples of amorphous lactose were investigated; a spray dried 100% amorphous material and a ball milled sample of crystalline lactose. The milled sample had less than 1% amorphous content by mass, but on investigation at 0% RH, yielded surface energies comparable to those obtained from the 100% amorphous material, indicating that the surface was amorphous. The effect of increasing humidity was to reduce the dispersive surface energy of the two samples from 36.0 +/- 0.14 and 41.6 +/- 1.4 mJ m(-2) at 0% RH for the spray dried and milled samples respectively, to a value comparable to that obtained for the crystalline alpha-lactose monohydrate of 31.3 +/- 0.41 mJ m(-2). The change in surface energy due to water sorption was only reversible up to 20% RH; after exposure to higher RH values subsequent drying did not result in a return to the original surface energy of the amorphous form. This shows that the surface is reorganising as the glass transition temperature (Tg) is reduced, even though the sample has not collapsed or crystallised. It was possible to follow the collapse behaviour in the column with ease, using a number of different methods.
A Silica-Supported Iron Oxide Catalyst Capable of Activating Hydrogen Peroxide at Neutral pH Values

PubMed Central

Pham, Anh Le-Tuan; Lee, Changha; Doyle, Fiona M.; Sedlak, David L.

2009-01-01

Iron oxides catalyze the conversion of hydrogen peroxide (H2O2) into oxidants capable of transforming recalcitrant contaminants. Unfortunately, the process is relatively inefficient at circumneutral pH values due to competing reactions that decompose H2O2 without producing oxidants. Silica- and alumina-containing iron oxides prepared by sol-gel processing of aqueous solutions containing Fe(ClO4)3, AlCl3 and tetraethyl orthosilicate efficiently catalyzed the decomposition of H2O2 into oxidants capable of transforming phenol at circumneutral pH values. Relative to hematite, goethite and amorphous FeOOH, the silica-iron oxide catalyst exhibited a stoichiometric efficiency, defined as the number of moles of phenol transformed per mole of H2O2 consumed, that was 10 to 40 times higher than that of the iron oxides. The silica-alumina-iron oxide catalyst had a stoichiometric efficiency that was 50 to 80 times higher than that of the iron oxides. The significant enhancement in oxidant production is attributable to the interaction of Fe with Al and Si in the mixed oxides, which alters the surface redox processes, favoring the production of strong oxidants during H2O2 decomposition. PMID:19943668
Biocompatibility of crystalline opal nanoparticles.

PubMed

Hernández-Ortiz, Marlen; Acosta-Torres, Laura S; Hernández-Padrón, Genoveva; Mendieta, Alicia I; Bernal, Rodolfo; Cruz-Vázquez, Catalina; Castaño, Victor M

2012-10-22

Silica nanoparticles are being developed as a host of biomedical and biotechnological applications. For this reason, there are more studies about biocompatibility of silica with amorphous and crystalline structure. Except hydrated silica (opal), despite is presents directly and indirectly in humans. Two sizes of crystalline opal nanoparticles were investigated in this work under criteria of toxicology. In particular, cytotoxic and genotoxic effects caused by opal nanoparticles (80 and 120 nm) were evaluated in cultured mouse cells via a set of bioassays, methylthiazolyldiphenyl-tetrazolium-bromide (MTT) and 5-bromo-2'-deoxyuridine (BrdU). 3T3-NIH cells were incubated for 24 and 72 h in contact with nanocrystalline opal particles, not presented significant statistically difference in the results of cytotoxicity. Genotoxicity tests of crystalline opal nanoparticles were performed by the BrdU assay on the same cultured cells for 24 h incubation. The reduction of BrdU-incorporated cells indicates that nanocrystalline opal exposure did not caused unrepairable damage DNA. There is no relationship between that particles size and MTT reduction, as well as BrdU incorporation, such that the opal particles did not induce cytotoxic effect and genotoxicity in cultured mouse cells.
Micro Fluidic Channel Machining on Fused Silica Glass Using Powder Blasting

PubMed Central

Jang, Ho-Su; Cho, Myeong-Woo; Park, Dong-Sam

2008-01-01

In this study, micro fluid channels are machined on fused silica glass via powder blasting, a mechanical etching process, and the machining characteristics of the channels are experimentally evaluated. In the process, material removal is performed by the collision of micro abrasives injected by highly compressed air on to the target surface. This approach can be characterized as an integration of brittle mode machining based on micro crack propagation. Fused silica glass, a high purity synthetic amorphous silicon dioxide, is selected as a workpiece material. It has a very low thermal expansion coefficient and excellent optical qualities and exceptional transmittance over a wide spectral range, especially in the ultraviolet range. The powder blasting process parameters affecting the machined results are injection pressure, abrasive particle size and density, stand-off distance, number of nozzle scanning, and shape/size of the required patterns. In this study, the influence of the number of nozzle scanning, abrasive particle size, and pattern size on the formation of micro channels is investigated. Machined shapes and surface roughness are measured using a 3-dimensional vision profiler and the results are discussed. PMID:27879730
Measurements of the sound velocity of shock-compressed liquid silica to 1100 GPa

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

McCoy, Chad August; Gregor, Michelle C.; Polsin, Danae N.

The sound velocity in a shocked material provides information about its off-Hugoniot behavior of a material at high pressures. This information can be used to extend the knowledge gained in Hugoniot experiments and to model the re-shock and release behavior. Silica is one of the most important materials for equation of state studies because of its prevalence in the earth’s interior and the well-defined properties of α-quartz. This paper presents sound velocity measurements of amorphous fused silica over the range 200 to 1100 GPa using laser-driven shocks and an α- quartz standard. These measurements demonstrate the technique proposed by Fratanduonomore » et al [J. Appl. Phys 116, 033517 (2014)] to determine the sound velocity from the arrival of acoustic perturbations. The results compare favorably to the SESAME 7386 equation-of-state table. The Grüneisen parameter was calculated from the sound velocity data and found to be Γ=0.66 ± 0.05 at densities above 6 g/cm 3, an increase in precision by a factor of two over previous measurements.« less
Measurements of the sound velocity of shock-compressed liquid silica to 1100 GPa

DOE PAGES

McCoy, Chad August; Gregor, Michelle C.; Polsin, Danae N.; ...

2016-12-19

The sound velocity in a shocked material provides information about its off-Hugoniot behavior of a material at high pressures. This information can be used to extend the knowledge gained in Hugoniot experiments and to model the re-shock and release behavior. Silica is one of the most important materials for equation of state studies because of its prevalence in the earth’s interior and the well-defined properties of α-quartz. This paper presents sound velocity measurements of amorphous fused silica over the range 200 to 1100 GPa using laser-driven shocks and an α- quartz standard. These measurements demonstrate the technique proposed by Fratanduonomore » et al [J. Appl. Phys 116, 033517 (2014)] to determine the sound velocity from the arrival of acoustic perturbations. The results compare favorably to the SESAME 7386 equation-of-state table. The Grüneisen parameter was calculated from the sound velocity data and found to be Γ=0.66 ± 0.05 at densities above 6 g/cm 3, an increase in precision by a factor of two over previous measurements.« less
Multifunctional mesoporous silica nanoparticles for combined therapeutic, diagnostic and targeted action in cancer treatment.

PubMed

Rosenholm, Jessica M; Sahlgren, Cecilia; Lindén, Mika

2011-07-01

The main objective in the development of nanomedicine is to obtain delivery platforms for targeted delivery of drugs or imaging agents for improved therapeutic efficacy, reduced side effects and increased diagnostic sensitivity. A (nano)material class that has been recognized for its controllable properties on many levels is ordered mesoporous inorganic materials, typically in the form of amorphous silica (SiO2). Characteristics for this class of materials include mesoscopic order, tunable pore dimensions in the (macro)molecular size range, a high pore volume and surface area, the possibility for selective surface functionality as well as morphology control. The robust but biodegradable ceramic matrix moreover provides shelter for incorporated agents (drugs, proteins, imaging agents, photosensitizers) leaving the outer particle surface free for further modification. The unique features make these materials particularly amenable to modular design, whereby functional moieties and features may be interchanged or combined to produce multifunctional nanodelivery systems combining targeting, diagnostic, and therapeutic actions. This review covers the latest developments related to the use of mesoporous silica nanoparticles (MSNs) as nanocarriers in biomedical applications, with special focus on cancer therapy and diagnostics.
Evaluation of rice husk ash as filler in tread compounds

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

Fernandes, M. R. S., E-mail: monica.fernandes@lanxess.com; Furtado, C. R. G., E-mail: russi@globo.com, E-mail: ana.furtado.sousa@gmail.com; Sousa, A. M. F. de, E-mail: russi@globo.com, E-mail: ana.furtado.sousa@gmail.com

Rice which is one of the largest agriculture crops produces around 22% of rice rusk during its milling process. This material is mainly used as fuel for energy generation, which results in an ash, which disposal represents an environmental issue. The rice husk ash (RHA) contains over than 70% of silica in an amorphous form and a lot of applications is being developed for it all over the world. The use of silica as a filler in the tire industry is growing since it contributes significantly to the reduction of fuel consumption of the automobiles, allowing at the same timemore » better traction (safety). This paper presents an evaluation of the use of RHA as filler in rubber tread compounds prepared in lab scale and compares its performance with compounds prepared with commercial silica and carbon black, the fillers normally used in tire industry. Mechanical and rheological properties are evaluated, with emphasis for tan delta as an indicator of tread performance related with rolling resistance (fuel consumption) and wet grip/traction (safety)« less
Nickel-impregnated silica nanoparticle synthesis and their evaluation for biocatalyst immobilization.

PubMed

Prakasham, Reddy Shetty; Devi, G Sarala; Rao, Chaganti Subba; Sivakumar, V S S; Sathish, T; Sarma, P N

2010-04-01

In the present investigation, impact of nickel-impregnated silica paramagnetic particles (NSP) as biocatalyst immobilization matrices was investigated. These nanoparticles were synthesized by sol-gel route using a nonionic surfactant block co polymer [poly (ethylene glycol)-block-poly-(propylene glycol)-block-poly (ethylene glycol)]. Diastase enzyme was immobilized on these particles (enzyme-impregnated NSP) as model enzyme and characterized using Fourier-transform infrared spectroscopy and X-ray crystallography. Analysis of enzyme-binding nature with these nanoparticles at different physiological conditions revealed that binding pattern and activity profile varied with the pH of the reaction mixture. The immobilized enzyme was further characterized for its biocatalytic activity with respect to kinetic properties such as Km and Vmax and compared with free enzyme. Paramagnetic nanoparticle-immobilized enzyme showed more affinity for substrate compared to free one. The nature of silica and nickel varied from amorphous to crystalline nature and vice versa upon immobilization of enzyme. To the best of our knowledge, this is the first report of its kind for change of nature from one form to other under normal temperatures upon diastase interaction with NSP.
Additive manufacturing of microfluidic glass chips

NASA Astrophysics Data System (ADS)

Kotz, F.; Helmer, D.; Rapp, B. E.

2018-02-01

Additive manufacturing has gained great interest in the microfluidic community due to the numerous channel designs which can be tested in the early phases of a lab-on-a-chip device development. High resolution additive manufacturing like microstereolithography is largely associated with polymers. Polymers are at a disadvantage compared to other materials due to their softness and low chemical resistance. Whenever high chemical and thermal resistance combined with high optical transparency is needed, glasses become the material of choice. However, glasses are difficult to structure at the microscale requiring hazardous chemicals for etching processes. In this work we present additive manufacturing and high resolution patterning of microfluidic chips in transparent fused silica glass using stereolithography and microlithography. We print an amorphous silica nanocomposite at room temperature using benchtop stereolithography printers and a custom built microlithography system based on a digital mirror device. Using microlithography we printed structures with tens of micron resolution. The printed part is then converted to a transparent fused silica glass using thermal debinding and sintering. Printing of a microfluidic chip can be done within 30 minutes. The heat treatment can be done within two days.
Solvothermal growth of a ruthenium metal-organic framework featuring HKUST-1 structure type as thin films on oxide surfaces.

PubMed

Kozachuk, Olesia; Yusenko, Kirill; Noei, Heshmat; Wang, Yuemin; Walleck, Stephan; Glaser, Thorsten; Fischer, Roland A

2011-08-14

Phase-pure crystalline thin films of a mixed-valence Ru(2)(II,III) metal-organic framework with 1,3,5-benzenetricarboxylate (btc) as a linker were solvothermally grown on amorphous alumina and silica surfaces. Based on the Rietveld refinement, the structure of Ru-MOF was assigned to be analogous to [Cu(3)(btc)(2)] (HKUST-1). This journal is © The Royal Society of Chemistry 2011
New insights into the toxicity of mineral fibres: A combined in situ synchrotron μ-XRD and HR-TEM study of chrysotile, crocidolite, and erionite fibres found in the tissues of Sprague-Dawley rats.

PubMed

Gualtieri, Alessandro F; Bursi Gandolfi, Nicola; Pollastri, Simone; Burghammer, Manfred; Tibaldi, Eva; Belpoggi, Fiorella; Pollok, Kilian; Langenhorst, Falko; Vigliaturo, Ruggero; Dražić, Goran

2017-05-15

Along the line of the recent research topic aimed at understanding the in vivo activity of mineral fibres and their mechanisms of toxicity, this work describes the morpho-chemical characteristics of the mineral fibres found in the tissues of Sprague-Dawley rats subjected to intraperitoneal/intrapleural injection of UICC chrysotile, UICC crocidolite and erionite-Na from Nevada (USA). The fibres are studied with in situ synchrotron powder diffraction and high resolution transmission electron microscopy to improve our understanding of the mechanisms of toxicity of these mineral fibres. In contact with the tissues of the rats, chrysotile fibres are prone to dissolve, with leaching of Mg and production of a silica rich relict. On the other hand, crocidolite and erionite-Na fibres are stable even for very long contact times within the tissues of the rats, showing just a thin dissolution amorphous halo. These findings support the model of a lower biopersistence of chrysotile with respect to crocidolite and erionite-Na but the formation of a silica-rich fibrous residue after the pseudo-amorphization of chrysotile may justify a higher cytotoxic potential and intense inflammatory activity of chrysotile in the short term in contact with the lung tissues. Copyright © 2017 Elsevier B.V. All rights reserved.
Wollastonite Carbonation in Water-Bearing Supercritical CO2: Effects of Particle Size.

PubMed

Min, Yujia; Li, Qingyun; Voltolini, Marco; Kneafsey, Timothy; Jun, Young-Shin

2017-11-07

The performance of geologic CO 2 sequestration (GCS) can be affected by CO 2 mineralization and changes in the permeability of geologic formations resulting from interactions between water-bearing supercritical CO 2 (scCO 2 ) and silicates in reservoir rocks. However, without an understanding of the size effects, the findings in previous studies using nanometer- or micrometer-size particles cannot be applied to the bulk rock in field sites. In this study, we report the effects of particle sizes on the carbonation of wollastonite (CaSiO 3 ) at 60 °C and 100 bar in water-bearing scCO 2 . After normalization by the surface area, the thickness of the reacted wollastonite layer on the surfaces was independent of particle sizes. After 20 h, the reaction was not controlled by the kinetics of surface reactions but by the diffusion of water-bearing scCO 2 across the product layer on wollastonite surfaces. Among the products of reaction, amorphous silica, rather than calcite, covered the wollastonite surface and acted as a diffusion barrier to water-bearing scCO 2 . The product layer was not highly porous, with a specific surface area 10 times smaller than that of the altered amorphous silica formed at the wollastonite surface in aqueous solution. These findings can help us evaluate the impacts of mineral carbonation in water-bearing scCO 2 .
The Role of H2O in the Carbonation of Forsterite in Supercritical CO2

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

Kwak, Ja Hun; Hu, Jian Z.; Turcu, Romulus VF

2011-07-01

The water concentration dependence of forsterite carbonation in supercritical CO2 (scCO2) at 80°C and 76 bars was investigated by a combination of NMR, XRD, TEM and XPS. Reaction products were not detected using scCO2 alone without added H2O. When trace amounts of water were included, limited reaction was observed. Below saturation, reaction products were a mixture of partially hydrated/hydroxylated magnesium carbonates and hydroxylated silica species that were mainly in an amorphous state, forming a non-resolved layer on the forsterite surface. At water concentrations above saturation, where forsterite was in contact with both a CO2-saturated aqueous fluid and a water-saturated scCO2more » fluid, solid reaction products were magnesite (MgCO3) and an amorphous polymerized SiO2 dominated by Q4, and to a lesser extent by Q3 silica coordination. Formation of these phases implies H2O initially bound in precursor hydrated/hydroxylated reaction products was liberated, inducing further reaction. Hence, for a given fluid/mineral ratio there is a water threshold above which a significant portion of the water serves in a catalytic role where more extensive carbonation reaction occurs. Defining the role of water, even in low water content environments, is therefore critical to determining the long term impact of CO2 reactivity in the subsurface.« less
Crystallization process of zeolite rho prepared by hydrothermal synthesis using 18-crown-6 ether as organic template.

PubMed

Araki, Sadao; Kiyohara, Yasato; Tanaka, Shunsuke; Miyake, Yoshikazu

2012-06-15

There are many viewpoints on the formation mechanisms for zeolites, but the details are not clear. An understanding of the elementary steps for their formation is important for the development of large-scale membranes and efficient manufacturing processes. In this study, the effects of silicon, aluminum, and the incorporation of 18-crown-6 (18C6) ether, on the formation of zeolite rho, using 18C6 as the structure directing agent (SDA) have been investigated by using field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray fluorescence spectrometry (EDX), nuclear magnetic resonance spectroscopy (NMR), thermo gravimetric analysis (TGA), and the pH measurement. These results suggested that a zeolite rho has four synthesis steps; (1) 0-3 h, the dehydration and condensation reaction between the silica and alumina to form amorphous aluminosilicates; (2) 3-20 h, the particle growth and aggregation process for the amorphous aluminosilicates; (3) 20-48 h, the crystallization and crystal growth of zeolite rho, with the incorporation of 18C6; and (4) 48-96 h, gentle growth with an increase in Na/Si ratio and a change in rate for the bounding state between the silica- and the alumina-based species. We consider the above to reflect the four steps for the formation of zeolite rho. Copyright © 2012 Elsevier Inc. All rights reserved.
The origin and determination of silica types in the silica occurrences from Altintaş region (Uşak-Western Anatolia) using multianalytical techniques

NASA Astrophysics Data System (ADS)

Koralay, Tamer; Kadıoğlu, Yusuf Kağan

2015-02-01

The studied area is located in Western Anatolia and situated on the NE-SW directed Uşak-Güre cross-graben that developed under a crustal extensional regime during the Late Miocene-Pliocene. Silica occurrences have been mostly found as mushroom-shaped big caps. They also show sedimentary structures such as stratification. Silica occurrences are milky white, yellowish white, yellow to chocolate brown and rarely pale blue, bluish gray in color and have no crystal forms in hand specimen. Some of the silica samples show conchoidal fracture. Silica minerals are mostly chalcedony, low-quartz (α-quartz) and sporadically opal-CT in spectras, according to confocal Raman spectrometry. The silica samples have enrichment of Fe (1000-24,600 ppm), Ca (100-10,200 ppm), P (4-3950 ppm) and Mn (8-3020 ppm). Other striking elements in fewer amounts are Ba (0.9-609.6 ppm), Ni (15.7-182.3 ppm) and Co (18.6-343.1 ppm). In chondrite-normalized spider diagram, silica samples display partial enrichment in LIL elements (Rb, Ba, Th). The δ18O (‰ V-SMOW) values for silica samples vary from 18.4‰ to 22.8‰ and are similar to low temperature hydrothermal silica. Confocal Raman spectrometry and oxygen isotope indicate that the silica minerals may precipitate from host fluid which is relatively has low temperatures hydrothermal solutions derived from the residual melt of basaltic magma.

Molecular dynamics study of shock compression in porous silica glass

NASA Astrophysics Data System (ADS)

Jones, Keith; Lane, J. Matthew D.; Vogler, Tracy J.

2017-06-01

The shock response of porous amorphous silica is investigated using classical molecular dynamics, over a range of porosity ranging from fully dense (2.21 g/cc) down to 0.14 g/cc. We observe an enhanced densification in the Hugoniot response at initial porosities above 50 %, and the effect increases with increasing porosity. In the lowest initial densities, after an initial compression response, the systems expand with increased pressure. These results show good agreement with experiments. Mechanisms leading to enhanced densification will be explored, which appear to differ from mechanisms observed in similar studies in silicon. Sandia National Laboratories is a multi mission laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.
Cement Type Influence on Alkali-Silica Reaction in Concrete with Crushed Gravel Aggregate

NASA Astrophysics Data System (ADS)

Rutkauskas, A.; Nagrockienė, D.; Skripkiūnas, G.

2017-10-01

Alkali-silica reaction is one of the chemical reactions which have a significant influence for durability of concrete. During alkali and silica reaction, silicon located in aggregates of the concrete, reacts with high alkali content. This way in the micropores of concrete is forming hygroscopic gel, which at wet environment, expanding and slowly but strongly destroying concrete structures. The goal of this paper- to determine the influence of cement type on alkali-silica reaction of mortars with crushed gravel. In the study crushed gravel with fraction 4/16 mm was used and four types of cements tested: CEM I 42.5 R; CEM I 42.5 SR; CEM II/A-S 42.5; CEM II/A-V 52.5. This study showed that crushed gravel is low contaminated on reactive particles containing of amorphous silica dioxide. The expansion after 14 days exceed 0.054 %, by RILEM AAR-2 research methodology (testing specimen dimension 40×40×160 mm). Continuing the investigation to 56 days for all specimens occurred alkaline corrosion features: microcracking and the surface plaque of gel. The results showed that the best resistance to alkaline corrosion after 14 days was obtained with cement CEM I 42.5 SR containing ash additive, and after 56 days with cement CEM II/A-V 52.5 containing low alkali content. The highest expansion after 14 and 56 days was obtained with cement CEM I 42.5 R without active mineral additives.
Tableting properties of silica aerogel and other silicates.

PubMed

Hentzschel, C M; Alnaief, M; Smirnova, I; Sakmann, A; Leopold, C S

2012-04-01

In solid oral dosage forms silicates are commonly used as glidants in low concentration. However, due to their large specific surface area, silicates may also be used as carrier materials for drugs. Moreover, silicates allow amorphisation of drugs by co-grinding or processing with supercritical fluids. The aim of this study was to investigate the physical and the tableting properties of Silica Aerogel (special type of silica with an extremely large specific surface area), Neusilin(®) US2 (magnesium aluminometasilicate), Florite(®) (calcium silicate) and Aerosil(®) 200 (colloidal silica). Powder blends of Avicel(®) PH102 (microcrystalline cellulose) and different amounts of the respective silicate were compacted and analyzed for their tabletability (tensile strength vs. compaction pressure) as well as their Heckel plot. With Neusilin(®) the tabletability appeared to be independent of the silicate concentration, whereas with Florite(®) an increasing silicate concentration led to a higher tensile strength. In contrast, the addition of Silica Aerogel and Aerosil(®) resulted in a decrease of the tensile strength. With Aerosil(®) a maximum tolerable concentration of 20% [w/w] was determined. Plastic deformation of all powder blends decreased with increasing silicate concentration. This effect was most pronounced with Aerosil(®) and least with Florite(®). Tablets with acceptable tensile strength were obtained with all plain silicates except for Aerosil(®). Therefore, these silicates may be used in tablet formulations, e.g. as carrier materials for liquid or amorphous drugs.
Noachian-Age Silica Deposits on Mars with Features Resembling Modern Hot Spring Biosignatures at El Tatio, Chile

NASA Astrophysics Data System (ADS)

Ruff, S. W.; Farmer, J. D.

2016-12-01

Hydrothermal spring deposits of silica (sinter) have long been targets in the search for fossil life on Mars and early Earth because of their ability to capture and preserve biosignatures. In 2007, the Spirit rover observed exposures of opaline silica (amorphous SiO2-*nH2O) adjacent to "Home Plate" in the inner basin of the Columbia Hills of Gusev crater. The presence of opaline silica in the context of a succession of volcanic rocks is interpreted as evidence of past volcanic hydrothermal activity. The silica occurs most commonly in nodular masses that have a rubbly appearance but are considered outcrops because of their stratiform expression and resistance to deformation by the rover wheels. An origin via either fumarole-related acid-sulfate leaching or precipitation from hot spring fluids was suggested previously. However, the potential significance of the characteristic nodular and mm-scale digitate opaline silica structures was not recognized. Our new observations of silica sinter deposits from the active volcanic hydrothermal system at El Tatio in northern Chile provide a basis for scale-integrated comparisons to the silica features at Home Plate, including geologic context, mesoscale structures in outcrops, mm-scale textures, and spectral signatures. The physical environment of El Tatio presents a rare combination of high elevation ( 4300 m), low precipitation rate (<100 mm/yr), high mean annual evaporation rate (132 mm), common diurnal freeze-thaw, and extremely high UV irradiance. Such conditions provide a better environmental analog for Mars than those of Yellowstone National Park (USA) and other well-known geothermal sites on Earth. Our results demonstrate that the more Mars-like conditions of El Tatio produce unique deposits with characteristics that compare favorably with the Home Plate silica outcrops. Halite (NaCl) encrusts the silica at El Tatio yielding thermal infrared spectra that are the best match yet to spectra from Spirit. Furthermore, the nodular and digitate silica structures at El Tatio that most closely resemble those on Mars include complex sedimentary structures produced by a combination of biotic and abiotic processes. Although fully abiotic processes are not ruled out for the Martian silica structures, they satisfy an a priori definition of potential biosignatures.
Preparation and recrystallization behavior of spray-dried co-amorphous naproxen-indomethacin.

PubMed

Beyer, Andreas; Radi, Lydia; Grohganz, Holger; Löbmann, Korbinian; Rades, Thomas; Leopold, Claudia S

2016-07-01

To improve the dissolution properties and the physical stability of amorphous active pharmaceutical ingredients, small molecule stabilizing agents may be added to prepare co-amorphous systems. The objective of the study was to investigate if spray-drying allows the preparation of co-amorphous drug-drug systems such as naproxen-indomethacin and to examine the influence of the process conditions on the resulting initial sample crystallinity and the recrystallization behavior of the drug(s). For this purpose, the process parameters inlet temperature and pump feed rate were varied according to a 2(2) factorial design and the obtained samples were analyzed with X-ray powder diffractometry and Fourier-transformed infrared spectroscopy. Evaluation of the data revealed that the preparation of fully amorphous samples could be achieved depending on the process conditions. The resulting recrystallization behavior of the samples, such as the total recrystallization rate, the individual recrystallization rates of naproxen and indomethacin as well as the polymorphic form of indomethacin that was formed were influenced by these process conditions. For initially amorphous samples, it was found that naproxen and indomethacin recrystallized almost simultaneously, which supports the theory of formation of drug-drug heterodimers in the co-amorphous phase. Copyright © 2016 Elsevier B.V. All rights reserved.
What We Might Know About Gusev Crater if the Mars Exploration Rover Spirit Mission were Coupled with a Mars Sample Return Mission

NASA Technical Reports Server (NTRS)

Morris, Richard V.

2008-01-01

The science instruments on the Mars Exploration Rover (MER) Spirit have provided an enormous amount of chemical and mineralogical data during more than 1450 sols of exploration at Gusev crater. The Moessbauer (MB) instrument identified 10 Fe-bearing phases at Gusev Crater: olivine, pyroxene, ilmenite, chromite, and magnetite as primary igneous phases and nanophase ferric oxide (npOx), goethite, hematite, a ferric sulfate, and pyrite/marcusite as secondary phases. The Miniature Thermal Emission Spectrometer (Mini-TES) identified some of these Fe-bearing phases (olivine and pyroxene), non- Fe-bearing phases (e.g., feldspar), and an amorphous high-SiO2 phase near Home Plate. Chemical data from the Alpha Particle X-Ray Spectrometer (APXS) provided the framework for rock classification, chemical weathering/alteration, and mineralogical constraints. APXS-based mineralogical constraints include normative calculations (with Fe(3+)/FeT from MB), elemental associations, and stoichiometry (e.g., 90% SiO2 implicates opalline silica). If Spirit had cached a set of representative samples and if those samples were returned to the Earth for laboratory analysis, what value is added by Mars Sample return (MSR) over and above the mineralogical and chemical data provided by MER?
Studies of the crystallization of amorphous trehalose using simultaneous gravimetric vapor sorption/near IR (GVS/NIR) and "modulated" GVS/NIR.

PubMed

Moran, Abigail; Buckton, Graham

2009-01-01

The purpose of this research was to investigate the influence of changes in the amorphous state on the crystallization of trehalose. Amorphous trehalose is known to stabilize biomaterials; hence, an understanding of crystallization is vital. Amorphous trehalose, prepared by spray-drying, was exposed to either a single step (0-75%) in relative humidity (RH) or to modulated 0-75-0% RH to cause crystallization. For the single-step experiment, two samples crystallized in a predictable manner to form the dihydrate. One sample, while notionally identical, did not crystallize in the same way and showed a mass loss throughout the time at 75% RH, with a final mass less than that expected for the dihydrate. The idiosyncratic sample was seen to have a starting near infrared (NIR) spectra similar to that exhibited by anhydrous crystalline trehalose, implying that short-range order in the amorphous material (or a small amount of crystalline seed, not detectable using powder X-ray diffraction) caused the sample to fail to form the dihydrate fully when exposed to high RH. The modulated RH study showed that the amorphous material interacted strongly with water; the intensity of the NIR traces was not proportional to mass of water but rather the extent of hydrogen bonding. Subsequent crystallization of this sample clearly was a partial formation of the dihydrate, but with the bulk of the sample then shielded such that it was unable to show significant sorption when exposed to elevated RH. It has been shown that the nature of the amorphous form will alter the way in which samples crystallize. With oscillation in RH, it was possible to further understand the interactions between water and amorphous trehalose.
A protected annealing strategy to enhanced light emission and photostability of YAG:Ce nanoparticle-based films

NASA Astrophysics Data System (ADS)

Revaux, Amelie; Dantelle, Geraldine; George, Nathan; Seshadri, Ram; Gacoin, Thierry; Boilot, Jean-Pierre

2011-05-01

A significant obstacle in the development of YAG:Ce nanoparticles as light converters in white LEDs and as biological labels is associated with the difficulty of finding preparative conditions that allow simultaneous control of structure, particle size and size distribution, while maintaining the optical properties of bulk samples. Preparation conditions frequently involve high-temperature treatments of precursors (up to 1400 °C), which result in increased particle size and aggregation, and lead to oxidation of Ce(iii) to Ce(iv). We report here a process that we term protected annealing, that allows the thermal treatment of preformed precursor particles at temperatures up to 1000 °C while preserving their small size and state of dispersion. In a first step, pristine nanoparticles are prepared by a glycothermal reaction, leading to a mixture of YAG and boehmite crystalline phases. The preformed nanoparticles are then dispersed in a porous silica. Annealing of the composite material at 1000 °C is followed by dissolution of the amorphous silica by hydrofluoric acid to recover the annealed particles as a colloidal dispersion. This simple process allows completion of YAG crystallization while preserving their small size. The redox state of Ce ions can be controlled through the annealing atmosphere. The obtained particles of YAG:Ce (60 +/- 10 nm in size) can be dispersed as nearly transparent aqueous suspensions, with a luminescence quantum yield of 60%. Transparent YAG:Ce nanoparticle-based films of micron thickness can be deposited on glass substrates using aerosol spraying. Films formed from particles prepared by the protected annealing strategy display significantly improved photostability over particles that have not been subject to such annealing.A significant obstacle in the development of YAG:Ce nanoparticles as light converters in white LEDs and as biological labels is associated with the difficulty of finding preparative conditions that allow simultaneous control of structure, particle size and size distribution, while maintaining the optical properties of bulk samples. Preparation conditions frequently involve high-temperature treatments of precursors (up to 1400 °C), which result in increased particle size and aggregation, and lead to oxidation of Ce(iii) to Ce(iv). We report here a process that we term protected annealing, that allows the thermal treatment of preformed precursor particles at temperatures up to 1000 °C while preserving their small size and state of dispersion. In a first step, pristine nanoparticles are prepared by a glycothermal reaction, leading to a mixture of YAG and boehmite crystalline phases. The preformed nanoparticles are then dispersed in a porous silica. Annealing of the composite material at 1000 °C is followed by dissolution of the amorphous silica by hydrofluoric acid to recover the annealed particles as a colloidal dispersion. This simple process allows completion of YAG crystallization while preserving their small size. The redox state of Ce ions can be controlled through the annealing atmosphere. The obtained particles of YAG:Ce (60 +/- 10 nm in size) can be dispersed as nearly transparent aqueous suspensions, with a luminescence quantum yield of 60%. Transparent YAG:Ce nanoparticle-based films of micron thickness can be deposited on glass substrates using aerosol spraying. Films formed from particles prepared by the protected annealing strategy display significantly improved photostability over particles that have not been subject to such annealing. Electronic supplementary information (ESI) available: Thermogravimetric analysis curve, picture of a YAG:Ce3+ thin film. See DOI: 10.1039/c0nr01000f
Silica fractionation and reactivity in soils

NASA Astrophysics Data System (ADS)

Unzué Belmonte, Dácil; Barão, Lúcia; Vandevenne, Floor; Schoelynck, Jonas; Struyf, Eric; Meire, Patrick

2014-05-01

The Si cycle is a globally important biogeochemical cycle, with strong connections to other biogeochemical cycles, including C. Silica is taken up by plants to form protective structures called phytoliths, which become a part of the soil and contribute strongly to soil Si cycling upon litter burial. Different silica fractions are found in soils, with phytoliths among the most easily soluble, especially compared to silicate minerals. A whole set of secondary non-biogenic fractions exist, that also have a high reactivity (adsorbed Si, reactive secondary minerals…). A good characterization of the different fractions of reactive silica is crucial to move forward knowledge on ecosystem Si cycling, which has been recognized in the last decade as crucial for terrestrial Si fluxes. A new method to analyze the different fractions of silica in soils has been described by Koning et al. (2002) and adapted by our research team (Barão et al. 2013). Using a continuous extraction of Si and aluminum in 0.5M NaOH, biogenic and non-biogenic reactive fractions are separated based on their Si/Al ratios and their reactivity in NaOH. Applying this new method I will investigate three emerging ideas on how humans can affect directly terrestrial Si fluxes. -Land use. I expect strong silica fractionation and reactivity differences in different land uses. These effects due to agricultural and forestry management have already been shown earlier in temperate soils (Vandevenne et al. 2012). Now we will test this hypothesis in recently deforested soils, in the south of Brazil. 'Pristine' forest, managed forest and tobacco field soils (with and without rotation crops) will be studied. This research belongs to an interdisciplinary project on soils and global change. -Fire. According to the IPCC report, extreme events such as fires (number and intensity) would increase due to climate change. We analyzed litter from spruce forest, beech forest and peat soils at two burning levels, after 350°C and 550°C burnings. The first results showed differences in silica fractions between treatments and between soil types. This project is a close collaboration with University of Dresden. -Fertilization. Humans use fertilizers to increase crops growth and to avoid plagues affecting soil biogeochemistry. We set up a greenhouse experiment where olivine (a relatively easily weatherable silicate mineral) fertilization is applied to two crops (barley and wheat), at two rain application regimes (daily rain and weekly heavy rain) and with different fertilizer grain sizes. The aim of this project is to investigate how olivine application affects Si fractionation and reactivity in the soil profile. Barão, L., Clymans, W., Vandevenne, F., Meire, P., Conley, D.J. and Struyf, E. Pedogenic and biogenic amorphous Si distribution along a temperate land use gradient. Submitted, European Journal of Soil Science, 2013. Koning, E., Epping, E., and Van Raaphorst, W.: Determining bio- genic silica in marine samples by tracking silicate and aluminium concentrations in alkaline leaching solutions, Aquat. Geochem., 8, 37-67, 2002. Vandevenne, F.I., Struyf, E., Clymans, W. & Meire, P. 2012. Agricultural silica harvest: have humans created a new and important loop in the global silica cycle? Frontiers in Ecology and the Environment 10: 243-248.
The origin and determination of silica types in the silica occurrences from Altintaş region (Uşak-Western Anatolia) using multianalytical techniques.

PubMed

Koralay, Tamer; Kadıoğlu, Yusuf Kağan

2015-02-25

The studied area is located in Western Anatolia and situated on the NE-SW directed Uşak-Güre cross-graben that developed under a crustal extensional regime during the Late Miocene-Pliocene. Silica occurrences have been mostly found as mushroom-shaped big caps. They also show sedimentary structures such as stratification. Silica occurrences are milky white, yellowish white, yellow to chocolate brown and rarely pale blue, bluish gray in color and have no crystal forms in hand specimen. Some of the silica samples show conchoidal fracture. Silica minerals are mostly chalcedony, low-quartz (α-quartz) and sporadically opal-CT in spectras, according to confocal Raman spectrometry. The silica samples have enrichment of Fe (1000-24,600 ppm), Ca (100-10,200 ppm), P (4-3950 ppm) and Mn (8-3020 ppm). Other striking elements in fewer amounts are Ba (0.9-609.6 ppm), Ni (15.7-182.3 ppm) and Co (18.6-343.1 ppm). In chondrite-normalized spider diagram, silica samples display partial enrichment in LIL elements (Rb, Ba, Th). The δ(18)O (‰ V-SMOW) values for silica samples vary from 18.4‰ to 22.8‰ and are similar to low temperature hydrothermal silica. Confocal Raman spectrometry and oxygen isotope indicate that the silica minerals may precipitate from host fluid which is relatively has low temperatures hydrothermal solutions derived from the residual melt of basaltic magma. Copyright © 2014 Elsevier B.V. All rights reserved.
Impact of nanoconfinement on the diisopropylammonium chloride (C6H16ClN) organic ferroelectric

NASA Astrophysics Data System (ADS)

Baryshnikov, S. V.; Charnaya, E. V.; Milinskiy, A. Yu.; Parfenov, V. A.; Egorova, I. V.

2018-03-01

The dielectric studies of diisopropylammonium chloride (DIPAC) nanoparticles embedded into opal and MCM-41 silica matrices are presented. It is shown that the ferroelectric phase transition shifts to low temperatures and broadens for DIPAC within the opal pores compared to bulk. The thermal hysteresis of the transition increases under opal nanoconfinement. No anomalies of the permittivity relevant to the ferroelectric transition are observed for DIPAC within the MCM-41 molecular sieves likely due to formation of the amorphous phase.
Chemical Warfare Agent Surface Adsorption: Hydrogen Bonding of Sarin and Soman to Amorphous Silica

DTIC Science & Technology

2014-03-17

Prior to experiments, the gas manifold and dosing lines were heated, under vacuum, to 100 °C to minimize water contamination. A stainless steel ...23 L UHV chamber constructed out of 316L stainless steel with all ports equipped with con-flat flanges (Kurt J. Lesker Company). The chamber is...dosed as a neat vapor using a multivalved stainless steel high-vacuum manifold. The entire path of the manifold was evacuated and heated to 100 °C
Silica exposure and silicosis among Ontario hardrock miners: II. Exposure estimates.

PubMed

Verma, D K; Sebestyen, A; Julian, J A; Muir, D C; Schmidt, H; Bernholz, C D; Shannon, H S

1989-01-01

An epidemiological investigation was carried out to determine the relationship between silicosis in hardrock miners in Ontario and cumulative exposure to silica (free crystalline silica--alpha quartz) dust. This second report describes a side-by-side air-sampling program used to derive a konimeter/gravimetric silica conversion curve. A total of 2,360 filter samples and 90,000 konimeter samples were taken over 2 years in two mines representing the ore types gold and uranium, both in existing conditions as well as in an experimental stope in which dry drilling was used to simulate the high dust conditions of the past. The method of calculating cumulative respirable silica exposure indices for each miner is reported.
Chemistry and Mineralogy of Martian Soils from In-Situ Analyses

NASA Astrophysics Data System (ADS)

Yen, A. S.

2017-12-01

In-situ analyses of typical martian soils by the Spirit, Opportunity and Curiosity rovers have shown remarkable planet-scale similarities in composition. The Alpha Particle X-ray Spectrometer data indicate that fine-grained, basaltic soils analyzed at Gusev Crater, Meridiani Planum and Gale Crater are nearly identical when cross-calibration uncertainties between the individual instruments are considered. Martian soils generally exhibit correlated increases in S, Cl and Zn with finer grain sizes, balanced by decreasing Si and Al from the feldspar component. The trends in S, Cl and Zn are consistent with condensates of volcanic exhalations and indicate minimal aqueous alteration of the soil samples after the accumulation of the volcanic volatiles. The mineralogy established by the CheMin X-ray diffractometer on the Curiosity rover show that soils are dominated by plagioclase feldspar, pyroxenes, olivine, and amorphous material. Minor phases include hematite, magnetite and anhydrite. These results are consistent with the Mössbauer spectrometer data from Spirit and Opportunity which indicate that the iron is contained in olivine, pyroxene, hematite, magnetite, and a nanophase ferric iron oxide/hydroxide. With the exception of the nanophase/amorphous component, typical martian soils are fundamentally basaltic in nature and remain relatively unaltered. Variations from typical basaltic soils have also been observed: Local contributions to the soil are evident in a number of samples which contain characteristic chemical signatures of nearby rocks. Larger sand grains on surfaces of aeolian bedforms have distinct compositions consistent with greater proportions of olivine, and in some cases, magnetite. Extensively altered fine-grained deposits dominated by sulfates and silica at Gusev Crater are distinct from basaltic soils and are consistent with fumarolic origins.
Influence of the cooling rate and the blend ratio on the physical stability of co-amorphous naproxen/indomethacin.

PubMed

Beyer, Andreas; Grohganz, Holger; Löbmann, Korbinian; Rades, Thomas; Leopold, Claudia S

2016-12-01

Co-amorphization represents a promising approach to increase the physical stability and dissolution rate of amorphous active pharmaceutical ingredients (APIs) as an alternative to polymer glass solutions. For amorphous and co-amorphous systems, it is reported that the preparation method and the blend ratio play major roles with regard to the resulting physical stability. Therefore, in the present study, co-amorphous naproxen-indomethacin (NAP/IND) was prepared by melt-quenching at three different cooling rates and at ten different NAP/IND blend ratios. The samples were analyzed using XRPD and FTIR, both directly after preparation and during storage to investigate their physical stabilities. All cooling methods led to fully amorphous samples, but with significantly different physical stabilities. Samples prepared by fast cooling had a higher degree of crystallinity after 300d of storage than samples prepared by intermediate cooling and slow cooling. Intermediate cooling was subsequently used to prepare co-amorphous NAP/IND at different blend ratios. In a previous study, it was postulated that the equimolar (0.5:0.5) co-amorphous blend of NAP/IND is most stable. However, in the present study the physically most stable blend was found for a NAP/IND ratio of 0.6:0.4, which also represents the eutectic composition of the crystalline NAP/γ-IND system. This indicates that the eutectic point may be of major importance for the stability of binary co-amorphous systems. Slight deviations from the optimal naproxen molar fraction led to significant recrystallization during storage. Either naproxen or γ-indomethacin recrystallized until a naproxen molar fraction of about 0.6 in the residual co-amorphous phase was reached again. In conclusion, the physical stability of co-amorphous NAP/IND may be significantly improved, if suitable preparation conditions and the optimal phase composition are chosen. Copyright Â© 2016 Elsevier B.V. All rights reserved.
Secondary structure and dynamics study of the intrinsically disordered silica-mineralizing peptide P 5 S 3 during silicic acid condensation and silica decondensation

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

Zerfaß, Christian; Buchko, Garry W.; Shaw, Wendy J.

The silica forming repeat R5 of sil1 from Cylindrotheca fusiformis was the blueprint for the design of P5S3, a 50-residue peptide which can be produced in large amounts by recombinant bacterial expression. It contains five protein kinase A target sites and is highly cationic due to 10 lysine and 10 arginine residues. In the presence of supersaturated ortho silicic acid P5S3 strongly enhances silica-formation whereas it retards the dissolution of amorphous silica (SiO2) at globally undersaturated concentrations. The secondary structure of P5S3 during these different functions was studied by circular dichroism (CD), complemented by nuclear magnetic resonance (NMR) studies ofmore » the peptide in the absence of silicate. The NMR studies of dual-labeled (13C, 15N) P5S3 revealed a disordered structure at pH 2.8 and 4.5. Within the pH range of 4.5 to 9.5, the CD data verified the disordered secondary structure but also suggested the presence of some polyproline II character in the absence of silicic acid. Upon silicic acid polymerization and during dissolution of preformed silica, the CD spectrum of P5S3 indicated partial transition into an α-helical conformation which was transient during silica-dissolution. Consequently, the secondary structural changes observed for P5S3 correlate with the presence of oli-gomeric/polymeric silicic acid, presumably due to P5S3-silicic acid interactions. These interactions appear, at least in part, ionic in nature since dodecylsulfate micelles, which are negatively charged, cause similar conformational shifts to P5S3 in the absence of silica while ß-D-dodecyl maltoside micelles, which are neutral, do not. Thus, P5S3 influences both the condensation of silicic acid into silica and its decondensation back to silicic acid. Moreover, the dynamics of these pro-cesses may be indirectly monitored by following structural changes to P5S3 with CD spectroscopy.« less
Evaluation of Laser-Induced Breakdown Spectroscopy (LIBS) for Measurement of Silica on Filter Samples of Coal Dust

PubMed Central

Stipe, Christopher B.; Miller, Arthur L.; Brown, Jonathan; Guevara, Edward; Cauda, Emanuele

2015-01-01

Airborne silica dust (quartz) is common in coal mines and represents a respiratory hazard that can lead to silicosis, a potentially fatal lung disease. With an eye toward developing a portable monitoring device for rapid analysis of silica dust, laser-induced breakdown spectroscopy (LIBS) was used to quantify quartz in coal dust samples collected on filter media. Pure silica (Min-U-Sil™ 5), Georgia kaolin, and Pittsburgh-4 and Illinois-6 coal dusts were deposited separately and at multiple mass loadings onto 37-mm polyvinylchloride (PVC) filters. LIBS-generated silicon emission was monitored at 288.16 nm, and non-silica contributions to that signal from kaolinite were removed by simultaneously detecting aluminum. Measurements of the four samples were used to calculate limits of detection (LOD) for silicon and aluminum of approximately 0.08 µg/cm2 and 0.05 µg/cm2, respectively (corresponding to 0.16 µg/cm2 and 0.20 µg/cm2 for silica and kaolinite, respectively). Relative errors of prediction are around 10%. Results demonstrate that LIBS can dependably quantify silica on filter samples of coal dust and confirm that accurate quantification can be achieved for very lightly loaded samples, which supports the potential application of LIBS for rapid, in-field monitoring. PMID:23146184
Evaluation of laser-induced breakdown spectroscopy (LIBS) for measurement of silica on filter samples of coal dust.

PubMed

Stipe, Christopher B; Miller, Arthur L; Brown, Jonathan; Guevara, Edward; Cauda, Emanuele

2012-11-01

Airborne silica dust (quartz) is common in coal mines and represents a respiratory hazard that can lead to silicosis, a potentially fatal lung disease. With an eye toward developing a portable monitoring device for rapid analysis of silica dust, laser-induced breakdown spectroscopy (LIBS) was used to quantify quartz in coal dust samples collected on filter media. Pure silica (Min-U-Sil™ 5), Georgia kaolin, and Pittsburgh-4 and Illinois-6 coal dusts were deposited separately and at multiple mass loadings onto 37-mm polyvinylchloride (PVC) filters. LIBS-generated silicon emission was monitored at 288.16 nm, and non-silica contributions to that signal from kaolinite were removed by simultaneously detecting aluminum. Measurements of the four samples were used to calculate limits of detection (LOD) for silicon and aluminum of approximately 0.08 μg/cm(2) and 0.05 μg/cm(2), respectively (corresponding to 0.16 μg/cm(2) and 0.20 μg/cm(2) for silica and kaolinite, respectively). Relative errors of prediction are around 10%. Results demonstrate that LIBS can dependably quantify silica on filter samples of coal dust and confirm that accurate quantification can be achieved for very lightly loaded samples, which supports the potential application of LIBS for rapid, in-field monitoring.
Synthesis and characterization of Fe(III)-silicate precipitation tubes

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

Parmar, K.; Pramanik, A.K.; Bandyopadhya, N.R.

2010-09-15

Fe(III)-silicate precipitation tubes synthesized through 'silica garden' route have been characterized using a number of analytical techniques including X-ray diffraction, infrared spectroscopy, atomic force microscopy, scanning and transmission electron microscopy. These tubes are brittle and amorphous and are hierarchically built from smaller tubes of 5-10 nm diameters. They remain amorphous at least up to 650 {sup o}C. Crystobalite and hematite are the major phases present in Fe(III)-silicate tubes heated at 850 {sup o}C. Morphology and chemical compositions at the external and internal walls of these tubes are remarkably different. These tubes are porous with high BET surface area of 291.2more » m{sup 2}/g. Fe(III)-silicate tubes contain significant amount of physically and chemically bound moisture. They show promise as an adsorbent for Pb(II), Zn(II), and Cr(III) in aqueous medium.« less
Nanoparticle interaction potentials constructed by multiscale computation

NASA Astrophysics Data System (ADS)

Lee, Cheng K.; Hua, Chi C.

2010-06-01

The van der Waals (vdW) potentials governing macroscopic objects have long been formulated in the context of classical theories, such as Hamaker's microscopic theory and Lifshitz's continuum theory. This work addresses the possibility of constructing the vdW interaction potentials of nanoparticle species using multiscale simulation schemes. Amorphous silica nanoparticles were considered as a benchmark example for which a series of (SiO2)n (n being an integer) has been systematically surveyed as the potential candidates of the packing units that reproduce known bulk material properties in atomistic molecular dynamics simulations. This strategy led to the identification of spherical Si6O12 molecules, later utilized as the elementary coarse-grained (CG) particles to compute the pair interaction potentials of silica nanoparticles ranging from 0.62 to 100 nm in diameter. The model nanoparticles so built may, in turn, serve as the children CG particles to construct nanoparticles assuming arbitrary sizes and shapes. Major observations are as follows. The pair interaction potentials for all the investigated spherical silica nanoparticles can be cast into a semiempirical, generalized Lennard-Jones 2α-α potential (α being a size-dependent, large integral number). In its reduced form, we discuss the implied universalities for the vdW potentials governing a certain range of amorphous nanoparticle species as well as how thermodynamic transferability can be fulfilled automatically. In view of future applications with colloidal suspensions, we briefly evaluated the vdW potential in the presence of a "screening" medium mimicking the effects of electrical double layers or grafting materials atop the nanoparticle core. The general observations shed new light on strategies to attain a microscopic control over interparticle attractions. In future perspectives, the proposed multiscale computation scheme shall help bridge the current gap between the modeling of polymer chains and macroscopic objects by introducing molecular models coarse-grained at a similar level so that the interactions between these two can be treated in a consistent and faithful way.

Shaping highly regular glass architectures: A lesson from nature

PubMed Central

Schoeppler, Vanessa; Reich, Elke; Vacelet, Jean; Rosenthal, Martin; Pacureanu, Alexandra; Rack, Alexander; Zaslansky, Paul; Zolotoyabko, Emil; Zlotnikov, Igor

2017-01-01

Demospongiae is a class of marine sponges that mineralize skeletal elements, the glass spicules, made of amorphous silica. The spicules exhibit a diversity of highly regular three-dimensional branched morphologies that are a paradigm example of symmetry in biological systems. Current glass shaping technology requires treatment at high temperatures. In this context, the mechanism by which glass architectures are formed by living organisms remains a mystery. We uncover the principles of spicule morphogenesis. During spicule formation, the process of silica deposition is templated by an organic filament. It is composed of enzymatically active proteins arranged in a mesoscopic hexagonal crystal-like structure. In analogy to synthetic inorganic nanocrystals that show high spatial regularity, we demonstrate that the branching of the filament follows specific crystallographic directions of the protein lattice. In correlation with the symmetry of the lattice, filament branching determines the highly regular morphology of the spicules on the macroscale. PMID:29057327
Diatomite releases silica during spirit filtration.

PubMed

Gómez, J; Gil, M L A; de la Rosa-Fox, N; Alguacil, M

2014-09-15

The purpose of this study was to ascertain whether diatomite is an inert filter aid during spirit filtration. Surely, any compound with a negative effect on the spirit composition or the consumer's health could be dissolved. In this study different diatomites were treated with 36% vol. ethanol/water mixtures and the amounts and structures of the extracted compounds were determined. Furthermore, Brandy de Jerez was diatomite- and membrane-filtered at different temperatures and the silicon content was analysed. It was found that up to 0.36% by weight of diatomite dissolved in the aqueous ethanol and amorphous silica, in the form of hollow spherical microparticles, was the most abundant component. Silicon concentrations in Brandy de Jerez increased by up to 163.0% after contact with diatomite and these changes were more marked for calcined diatomite. In contrast, reductions of more than 30% in silicon concentrations were achieved after membrane filtration at low temperatures. Copyright © 2014 Elsevier Ltd. All rights reserved.
Insight in the 3D morphology of silica-based nanotubes using electron microscopy.

PubMed

Dennenwaldt, Teresa; Wisnet, Andreas; Sedlmaier, Stefan J; Döblinger, Markus; Schnick, Wolfgang; Scheu, Christina

2016-11-01

Amorphous silica-based nanotubes (SBNTs) were synthesized from phosphoryl triamide, OP(NH 2 ) 3 , thiophosphoryl triamide, SP(NH 2 ) 3 , and silicon tetrachloride, SiCl 4 , at different temperatures and with varying amount of the starting material SiCl 4 using a recently developed template-free synthesis approach. Diameter and length of the SBNTs are tunable by varying the synthesis parameters. The 3D mesocrystals of the SBNTs were analyzed with focused ion beam sectioning and electron tomography in the transmission electron microscope showing the hollow tubular structure of the SBNTs. The reconstruction of a small SBNT assembly was achieved from a high-angle annular-dark field scanning transmission electron microscopy tilt series containing only thirteen images allowing analyzing beam sensitive material without altering the structure. The reconstruction revealed that the individual nanotubes are forming an interconnected array with an open channel structure. Copyright © 2016 Elsevier Ltd. All rights reserved.
Formation of a low-crystalline Zn-silicate in a stream in SW Sardinia, Italy

USGS Publications Warehouse

Wanty, Richard B.; De Giudici, G.; Onnis, P.; Rutherford, D.; Kimball, B.A.; Podda, F.; Cidu, R.; Lattanzi, P.; Medas, D.

2013-01-01

n southwestern Sardinia, Italy, the Rio Naracauli drains a catchment that includes several abandoned mines. The drainage from the mines and associated waste rocks has led to extreme concentrations of dissolved Zn, but because of the near-neutral pH, concentrations of other metals remain low. In the reach from approximately 2300 to 3000 m downstream from the headwaters area, an amorphous Zn-silicate precipitates from the water. In this reach, concentrations of both Zn and silica remain nearly constant, but the loads (measured in mass/time) of both increase, suggesting that new Zn and silica are supplied to the stream, likely from emerging groundwater. Zinc isotope signatures of the solid are heavier than the dissolved Zn by about 0.5 permil in 66/64Zn, suggesting that an extracellular biologically mediated adsorption process may be involved in the formation of the Zn-silicate.
Synthesis of Fe5C2@SiO2 core@shell nanoparticles as a potential candidate for biomedical application

NASA Astrophysics Data System (ADS)

Ahmadpoor, Fatemeh; Shojaosadati, Seyed Abbas; Delavari H, Hamid; Christiansen, Gunna; Saber, Reza

2018-05-01

A new strategy for water-dispersibility of hydrophobic carbide nanostructures was proposed. In this regard, hydrophobic Fe5C2 nanoparticles (NPs) with size ranging 25–40 nm were synthesized and coated with 12–15 nm silica shell for biomedical applications. X-ray diffraction (XRD) results revealed that Fe5C2 NPs with monoclinic structure were successfully prepared. The crystalline structure of Fe5C2 NPs was remained unchanged and saturation magnetization of core remained nearly constant after coating with silica shell. Moreover, Raman spectroscopy identified D-band of amorphous carbon shells which was also confirmed by transmission electron microscopy (TEM). Finally, Fe5C2@SiO2 core@shell NPs demonstrated no significant cytotoxicity and appropriate heat generating which makes them a promising candidate for magnetic fluid hyperthermia applications.
Stable Formamidinium-Based Perovskite Solar Cells via In Situ Grain Encapsulation

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

Zhu, Kai; Li, Zhen; Yang, Ye

Formamidinium (FA)-based lead iodide perovskites have emerged as the most promising light-absorber materials in the prevailing perovskite solar cells (PSCs). However, they suffer from the phase-instability issue in the ambient atmosphere, which is holding back the realization of the full potential of FA-based PSCs in the context of high efficiency and stability. Herein, the tetraethylorthosilicate hydrolysis process is integrated with the solution crystallization of FA-based perovskites, forming a new film structure with individual perovskite grains encapsulated by amorphous silica layers that are in situ formed at the nanoscale. The silica not only protects perovskite grains from the degradation but alsomore » enhances the charge-carrier dynamics of perovskite films. The underlying mechanism is discussed using a joint experiment-theory approach. Through this in situ grain encapsulation method, PSCs show an efficiency close to 20% with an impressive 97% retention after 1000-h storage under ambient conditions.« less
Defect studies of thin ZnO films prepared by pulsed laser deposition

NASA Astrophysics Data System (ADS)

Vlček, M.; Čížek, J.; Procházka, I.; Novotný, M.; Bulíř, J.; Lančok, J.; Anwand, W.; Brauer, G.; Mosnier, J.-P.

2014-04-01

Thin ZnO films were grown by pulsed laser deposition on four different substrates: sapphire (0 0 0 1), MgO (1 0 0), fused silica and nanocrystalline synthetic diamond. Defect studies by slow positron implantation spectroscopy (SPIS) revealed significantly higher concentration of defects in the studied films when compared to a bulk ZnO single crystal. The concentration of defects in the films deposited on single crystal sapphire and MgO substrates is higher than in the films deposited on amorphous fused silica substrate and nanocrystalline synthetic diamond. Furthermore, the effect of deposition temperature on film quality was investigated in ZnO films deposited on synthetic diamond substrates. Defect studies performed by SPIS revealed that the concentration of defects firstly decreases with increasing deposition temperature, but at too high deposition temperatures it increases again. The lowest concentration of defects was found in the film deposited at 450° C.
Magnetocaloric effect in amorphous and partially crystallized Fe{sub 40}Ni{sub 38}Mo{sub 4}B{sub 18} alloys

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

Thanveer, T.; Thomas, S., E-mail: senoythomas@gmail.com; Ramanujan, R. V.

A study of magnetocaloric effect in amorphous and partially crystallized Fe{sub 40}Ni{sub 38}Mo{sub 4}B{sub 18} alloys is reported. Amorphous Fe{sub 40}Ni{sub 38}Mo{sub 4}B{sub 18}, near its magnetic ordering temperature (600 K) showed a magnetic entropy change ΔS{sub M} of 1.1 J/KgK and a relative cooling power of 36 J/Kg in a field change of 10 kOe. Amorphous samples were partially crystallized by annealing at 700 K at different time intervals. Partially crystallized samples showed two distinct magnetic ordering temperature, one corresponding to the precipitated FeNi nanocrystals and the other one corresponding to the boron rich amorphous matrix. Magnetic ordering temperaturemore » of the residual amorphous matrix got shifted to the lower temperatures on increasing the annealing duration. Partially crystallised samples showed a magnetic entropy change of about 0.27 J/kgK near the magnetic ordering temperature of the amorphous matrix (540 K) in a field change of 10 kOe. The decrease in ΔS{sub M} on partial crystallisation is attributed to the biphasic magnetic nature of the sample.« less
The Effects of the Addition of Silica Mol Fraction (x = 1.5; 2; 2.5) as a Solid Electrolyte on Ion Conductivity of NASICON (Na1-xZr2SixP3-xO12) Using Solid-State Method

NASA Astrophysics Data System (ADS)

Pratiwi, V. M.; Purwaningsih, H.; Widyastuti; Fajarin, R.; Setyawan, H.

2017-05-01

Energy is a very important in modern life and need innovations to develop it. One innovation is the application of energyfor storage devices, such as batteries, capacitors, fuel cells, etc. For 30 years, the application of the NASICON (Na1+xZr2SixP3-xO12) into the NASICON gas sensor material was successfully prepared by using solid-state method. The raw materials such as SiO2, Na2CO3, ZrO2, and NaH2PO4 with a little methanol were mixed in Ballmill equipment. The silica powder was made by the extraction of bagasse ash by using sol-gel method. The x-ray diffraction patternshowedthat the result of silica extraction was amorphous and the NASICON structure wassynthesizedto bemonoclinic. The scanning electron microscopy results indicated that silica had non-uniform surface morphology and the NASICON had good surface morphology only on the form of Na3Zr2Si2PO12. The ionic conductivty of NASICON wasshown on LCR Nyquist plot of the three compositions. The highest NASICON conductivity was found inthe composition of x = 2.0, i.e. 1.142x10-8 S/m.
Effect of Surface Functionalization on Structural and Optical Properties of Luminescent LaF₃:Sm Nanoparticles.

PubMed

Ansari, Anees A

2018-02-01

Samarium (Sm3+)-doped LaF3 nanoparticles (NPs) subsequently encapsulated with inert crystalline LaF3 and amorphous silica layers were prepared by polyol and sol-gel chemical process, respectively. These surface modified core/shell/SiO2-nanostructured were characterized by X-ray diffraction (XRD), FE-transmission electron microscopy (TEM), thermal analysis, FTIR, UV/Vis absorption, bang gap energy and photoluminescence spectroscopy. The FETEM, EDX and FTIR spectral studies clearly revealed that the silica layer has been formed surrounding the core-NPs. Comparative spectral analysis indicated that core/shell/SiO2-NPs revealed high solubility in aqueous and non-aqueous solvents. The decrease in band gap energy after surface growth of an inert LaF3 and silica shells is directly correlated to the increase in grain size. On comparing the emission intensity, a significant enhancement was observed after inert layer coating, whereas, it suppress after silica encapsulation due to the non-radiative transitions. The increase luminescent intensity after inert shell growth indicates that a significant amount of non-radiative centers existing on the surface of core/shell nanoparticles can be eliminated by the shielding effect of LaF3 shells. These observed results indicate that the as-prepared core/shell/SiO2-NPs could be highly useful in broad photonic based applications such as optical sensor/optical bio-probe and light emitting diode.
Downstream processing of reverse osmosis brine: Characterisation of potential scaling compounds.

PubMed

Zaman, Masuduz; Birkett, Greg; Pratt, Christopher; Stuart, Bruce; Pratt, Steven

2015-09-01

Reverse osmosis (RO) brine produced at a full-scale coal seam gas (CSG) water treatment facility was characterized with spectroscopic and other analytical techniques. A number of potential scalants including silica, calcium, magnesium, sulphates and carbonates, all of which were present in dissolved and non-dissolved forms, were characterized. The presence of spherical particles with a size range of 10-1000 nm and aggregates of 1-10 microns was confirmed by transmission electron microscopy (TEM). Those particulates contained the following metals in decreasing order: K, Si, Sr, Ca, B, Ba, Mg, P, and S. Characterization showed that nearly one-third of the total silicon in the brine was present in the particulates. Further, analysis of the RO brine suggested supersaturation and precipitation of metal carbonates and sulphates during the RO process should take place and could be responsible for subsequently capturing silica in the solid phase. However, the precipitation of crystalline carbonates and sulphates are complex. X-ray diffraction analysis did not confirm the presence of common calcium carbonates or sulphates but instead showed the presence of a suite of complex minerals, to which amorphous silica and/or silica rich compounds could have adhered. A filtration study showed that majority of the siliceous particles were less than 220 nm in size, but could still be potentially captured using a low molecular weight ultrafiltration membrane. Copyright © 2015 Elsevier Ltd. All rights reserved.
Layer-by-Layer Templated Assembly of Silica at the Nanoscale

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

Hinestrosa, Juan Pablo; Sutton, Jonathan E.; Allison, David P.

2013-01-29

Bioinspired bottom-up assembly and layer-by-layer (LbL) construction of inorganic materials from lithographically defined organic templates enables the fabrication of nanostructured systems under mild temperature and pH conditions. Such processes open the door to low-impact manufacturing and facile recycling of hybrid materials for energy, biology, and information technologies. Here, templated LbL assembly of silica was achieved using a combination of electron beam lithography, chemical lift-off, and aqueous solution chemistry. Nanopatterns of lines, honeycomb-lattices, and dot arrays were defined in polymer resist using electron beam lithography. Following development, exposed areas of silicon were functionalized with a vapor deposited amine-silane monolayer. Silicic acidmore » solutions of varying pH and salt content were reacted with the patterned organic amine-functional templates. Vapor treatment and solution reaction could be repeated, allowing LbL deposition. Conditions for the silicic acid deposition had a strong effect on thickness of each layer, and the morphology of the amorphous silica formed. Defects in the arrays of silica nanostructures were minor and do not affect the overall organization of the layers. In conclusion, the bioinspired method described here facilitates the bottom-up assembly of inorganic nanostructures defined in three dimensions and provides a path, via LbL processing, for the construction of layered hybrid materials under mild conditions.« less
Silica-modified luminescent LaPO4 :Eu@LaPO4 @SiO2 core/shell nanorods: Synthesis, structural and luminescent properties.

PubMed

Ansari, Anees A

2018-02-01

Monoclinic-type tetragonal LaPO 4 :Eu (core) and LaPO 4 :Eu@LaPO 4 (core/shell) nanorods (NRs) were successfully prepared using a urea-based co-precipitation process under ambient conditions. An amorphous silica layer was coated around the luminescent core/shell NRs via the sol-gel process to improve their solubility and colloidal stability in aqueous and non-aqueous media. The prepared nano-products were systematically characterized by X-ray diffraction pattern, transmission electron microscopy, energy dispersive X-ray analysis, and FTIR, UV/Vis, and photoluminescence spectroscopy to examine their phase purity, crystal phase, surface chemistry, solubility and luminescence characteristics. The length and diameter of the nano-products were in the range 80-120 nm and 10-15 nm, respectively. High solubility of the silica-modified core/shell/Si NRs was found for the aqueous medium. The luminescent core NRs exhibited characteristic excitation and emission transitions in the visible region that were greatly affected by surface growth of insulating LaPO 4 and silica layers due to the multiphonon relaxation rate. Our luminescence spectral results clearly show a distinct difference in intensities for core, core/shell, and core/shell/Si NRs. Highly luminescent NRs with good solubility could be useful candidates for a variety of photonic-based biomedical applications. Copyright © 2017 John Wiley & Sons, Ltd.
Insights into effects and mechanism of pre-dispersant on surface morphologies of silica or alumina coated rutile TiO2 particles

NASA Astrophysics Data System (ADS)

Dong, Xiongbo; Sun, Zhiming; Liu, Yangyu; Jiang, Lei; Zheng, Shuilin

2018-05-01

Silica and alumina coated rutile TiO2 samples with various surface morphologies were fabricated using four different pre-dispersants. Using sodium silicate nonahydrate (SSNH) as pre-dispersant, the received sample displayed the best acidic stability. The addition of SSNH could induce layer-by-layer growth of hydrous silica via enhancing the dispersion of hydrous silica nucleus and accelerating the dehydration condensation rate of silica film. Alumina coated rutile TiO2 sample obtained by polyethyleneglycol 1000 (PEG) presented the highest dispersion stability. The existence of PEG can induce the formation of fibrous hydrous alumina film, which would increase the steric hindrance and the promotion of dispersion stability.
Effect of Siloxane Ring Strain and Cation Charge Density on the Formation of Coordinately Unsaturated Metal Sites on Silica: Insights from Density Functional Theory (DFT) Studies

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

Das, Ujjal; Zhang, Guanghui; Hu, Bo

2015-10-28

Amorphous silica (SiO 2) is commonly used as a support in heterogeneous catalysis. However, due to the structural disorder and temperature induced change of surface morphology, the structures of silica supported metal catalysts are difficult to determine. Most studies are primarily focused on understanding the interactions of different types of surface hydroxyl groups with metal ions. In comparison, the effect of siloxane ring size on the structure of silica supported metal catalysts and how it affects catalytic activity is poorly understood. Here, we have used density functional theory calculations to understand the effect of siloxane ring strain on structure andmore » activity of different monomeric Lewis acid metal sites on silica. In particular, we have found that large siloxane rings favor strong dative bonding interaction between metal ion and surface hydroxyls, leading to the formation of high-coordinate metal sites. In comparison, metal-silanol interaction is weak in small siloxane rings, resulting in low-coordinate metal sites. The physical origin of this size dependence is associated with siloxane ring strain, and, a correlation between metal-silanol interaction energy and ring strain energy has been observed. In addition to ring strain, the strength of the metal-silanol interaction also depends on the positive charge density of the cations. In fact, a correlation also exists between metal-silanol interaction energy and charge density of several first-row transition and post-transition metals. The theoretical results are compared with the EXAFS data of monomeric Zn(II) and Ga(III) ions grafted on silica. In conclusion, the molecular level insights of how metal ion coordination on silica depends on siloxane ring strain and cation charge density will be useful in the synthesis of new catalysts.« less
The effect of impeller type on silica sol formation in laboratory scale agitated tank

NASA Astrophysics Data System (ADS)

Nurtono, Tantular; Suprana, Yayang Ade; Latif, Abdul; Dewa, Restu Mulya; Machmudah, Siti; Widiyastuti, Winardi, Sugeng

2016-02-01

The multiphase polymerization reaction of the silica sol formation produced from silicic acid and potassium hydroxide solutions in laboratory scale agitated tank was studied. The reactor is equipped with four segmental baffle and top entering impeller. The inside diameter of reactor is 9 cm, the baffle width is 0.9 cm, and the impeller position is 3 cm from tank bottom. The diameter of standard six blades Rushton and three blades marine propeller impellers are 5 cm. The silicic acid solution was made from 0.2 volume fraction of water glass (sodium silicate) solution in which the sodium ion was exchanged by hydrogen ion from cation resin. The reactor initially filled with 286 ml silicic acid solution was operated in semi batch mode and the temperature was kept constant in 60 °C. The 3 ml/minute of 1 M potassium hydroxide solution was added into stirred tank and the solution was stirred. The impeller rotational speed was varied from 100 until 700 rpm. This titration was stopped if the solution in stirred tank had reached the pH of 10-The morphology of the silica particles in the silica sol product was analyzed by Scanning Electron Microscope (SEM). The size of silica particles in silica sol was measured based on the SEM image. The silica particle obtained in this research was amorphous particle and the shape was roughly cylinder. The flow field generated by different impeller gave significant effect on particle size and shape. The smallest geometric mean of length and diameter of particle (4.92 µm and 2.42 µm, respectively) was generated in reactor with marine propeller at 600 rpm. The reactor with Rushton impeller produced particle which the geometric mean of length and diameter of particle was 4.85 µm and 2.36 µm, respectively, at 150 rpm.
The effect of impeller type on silica sol formation in laboratory scale agitated tank

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

Nurtono, Tantular; Suprana, Yayang Ade; Latif, Abdul

2016-02-08

The multiphase polymerization reaction of the silica sol formation produced from silicic acid and potassium hydroxide solutions in laboratory scale agitated tank was studied. The reactor is equipped with four segmental baffle and top entering impeller. The inside diameter of reactor is 9 cm, the baffle width is 0.9 cm, and the impeller position is 3 cm from tank bottom. The diameter of standard six blades Rushton and three blades marine propeller impellers are 5 cm. The silicic acid solution was made from 0.2 volume fraction of water glass (sodium silicate) solution in which the sodium ion was exchanged by hydrogen ion from cationmore » resin. The reactor initially filled with 286 ml silicic acid solution was operated in semi batch mode and the temperature was kept constant in 60 °C. The 3 ml/minute of 1 M potassium hydroxide solution was added into stirred tank and the solution was stirred. The impeller rotational speed was varied from 100 until 700 rpm. This titration was stopped if the solution in stirred tank had reached the pH of 10-The morphology of the silica particles in the silica sol product was analyzed by Scanning Electron Microscope (SEM). The size of silica particles in silica sol was measured based on the SEM image. The silica particle obtained in this research was amorphous particle and the shape was roughly cylinder. The flow field generated by different impeller gave significant effect on particle size and shape. The smallest geometric mean of length and diameter of particle (4.92 µm and 2.42 µm, respectively) was generated in reactor with marine propeller at 600 rpm. The reactor with Rushton impeller produced particle which the geometric mean of length and diameter of particle was 4.85 µm and 2.36 µm, respectively, at 150 rpm.« less
Characteristics of amorphous kerogens fractionated from terrigenous sedimentary rocks

NASA Astrophysics Data System (ADS)

Suzuki, Noriyuki

1984-02-01

A preliminary attempt to fractionate amorphous kerogens from terrigenous bulk kerogen by a benzene-water two phase partition method under acidic condition was made. Microscopic observation revealed that amorphous kerogens and structured kerogens were fractionated effectively by this method. Characteristics of the amorphous and structured kerogens fractionated by this method were examined by some chemical analyses and compared with those of the bulk kerogen and humic acid isolated from the same rock sample (Haizume Formation, Pleistocene, Japan). The elemental and infrared (IR) analyses showed that the amorphous kerogen fraction had the highest atomic H/C ratio and the lowest atomic N/C ratio and was the richest in aliphatic structures and carbonyl and carboxyl functional groups. Quantities of fatty acids from the saponification products of each geopolymer were in agreement with the results of elemental and IR analyses. Distribution of the fatty acids was suggestive that more animal lipids participate in the formation of amorphous kerogens because of the abundance of relatively lower molecular weight fatty acids (such as C 16 and C 18 acids) in saponification products of amorphous kerogens. On the other hand, although the amorphous kerogen fraction tends to be rich in aliphatic structures compared with bulk kerogen of the same rock samples, van Krevelen plots of elemental compositions of kerogens from the core samples (Nishiyama Oil Field, Tertiary, Japan) reveal that the amorphous kerogen fraction is not necessarily characterized by markedly high atomic H/C ratio. This was attributed to the oxic environment of deposition and the abundance of biodegraded terrestrial amorphous organic matter in the amorphous kerogen fraction used in this work.
Arsenic removal from water using a novel amorphous adsorbent developed from coal fly ash.

PubMed

Zhang, Kaihua; Zhang, Dongxue; Zhang, Kai

2016-01-01

A novel effective adsorbent of alumina/silica oxide hydrate (ASOH) for arsenic removal was developed through simple chemical reactions using coal fly ash. The iron-modified ASOH with enhancing adsorption activity was further developed from raw fly ash based on the in situ technique. The adsorbents were characterized by X-ray diffraction, Fourier transform infrared spectrometry, scanning electron micrograph, laser particle size and Brunauer-Emmet-Teller surface area. The results show that the adsorbents are in amorphous and porous structure, the surface areas of which are 8-12 times that of the raw ash. The acidic hydrothermal treatment acts an important role in the formation of the amorphous structure of ASOH rather than zeolite crystal. A series of adsorption experiments for arsenic on them were studied. ASOH can achieve a high removal efficiency for arsenic of 96.4% from water, which is more than 2.5 times that of the raw ash. Iron-modified ASOH can enhance the removal efficiency to reach 99.8% due to the in situ loading of iron (Fe). The condition of synthesis pH = 2-4 is better for iron-modified ASOH to adsorb arsenic from water.
Silica in a Mars analog environment: Ka u Desert, Kilauea Volcano, Hawaii

USGS Publications Warehouse

Seelos, K.D.; Arvidson, R. E.; Jolliff, B.L.; Chemtob, S.M.; Morris, R.V.; Ming, D. W.; Swayze, G.A.

2010-01-01

Airborne Visible/Near-Infrared Imaging Spectrometer (AVIRIS) data acquired over the Ka u Desert are atmospherically corrected to ground reflectance and used to identify the mineralogic components of relatively young basaltic materials, including 250-700 and 200-400 year old lava flows, 1971 and 1974 flows, ash deposits, and solfatara incrustations. To provide context, a geologic surface units map is constructed, verified with field observations, and supported by laboratory analyses. AVIRIS spectral endmembers are identified in the visible (0.4 to 1.2 ??m) and short wave infrared (2.0 to 2.5 ??m) wavelength ranges. Nearly all the spectral variability is controlled by the presence of ferrous and ferric iron in such minerals as pyroxene, olivine, hematite, goethite, and poorly crystalline iron oxides or glass. A broad, nearly ubiquitous absorption feature centered at 2.25 ??m is attributed to opaline (amorphous, hydrated) silica and is found to correlate spatially with mapped geologic surface units. Laboratory analyses show the silica to be consistently present as a deposited phase, including incrustations downwind from solfatara vents, cementing agent for ash duricrusts, and thin coatings on the youngest lava flow surfaces. A second, Ti-rich upper coating on young flows also influences spectral behavior. This study demonstrates that secondary silica is mobile in the Ka u Desert on a variety of time scales and spatial domains. The investigation from remote, field, and laboratory perspectives also mimics exploration of Mars using orbital and landed missions, with important implications for spectral characterization of coated basalts and formation of opaline silica in arid, acidic alteration environments. Copyright 2010 by the American Geophysical Union.

Submarine fissure eruptions and hydrothermal vents on the southern Juan de Fuca Ridge: preliminary observations from the submersible Alvin

USGS Publications Warehouse

Normark, W.R.

1986-01-01

The submersible Alvin was used to investigate 3 active hydrothermal discharge sites along the S Juan de Fuca Ridge in September 1984. The hydrothermal zones occur within a 10-30m-deep, 30-50m-wide cleft marking the center of the axial valley. This cleft is the eruptive locus for the axial valley. The hydrothermal vents coincide with the main eruptive vents along the cleft. Each hydrothermal zone has multiple discharge sites extending as much as 500m along the cleft. Sulfide deposits occur as clusters (15-100m2 area) of small chimneys (= or <2m high) and as individual and clustered fields of large, branched chimneys (= or <10m high). Recovered sulfide samples are predominantly the tops of chimneys and spires and typically contain more than 80% sphalerite and wurtzite with minor pyrrhotite, pyrite, marcasite, isocubanite, chalcopyrite, anhydrite, anhydrite, and amorphous silica. The associated hydrothermal fluids have the highest chlorinity of any reported to date.-Authors
Preparation and characteristics of biosilica derived from marine diatom biomass of Nitzschia closterium and Thalassiosira

NASA Astrophysics Data System (ADS)

Qi, Yarong; Wang, Xin; Cheng, Jay Jiayang

2017-05-01

In this study, biosilica of high purity was successfully prepared from marine diatom ( Nitzschia closterium and Thalassiosira) biomass using an optimized novel method with acid washing treatment followed by thermal treatment of the biomass. The optimal condition of the method was 2% diluted HCl washing and baking at 600°C. The SiO2 contents of N. closterium biosilica and Thalassiosira biosilica were 92.23% and 91.52%, respectively, which were both higher than that of diatomite biosilica. The SiO2 morphologies of both biosilica are typical amorphous silica. Besides, N. closterium biosilica possessed micropores and fibers with a surface area of 59.81m2/g. And Thalassiosira biosilica possessed a mesoporous hierarchical skeleton with a surface area of 9.91m2/g. The results suggest that the biosilica samples obtained in this study present highly porous structures. The prepared porous biosilica material possesses great potential to be used as drug delivery carrier, biosensor, biocatalyst as well as adsorbent in the future.
Time-resolved diffraction of shock-released SiO 2 and diaplectic glass formation

DOE PAGES

Gleason, A. E.; Bolme, C. A.; Lee, H. J.; ...

2017-11-14

Understanding how rock-forming minerals transform under shock loading is critical for modeling collisions between planetary bodies, interpreting the significance of shock features in minerals and for using them as diagnostic indicators of impact conditions, such as shock pressure. To date, our understanding of the formation processes experienced by shocked materials is based exclusively on ex situ analyses of recovered samples. Formation mechanisms and origins of commonly observed mesoscale material features, such as diaplectic (i.e., shocked) glass, remain therefore controversial and unresolvable. Here in this paper we show in situ pump-probe X-ray diffraction measurements on fused silica crystallizing to stishovite onmore » shock compression and then converting to an amorphous phase on shock release in only 2.4 ns from 33.6 GPa. Recovered glass fragments suggest permanent densification. These observations of real-time diaplectic glass formation attest that it is a back-transformation product of stishovite with implications for revising traditional shock metamorphism stages.« less
Time-resolved diffraction of shock-released SiO 2 and diaplectic glass formation

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

Gleason, A. E.; Bolme, C. A.; Lee, H. J.

Understanding how rock-forming minerals transform under shock loading is critical for modeling collisions between planetary bodies, interpreting the significance of shock features in minerals and for using them as diagnostic indicators of impact conditions, such as shock pressure. To date, our understanding of the formation processes experienced by shocked materials is based exclusively on ex situ analyses of recovered samples. Formation mechanisms and origins of commonly observed mesoscale material features, such as diaplectic (i.e., shocked) glass, remain therefore controversial and unresolvable. Here in this paper we show in situ pump-probe X-ray diffraction measurements on fused silica crystallizing to stishovite onmore » shock compression and then converting to an amorphous phase on shock release in only 2.4 ns from 33.6 GPa. Recovered glass fragments suggest permanent densification. These observations of real-time diaplectic glass formation attest that it is a back-transformation product of stishovite with implications for revising traditional shock metamorphism stages.« less
Origin of melting point depression for rare gas solids confined in carbon pores

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

Morishige, Kunimitsu, E-mail: morishi@chem.ous.ac.jp; Kataoka, Takaaki

To obtain insights into the mechanism of the melting-point depression of rare gas solids confined in crystalline carbon pores, we examined the freezing and melting behavior of Xe and Ar confined to the crystalline pores of ordered mesoporous carbons as well as compressed exfoliated graphite compared to the amorphous pores of ordered mesoporous silicas, by means of X-ray diffraction. For the Xe and Ar confined to the crystalline carbon pores, there was no appreciable thermal hysteresis between freezing and melting. Furthermore, the position of the main diffraction peak did not change appreciably on freezing and melting. This strongly suggests thatmore » the liquids confined in the carbon pores form a multilayered structure parallel to the smooth walls. For the Xe and Ar confined to the amorphous silica pores, on the other hand, the position of the main diffraction peak shifted into higher scattering angle on freezing suggested that the density of the confined solid is distinctly larger than for the confined liquid. Using compressed exfoliated graphite with carbon walls of higher crystallinity, we observed that three-dimensional (3D) microcrystals of Xe confined in the slit-shaped pores melted to leave the unmelted bilayers on the pore walls below the bulk triple point. The lattice spacing of the 3D microcrystals confined is larger by ∼0.7% than that of the bilayer next to the pore walls in the vicinity of the melting point.« less
Effect of amorphous silica ash used as a partial replacement for cement on the compressive and flexural strengths cement mortar.

NASA Astrophysics Data System (ADS)

Usman, Aliyu; Ibrahim, Muhammad B.; Bala, Nura

2018-04-01

This research is aimed at investigating the effect of using amorphous silica ash (ASA) obtained from rice husk as a partial replacement of ordinary Portland cement (OPC) on the compressive and flexural strength of mortar. ASA was used in partial replacement of ordinary Portland cement in the following percentages 2.5 percent, 5 percent, 7.5 percent and 10 percent. These partial replacements were used to produce Cement-ASA mortar. ASA was found to contain all major chemical compounds found in cement with the exception of alumina, which are SiO2 (91.5%), CaO (2.84%), Fe2O3 (1.96%), and loss on ignition (LOI) was found to be 9.18%. It also contains other minor oxides found in cement. The test on hardened mortar were destructive in nature which include flexural strength test on prismatic beam (40mm x 40mm x 160mm) and compressive strength test on the cube size (40mm x 40mm, by using the auxiliary steel plates) at 2,7,14 and 28 days curing. The Cement-ASA mortar flexural and compressive strengths were found to be increasing with curing time and decreases with cement replacement by ASA. It was observed that 5 percent replacement of cement with ASA attained the highest strength for all the curing ages and all the percentage replacements attained the targeted compressive strength of 6N/mm2 for 28 days for the cement mortar
Protein corona changes mediated by surface modification of amorphous silica nanoparticles suppress acute toxicity and activation of intrinsic coagulation cascade in mice

NASA Astrophysics Data System (ADS)

Yoshida, Tokuyuki; Yoshioka, Yasuo; Morishita, Yuki; Aoyama, Michihiko; Tochigi, Saeko; Hirai, Toshiro; Tanaka, Kota; Nagano, Kazuya; Kamada, Haruhiko; Tsunoda, Shin-ichi; Nabeshi, Hiromi; Yoshikawa, Tomoaki; Higashisaka, Kazuma; Tsutsumi, Yasuo

2015-06-01

Recently, nanomaterial-mediated biological effects have been shown to be governed by the interaction of nanomaterials with some kinds of proteins in biological fluids, and the physical characteristics of the nanomaterials determine the extent and type of their interactions with proteins. Here, we examined the relationships between the surface properties of amorphous silica nanoparticles with diameters of 70 nm (nSP70), their interactions with some proteins in biological fluids, and their toxicity in mice after intravenous administration. The surface modification of nSP70 with amino groups (nSP70-N) prevented acute lethality and abnormal activation of the coagulation cascade found in the nSP70-treated group of mice. Since our previous study showed that coagulation factor XII played a role in the nSP70-mediated abnormal activation of the coagulation cascade, we examined the interaction of nSP70 and nSP70-N with coagulation factor XII. Coagulation factor XII bonded to the surface of nSP70 to a greater extent than that observed for nSP70-N, and consequently more activation of coagulation factor XII was observed for nSP70 than for nSP70-N. Collectively, our results suggest that controlling the interaction of nSP70 with blood coagulation factor XII by modifying the surface properties would help to inhibit the nSP70-mediated abnormal activation of the blood coagulation cascade.
Insights into Silicate and Oxide Melt Structure from Amorphous, Non-Glass-Forming Materials

NASA Astrophysics Data System (ADS)

Stebbins, J. F.

2015-12-01

Many silicate and oxide liquids of interest in the Earth sciences and in technology cannot readily be quenched to glasses, either because of low silica contents (and hence low viscosity at the melting point and accompanying liquid 'fragility') or because of liquid-liquid unmixing at high temperature. Although in-situ, high temperature structural tools have been in use for decades and are rapidly developing, many methods are still most informative for glass samples quenched to ambient pressure and temperature, e.g. high-resolution solid-state NMR. Amorphous oxides, including alumina and silicate compositions, have widespread technological applications. These are generally deposited by a variety of high-energy sputtering methods, as films of thicknesses of 10's to 100's of nm. Using Al-27, Si-29, and O-17 NMR, we have recently shown that for such films, very similar short-range structure is seen in materials made by very different kinetic pathways, such as sol-gel synthesis vs. ion-beam sputtering. This path-independent structure suggests that these materials pass through transient equilibrium states during their formation, probably that of deeply supercooled liquids just above glass transition temperatures. In the HfO2-SiO2 and ZrO2-SiO2 systems, for example, samples have well-resolved O-17 NMR spectra, allowing quantitation of O sites with only Hf(Zr) neighbors (so-called "free" oxide ions), with mixed Hf(Zr) and Si neighbors, and Si only. The observed oxygen speciation agrees well with a simple thermodynamic model of one of the most fundamental equilibria in silicate systems, namely the reaction of bridging (Si-O-Si) and "free" (e.g. OHf3 and OHf4) oxide ions to produce "non-bridging" oxygens (e.g. Si-OHf2). This new approach to sampling such structural equilibria in compositions far outside the range of normal glass-forming liquids may provide new insights into more geological compositions as well, as well as in more general models of silicate melt chemistry.
In situ synthesis, characterization, and catalytic performance of tungstophosphoric acid encapsulated into the framework of mesoporous silica pillared clay.

PubMed

Li, Baoshan; Liu, Zhenxing; Han, Chunying; Ma, Wei; Zhao, Songjie

2012-07-01

Mesoporous silica pillared clay (SPC) incorporated with tungstophosphoric acid (HPW) has been synthesized via in situ introducing P and W source in the acidic suspension of the clay interlayer template during the formation of the silica pillared clay. The samples were characterized by XRD, XRF, FT-IR, TG-DTA, N(2) adsorption-desorption, and SEM techniques. The results showed that the HPW formed by in situ method has been effectively introduced into the framework of mesoporous silica pillared clay and its Keggin structure remained perfectly after formation of the materials. In addition, samples with similar HPW loadings were also prepared by impregnation method using SPC as the support. HPW in the incorporated samples was better dispersed into the silica pillared clay than in the impregnated samples. The results of catalytic tests indicated that the encapsulated materials demonstrated better catalytic performance than the impregnated samples in oxidative desulfurization (ODS) of dibenzothiophene (DBT). Copyright © 2012 Elsevier Inc. All rights reserved.
Determination of acrolein and other carbonyls in cigarette smoke using coupled silica cartridges impregnated with hydroquinone and 2,4-dinitrophenylhydrazine.

PubMed

Uchiyama, Shigehisa; Inaba, Yohei; Kunugita, Naoki

2010-06-25

A new method for the determination of acrolein and other carbonyls in cigarette smoke using a dual cartridge system has been developed. Each cartridge consists of reagent-impregnated silica particles. The first contains hydroquinone (HQ) for the inhibition of acrolein polymerization, while the second contains 2,4-dinitrophenylhydrazine (DNPH) for the derivatization of carbonyls. Smoke samples were firstly drawn through the cartridge containing HQ-impregnated silica (HQ-silica) and then through the DNPH-impregnated silica (DNPH-silica). Acrolein in the sample was completely trapped in the first HQ-silica cartridge. Some other airborne carbonyls were also trapped by the HQ-silica, and those that pass through were trapped in the second DNPH-silica cartridge. Extraction was performed in the reverse direction to air sampling. When solvent was eluted through the dual-cartridges, excess DNPH was washed into the HQ bed where it reacted with acrolein and other trapped carbonyls to form the corresponding hydrazone derivatives. All of the hydrazones derived from airborne carbonyls were completely separated and measured using high-performance liquid chromatography. This HQ-DNPH-method can be applied for the determination of acrolein and other alpha,beta-unsaturated aldehydes, such as crotonaldehyde, in cigarette smoke. Copyright 2010 Elsevier B.V. All rights reserved.
Biocompatibility of crystalline opal nanoparticles

PubMed Central

2012-01-01

Background Silica nanoparticles are being developed as a host of biomedical and biotechnological applications. For this reason, there are more studies about biocompatibility of silica with amorphous and crystalline structure. Except hydrated silica (opal), despite is presents directly and indirectly in humans. Two sizes of crystalline opal nanoparticles were investigated in this work under criteria of toxicology. Methods In particular, cytotoxic and genotoxic effects caused by opal nanoparticles (80 and 120 nm) were evaluated in cultured mouse cells via a set of bioassays, methylthiazolyldiphenyl-tetrazolium-bromide (MTT) and 5-bromo-2′-deoxyuridine (BrdU). Results 3T3-NIH cells were incubated for 24 and 72 h in contact with nanocrystalline opal particles, not presented significant statistically difference in the results of cytotoxicity. Genotoxicity tests of crystalline opal nanoparticles were performed by the BrdU assay on the same cultured cells for 24 h incubation. The reduction of BrdU-incorporated cells indicates that nanocrystalline opal exposure did not caused unrepairable damage DNA. Conclusions There is no relationship between that particles size and MTT reduction, as well as BrdU incorporation, such that the opal particles did not induce cytotoxic effect and genotoxicity in cultured mouse cells. PMID:23088559
Polymer-ceramic nanocomposites for applications in the bone surgery

NASA Astrophysics Data System (ADS)

Stodolak, E.; Gadomska, K.; Lacz, A.; Bogun, M.

2009-01-01

The subject of this work was preparation and investigation of properties of a nanocomposite material based on polymer matrix modified with nanometric silica particles (SiO2). The composite matrix consisted of resorbable P(L/DL)LA polymer with certified biocompatibility. Nanometric silica was introduced into the matrix by means of ultrasonic homogenisation and/or mechanical stirring. The silica was introduced directly e.g. as nanoparticles or inside calcium alginate fibres which contained 3 wt.% of amorphous SiO2. Proper dispersion of nano-filliers was confirmed by means of thermal analysis (TG/DTA, DSC). It was observed, that the presence of inorganic nanoparticles influenced several surface parameters of the nanocomposites i.e. hydrophility (a decrease of surface energy) and topography (both in micro- and nano-scale). Additionally, the nanocomposites exhibited enhanced mechanical properties (Young's modulus, tensile strength) compared to the pure polymer. The nanocomposites were bioactive materials (SBF/3 days/37oC). Biological tests (MTT test) showed a good viability of human osteoblasts (hFOB 1.19) in contact with the nanocomposites surface. Results of preliminary biological tests carried out with the use of mother cells extracted from human bone marrow showed that the nanocomposites may provide differenation of bone cells.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Ambrosone, Alfredo; Scotto di Vettimo, Maria Rosaria; Malvindi, Maria Ada

It is generally accepted that silica (SiO{sub 2}) is not toxic. But the increasing use of silica nanoparticles (SiO{sub 2}NPs) in many different industrial fields has prompted the careful investigation of their toxicity in biological systems. In this report, we describe the effects elicited by SiO{sub 2}NPs on animal and cell physiology. Stable and monodisperse amorphous silica nanoparticles, 25 nM in diameter, were administered to living Hydra vulgaris (Cnidaria). The dose-related effects were defined by morphological and behavioral assays. The results revealed an all-or-nothing lethal toxicity with a rather high threshold (35 nM NPs) and a LT50 of 38 h.more » At sub lethal doses, the morphophysiological effects included: animal morphology alterations, paralysis of the gastric region, disorganization and depletion of tentacle specialized cells, increase of apoptotic and collapsed cells, and reduction of the epithelial cell proliferation rate. Transcriptome analysis (RNAseq) revealed 45 differentially expressed genes, mostly involved in stress response and cuticle renovation. Our results show that Hydra reacts to SiO{sub 2}NPs, is able to rebalance the animal homeostasis up to a relatively high doses of SiO{sub 2}NPs, and that the physiological modifications are transduced to gene expression modulation.« less
Influence of sample preparation on the transformation of low-density to high-density amorphous ice: An explanation based on the potential energy landscape

NASA Astrophysics Data System (ADS)

Giovambattista, Nicolas; Starr, Francis W.; Poole, Peter H.

2017-07-01

Experiments and computer simulations of the transformations of amorphous ices display different behaviors depending on sample preparation methods and on the rates of change of temperature and pressure to which samples are subjected. In addition to these factors, simulation results also depend strongly on the chosen water model. Using computer simulations of the ST2 water model, we study how the sharpness of the compression-induced transition from low-density amorphous ice (LDA) to high-density amorphous ice (HDA) is influenced by the preparation of LDA. By studying LDA samples prepared using widely different procedures, we find that the sharpness of the LDA-to-HDA transformation is correlated with the depth of the initial LDA sample in the potential energy landscape (PEL), as characterized by the inherent structure energy. Our results show that the complex phenomenology of the amorphous ices reported in experiments and computer simulations can be understood and predicted in a unified way from knowledge of the PEL of the system.
Use of Raman microscopy and multivariate data analysis to observe the biomimetic growth of carbonated hydroxyapatite on bioactive glass.

PubMed

Seah, Regina K H; Garland, Marc; Loo, Joachim S C; Widjaja, Effendi

2009-02-15

In the present contribution, the biomimetic growth of carbonated hydroxyapatite (HA) on bioactive glass were investigated by Raman microscopy. Bioactive glass samples were immersed in simulated body fluid (SBF) buffered solution at pH 7.40 up to 17 days at 37 degrees C. Raman microscopy mapping was performed on the bioglass samples immersed in SBF solution for different periods of time. The collected data was then analyzed using the band-target entropy minimization technique to extract the observable pure component Raman spectral information. In this study, the pure component Raman spectra of the precursor amorphous calcium phosphate, transient octacalcium phosphate, and matured HA were all recovered. In addition, pure component Raman spectra of calcite, silica glass, and some organic impurities were also recovered. The resolved pure component spectra were fit to the normalized measured Raman data to provide the spatial distribution of these species on the sample surfaces. The current results show that Raman microscopy and multivariate data analysis provide a sensitive and accurate tool to characterize the surface morphology, as well as to give more specific information on the chemical species present and the phase transformation of phosphate species during the formation of HA on bioactive glass.
Hydrothermal Signatures at Gale Crater, Mars, and Possible In-Situ Formation of Tridymite

NASA Astrophysics Data System (ADS)

Yen, A. S.; Morris, R. V.; Gellert, R.; Berger, J. A.; Sutter, B.; Downs, R. T.; Bristow, T.; Treiman, A. H.; Ming, D. W.; Achilles, C.; Blake, D. F.; Chipera, S.; Clark, B. C.; Craig, P.; Morrison, S. M.; Rampe, E. B.; Schmidt, M. E.; Schwenzer, S. P.; Thompson, L. M.; Vaniman, D.

2017-12-01

The occurrence of tridymite, a high temperature SiO2 polymorph definitively identified by the Curiosity rover in the Buckskin mudstone sample at Gale crater, Mars, has been attributed to detrital accumulation of rhyolitic material. This interpretation of a detrital origin is revisited in light of the observation that the tridymite-hosting sediments appear to have interacted with the same fluids that produced alteration halos in the overlying sandstone. The alteration halos in the Stimson sandstone are light-toned, elevated silica zones within 50 cm of a central fracture. They have likely experienced chemical leaching under acidic conditions resulting in depletion of metals (including Al), retention of Ti, formation of amorphous iron sulfates, 50% reduction of the pyroxene:plagioclase ratio, a factor of two increase in the Fe/Mn ratio, and passive enrichment of Si. This alteration is not constrained (nor precluded) to have occurred at elevated temperatures, but there are abundant indicators of hydrothermal activity within Gale crater. High concentrations of Ge, Zn, Ni, Pb, Cu, Se and Ga in a variety of samples analyzed by the Alpha Particle X-ray Spectrometer are indicative of mobility in hydrothermal solutions. Mineralogy of Gale crater samples determined by the CheMin X-ray diffraction instrument includes phases which may be associated with hydrothermal activity (smectites, anhydrite, hematite), but definitive detections of mineral assemblages that are necessarily hydrothermal in origin remain absent. The nearly identical patterns of enriched and depleted elements of the Stimson alteration halos (relative to parent rocks) and the tridymite-bearing unit (relative to typical mudstone samples) require the consideration of co-genetic origins. Cristobalite, a SiO2 polymorph stable above 1470°C found in the Buckskin sample, is known to form in hydrothermal solutions at temperatures well below its stability field (Henderson et al., 1971). Formation of well-crystalline tridymite at temperatures below its thermodynamic stability range (870-1470°C) has not been established, but cannot be excluded. Thus, the possibility that the fluids responsible for the passive enrichment of silica in the Stimson alteration halos also resulted in the in-situ formation of tridymite deserves further consideration.
Recent Results from the Spirit Rover at Home Plate and "Silica Valley"

NASA Astrophysics Data System (ADS)

Squyres, S. W.

2007-12-01

The Mars Exploration Rover Spirit has spent more than 500 sols exploring Home Plate in the inner basin of the Columbia Hills, and adjacent materials. Home Plate is a plateau of layered rocks 80-90 meters in diameter and ~2 meters high. The rocks are clastic and of moderately altered alkali basalt composition, enriched in some volatile elements. A coarse-grained lower unit is overlain by a finer-grained upper unit. Textural observations, including a prominent bomb sag, indicate that the lower strata were emplaced in an explosive event. Geochemical similarities to nearby volcanic rocks and the enrichment in volatile elements favor an explosive volcanic origin. Along the northern portion of Home Plate, the upper unit is very well sorted and composed of well rounded sand sized grains, pointing to textural maturity and suggesting an eolian origin. Along the southeastern portion, however, the upper unit contains some coarser granules too large to be transported by saltation. While their size is comparable to other clasts on Mars that have moved by saltation-induced creep, the observed textures clearly are consistent with emplacement as a pyroclastic surge. The upper and lower units are effectively identical in composition, so the upper unit probably represents a finer-grained fraction of pyroclastic materials that may have undergone some local reworking by wind. Rocks along the margins of Home Plate show a consistent dip toward the center of the plateau. We interpret Home Plate to be the eroded remnants of a formerly more extensive sheet of pyroclastic materials, perhaps produced in a phreatomagmatic eruption. The inward dips may have arisen when pyroclastic materials overrode and partially buried a pre-existing bowl-shaped depression such as an impact crater, draping the topography. Immediately to the east of Home Plate is a narrow valley bounded on one side by Home Plate and on the other by Mitcheltree Ridge. While operating within this valley, Spirit's inoperative right front wheel excavated a small patch of high albedo soil. Mini-TES spectra of this soil were well fit by amorphous silica, and subsequent investigation with the APXS showed a composition that was more than 90% SiO2. The deposits are also enriched in Ti. Mini-TES spectra of nearby rocks also show a strong signature of amorphous silica, and APXS spectra of these rocks also confirm a high silica content. We consider two hypotheses for the formation of these silica-rich deposits. One is that they developed via precipitation from hydrothermal fluids. Siliceous sinter deposits are common in terrestrial hydrothermal environments where fluids dissolve Si from host rocks at high temperatures and then reprecipitate silica at lower temperatures. Alternatively, the Si-rich materials may represent the remnants of formerly basaltic materials that have been extensively leached in a fumarolic environment under acid sulfate conditions. In either case, the proximity to Home Plate is consistent with formation via the interaction of basaltic volcanism with groundwater. The astrobiological implications of these Si-rich deposits may be significant. Both hydrothermal systems and fumaroles are capable of supporting microbial ecosystems on Earth, and precipitated silica deposits in both environments can preserve strong textural evidence of microbial life.
Elemental properties of copper slag and measured airborne exposures at a copper slag processing facility.

PubMed

Mugford, Christopher; Gibbs, Jenna L; Boylstein, Randy

2017-08-01

In 1974, the National Institute for Occupational Safety and Health recommended a ban on the use of abrasives containing >1% silica, giving rise to abrasive substitutes like copper slag. We present results from a National Institute for Occupational Safety and Health industrial hygiene survey at a copper slag processing facility that consisted of the collection of bulk samples for metals and silica; and full-shift area and personal air samples for dust, metals, and respirable silica. Carcinogens, suspect carcinogens, and other toxic elements were detected in all bulk samples, and area and personal air samples. Area air samples identified several areas with elevated levels of inhalable and respirable dust, and respirable silica: quality control check area (236 mg/m 3 inhalable; 10.3 mg/m 3 respirable; 0.430 mg/m 3 silica), inside the screen house (109 mg/m 3 inhalable; 13.8 mg/m 3 respirable; 0.686 mg/m 3 silica), under the conveyor belt leading to the screen house (19.8 mg/m 3 inhalable), and inside a conveyor access shack (11.4 mg/m 3 inhalable; 1.74 mg/m 3 respirable; 0.067 mg/m 3 silica). Overall, personal dust samples were lower than area dust samples and did not exceed published occupational exposure limits. Silica samples collected from a plant hand and a laborer exceeded the American Conference of Governmental Industrial Hygienist Threshold Limit Value of 0.025 µg/m 3 . All workers involved in copper slag processing (n = 5) approached or exceeded the Occupational Safety and Health Administration permissible exposure limit of 10 µg/m 3 for arsenic (range: 9.12-18.0 µg/m 3 ). Personal total dust levels were moderately correlated with personal arsenic levels (R s = 0.70) and personal respirable dust levels were strongly correlated with respirable silica levels (R s = 0.89). We identified multiple areas with elevated levels of dust, respirable silica, and metals that may have implications for personal exposure at other facilities if preventive measures are not taken. To our knowledge, this is the first attempt to characterize exposures associated with copper slag processing. More in-depth air monitoring and health surveillance is needed to understand occupational exposures and health outcomes in this industry.
Silica nanoparticles are less toxic to human lung cells when deposited at the air–liquid interface compared to conventional submerged exposure

PubMed Central

Saathoff, Harald; Leisner, Thomas; Al-Rawi, Marco; Simon, Michael; Seemann, Gunnar; Dössel, Olaf; Mülhopt, Sonja; Paur, Hanns-Rudolf; Fritsch-Decker, Susanne

2014-01-01

Summary Background: Investigations on adverse biological effects of nanoparticles (NPs) in the lung by in vitro studies are usually performed under submerged conditions where NPs are suspended in cell culture media. However, the behaviour of nanoparticles such as agglomeration and sedimentation in such complex suspensions is difficult to control and hence the deposited cellular dose often remains unknown. Moreover, the cellular responses to NPs under submerged culture conditions might differ from those observed at physiological settings at the air–liquid interface. Results: In order to avoid problems because of an altered behaviour of the nanoparticles in cell culture medium and to mimic a more realistic situation relevant for inhalation, human A549 lung epithelial cells were exposed to aerosols at the air–liquid interphase (ALI) by using the ALI deposition apparatus (ALIDA). The application of an electrostatic field allowed for particle deposition efficiencies that were higher by a factor of more than 20 compared to the unmodified VITROCELL deposition system. We studied two different amorphous silica nanoparticles (particles produced by flame synthesis and particles produced in suspension by the Stöber method). Aerosols with well-defined particle sizes and concentrations were generated by using a commercial electrospray generator or an atomizer. Only the electrospray method allowed for the generation of an aerosol containing monodisperse NPs. However, the deposited mass and surface dose of the particles was too low to induce cellular responses. Therefore, we generated the aerosol with an atomizer which supplied agglomerates and thus allowed a particle deposition with a three orders of magnitude higher mass and of surface doses on lung cells that induced significant biological effects. The deposited dose was estimated and independently validated by measurements using either transmission electron microscopy or, in case of labelled NPs, by fluorescence analyses. Surprisingly, cells exposed at the ALI were less sensitive to silica NPs as evidenced by reduced cytotoxicity and inflammatory responses. Conclusion: Amorphous silica NPs induced qualitatively similar cellular responses under submerged conditions and at the ALI. However, submerged exposure to NPs triggers stronger effects at much lower cellular doses. Hence, more studies are warranted to decipher whether cells at the ALI are in general less vulnerable to NPs or specific NPs show different activities dependent on the exposure method. PMID:25247141
Infrared Spectroscopy for Rapid Characterization of Drill Core and Cutting Mineralogy

NASA Astrophysics Data System (ADS)

Calvin, W. M.; Kratt, C.; Kruse, F. A.

2009-12-01

Water geochemistry can vary with depth and location within a geothermal reservoir, owing to natural factors such as changing rock type, gas content, fluid source and temperature. The interaction of these variable fluids with the host rock will cause well known changes in alteration mineral assemblages that are commonly factored into the exploration of hydrothermal systems for economic metals, but are less utilized with regard to mapping borehole geology for geothermal energy production. Chemistry of geothermal fluids and rock alteration products can impact production factors such as pipeline corrosion and scaling and early studies explored the use of both silica and chlorites as geothermometers. Infrared spectroscopy is particularly good at identifying a wide variety of alteration minerals, especially in discrimination among clay minerals, with no sample preparation. The technique has been extensively used in the remote identification of materials, but is not commonly used on drill core or chips. We have performed several promising pilot studies that suggest the power of the technique to sample continuously and provide mineral logs akin to geophysical ones. We have surveyed a variety of samples, including drill chip boards, boxed core, and drill cuttings from envelopes, sample bottles and chip trays. This work has demonstrated that core and drill chips can be rapidly surveyed, acquiring spectra every few to tens of cm of section, or the vertical resolution of the chip tray (typically 10 feet). Depending on the sample type we can acquire spectral data over thousands of feet depth at high vertical resolution in a fraction of the time that is needed for traditional analytical methods such as XRD or TEM with better accuracy than traditional geologic drill or chip logging that uses visual inspection alone. We have successfully identified layered silicates such as illite, kaolinite, montmorillonite chlorite and prehnite, zeolites, opal, calcite, jarosite and iron oxides and hydroxides in geothermal drill samples. We are currently developing automated analysis techniques to convert this detailed spectral logging data into high-vertical-resolution mineral depth profiles that can be linked to lithology, stratigraphy, fracture zones and potential for geothermal production. Also in development are metrics that would link mapped mineralogy to known geothermometers such as Na-K, Mg depletion, discrimination among illite, montmorillonite, and beidellite, and kaolinite crystallinity. Identification of amorphous and crystalline silica components (chalcedony, crystobalite and quartz) can also constrain silica geothermometry. The degree of alteration and some mineral types have been shown to be a proxy for host rock permeability, natural circulation, and the potential for reservoir sealing. Analysis of alteration intensity is also under way. We will present a synthesis of results to date.

[Free crystalline silica: a comparison of methods for its determination in total dust].

PubMed

Maciejewska, Aleksandra; Szadkowska-Stańczyk, Irena; Kondratowicz, Grzegorz

2005-01-01

The major objective of the study was to compare and investigate the usefulness of quantitative analyses of free crystalline silica (FCS) in the assessment of dust exposure in samples of total dust of varied composition, using three methods: chemical method in common use in Poland; infrared spectrometry; and x-ray powder diffraction. Mineral composition and FCS contents were investigated in 9 laboratory samples of raw materials, materials, and industrial wastes, containing from about 2 to over 80% of crystalline silica and reduced to particles of size corresponding with that of total dust. Sample components were identified using XRD and FT-IR methods. Ten independent determinations of FCS with each of the three study methods were performed in dust samples. An analysis of linear correlation was applied to investigate interrelationship between mean FCS determinations. In analyzed dust samples, along with silica dust there were numerous minerals interfering with silica during the quantitative analysis. Comparison of mean results of FCS determinations showed that the results obtained using the FT-IR method were by 12-13% lower than those obtained with two other methods. However, the differences observed were within the limits of changeability of results associated with their precision and dependence on reference materials used. Assessment of occupational exposure to dusts containing crystalline silica can be performed on the basis of quantitative analysis of FCS in total dusts using each of the compared methods. The FT-IR method is most appropriate for the FCS determination in samples of small amount of silica or collected at low dust concentrations; the XRD method for the analysis of multicomponent samples; and the chemical method in the case of medium and high FCS contents in samples or high concentrations of dusts in the work environment.
Preparation of electrochemically active silicon nanotubes in highly ordered arrays

PubMed Central

Grünzel, Tobias; Lee, Young Joo; Kuepper, Karsten

2013-01-01

Summary Silicon as the negative electrode material of lithium ion batteries has a very large capacity, the exploitation of which is impeded by the volume changes taking place upon electrochemical cycling. A Si electrode displaying a controlled porosity could circumvent the difficulty. In this perspective, we present a preparative method that yields ordered arrays of electrochemically competent silicon nanotubes. The method is based on the atomic layer deposition of silicon dioxide onto the pore walls of an anodic alumina template, followed by a thermal reduction with lithium vapor. This thermal reduction is quantitative, homogeneous over macroscopic samples, and it yields amorphous silicon and lithium oxide, at the exclusion of any lithium silicides. The reaction is characterized by spectroscopic ellipsometry for thin silica films, and by nuclear magnetic resonance and X-ray photoelectron spectroscopy for nanoporous samples. After removal of the lithium oxide byproduct, the silicon nanotubes can be contacted electrically. In a lithium ion electrolyte, they then display the electrochemical waves also observed for other bulk or nanostructured silicon systems. The method established here paves the way for systematic investigations of how the electrochemical properties (capacity, charge/discharge rates, cyclability) of nanoporous silicon negative lithium ion battery electrode materials depend on the geometry. PMID:24205460
Attenuated total reflectance spectroscopy of plant leaves: A tool for ecological and botanical studies

USGS Publications Warehouse

Ribeiro da Luz, B.

2006-01-01

??? Attenuated total reflectance (ATR) spectra of plant leaves display complex absorption features related to organic constituents of leaf surfaces. The spectra can be recorded rapidly, both in the field and in the laboratory, without special sample preparation. ??? This paper explores sources of ATR spectral variation in leaves, including compositional, positional and temporal variations. Interspecific variations are also examined, including the use of ATR spectra as a tool for species identification. ??? Positional spectral variations generally reflected the abundance of cutin and the epicuticular wax thickness and composition. For example, leaves exposed to full sunlight commonly showed more prominent cutin- and wax-related absorption features compared with shaded leaves. Adaxial vs. abaxial leaf surfaces displayed spectral variations reflecting differences in trichome abundance and wax composition. Mature vs. young leaves showed changes in absorption band position and intensity related to cutin, polysaccharide, and possibly amorphous silica development on and near the leaf surfaces. ??? Provided that similar samples are compared (e.g. adaxial surfaces of mature, sun-exposed leaves) same-species individuals display practically identical ATR spectra. Using spectral matching procedures to analyze an ATR database containing 117 individuals, including 32 different tree species, 83% of the individuals were correctly identified. ?? The Authors (2006).
Radiation damage in a-SiO 2 exposed to intense positron pulses

NASA Astrophysics Data System (ADS)

Cassidy, D. B.; Mills, A. P.

2007-08-01

In addition to its numerous technological applications amorphous silica (a-SiO 2) is also well suited to the creation and study of exotic atoms such as positronium (Ps) and muonium. In particular, a dense Ps gas may be created by implanting an intense positron pulse into a porous a-SiO 2 sample. However, such positron pulses can constitute a significant dose of radiation, which may damage the sample. We have observed a reduction in the amount of Ps formed in a thin film of porous a-SiO 2 following irradiation by intense positron pulses, indicating the creation of paramagnetic centers. The data show that the primary effect of the irradiation is the inhibition of Ps formation, with no significant change in the subsequent Ps lifetime, from which we deduce that damage centers are created primarily in the bulk material and not on the internal surfaces of the pores, where they would be accessible to the long-lived Ps. We find that the damage is reversible, and that the system may be returned to its original state by heating to 700 K. The implications of these results for experiments with dense Ps in porous materials are discussed.
Characterization of laser damage performance of fused silica using photothermal absorption technique

NASA Astrophysics Data System (ADS)

Wan, Wen; Shi, Feng; Dai, Yifan; Peng, Xiaoqiang

2017-06-01

The subsurface damage and metal impurities have been the main laser damage precursors of fused silica while subjected to high power laser irradiation. Light field enhancement and thermal absorption were used to explain the appearance of damage pits while the laser energy is far smaller than the energy that can reach the intrinsic threshold of fused silica. For fused silica optics manufactured by magnetorheological finishing or advanced mitigation process, no scratch-related damage site occurs can be found on the surface. In this work, we implemented a photothermal absorption technique based on thermal lens method to characterize the subsurface defects of fused silica optics. The pump beam is CW 532 nm wavelength laser. The probe beam is a He-Ne laser. They are collinear and focused through the same objective. When pump beam pass through the sample, optical absorption induces the local temperature rise. The lowest absorptance that we can detect is about the order of magnitude of 0.01 ppm. When pump beam pass through the sample, optical absorption induces the local temperature rise. The photothermal absorption value of fused silica samples range from 0.5 to 10 ppm. The damage densities of the samples were plotted. The damage threshold of samples at 8J/cm2 were gived to show laser damage performance of fused silica.The results show that there is a strong correlation between the thermal absorption and laser damage density. The photothermal absorption technique can be used to predict and evaluate the laser damage performance of fused silica optics.
Biosilica: Molecular Biology, Biochemistry and Function in Demosponges as well as its Applied Aspects for Tissue Engineering.

PubMed

Wang, Xiaohong; Schröder, Heinz C; Wiens, Matthias; Schloßmacher, Ute; Müller, Werner E G

2012-01-01

Biomineralization, biosilicification in particular (i.e. the formation of biogenic silica, SiO(2)), has become an exciting source of inspiration for the development of novel bionic approaches following 'nature as model'. Siliceous sponges are unique among silica-forming organisms in their ability to catalyze silica formation using a specific enzyme termed silicatein. In this study, we review the present state of knowledge on silicatein-mediated 'biosilica' formation in marine demosponges, the involvement of further molecules in silica metabolism and their potential applications in nano-biotechnology and bio-medicine. While most forms of multicellular life have developed a calcium-based skeleton, a few specialized organisms complement their body plan with silica. Only sponges (phylum Porifera) are able to polymerize silica enzymatically mediated in order to generate massive siliceous skeletal elements (spicules) during a unique reaction, at ambient temperature and pressure. During this biomineralization process (i.e. biosilicification), hydrated, amorphous silica is deposited within highly specialized sponge cells, ultimately resulting in structures that range in size from micrometres to metres. This peculiar phenomenon has been comprehensively studied in recent years, and in several approaches, the molecular background was explored to create tools that might be employed for novel bioinspired biotechnological and biomedical applications. Thus, it was discovered that spiculogenesis is mediated by the enzyme silicatein and starts intracellularly. The resulting silica nanoparticles fuse and subsequently form concentric lamellar layers around a central protein filament, consisting of silicatein and the scaffold protein silintaphin-1. Once the growing spicule is extruded into the extracellular space, it obtains final size and shape. Again, this process is mediated by silicatein and silintaphin-1/silintaphin-1, in combination with other molecules such as galectin and collagen. The molecular toolbox generated so far allows the fabrication of novel micro- and nano-structured composites, contributing to the economical and sustainable synthesis of biomaterials with unique characteristics. In this context, first bioinspired approaches implement recombinant silicatein and silintaphin-1 for applications in the field of biomedicine (biosilica-mediated regeneration of tooth and bone defects) with promising results. Copyright © 2012 Elsevier Ltd. All rights reserved.
Nano-biosilica from marine diatoms: A brand new material for photonic applications

NASA Astrophysics Data System (ADS)

De Stefano, L.; Maddalena, P.; Moretti, L.; Rea, I.; Rendina, I.; De Tommasi, E.; Mocella, V.; De Stefano, M.

2009-07-01

Several biological organisms, from some sea shells to butterflies, exhibit sophisticated optical systems, which have been developed during the evolution of each species. The diatoms are microscopic algae enclosed between two valves of hydrated amorphous silica. These intricate structures, called frustules, show quite symmetric patterns of micrometric and nanometric pores. Their strong similarity with man-made objects suggests to exploit the optical properties of the frustules in light guiding and optical transducing. We have found very interesting results, both from the experimental and numerical points of view.
Microgravity

NASA Image and Video Library

2004-04-15

Marshall Space Flight Center's researchers have conducted suborbital experiments with ZBLAN, an optical material capable of transmitting 100 times more signal and information than silica fibers. The next step is to process ZBLAN in a microgravity environment to stop the formation of crystallites, small crystals caused by a chemical imbalances. Scientists want to find a way to make ZBLAN an amorphous (without an internal shape) material. Producing a material such as this will have far-reaching implications on advanced communications, medical and manufacturing technologies using lasers, and a host of other products well into the 21st century.
Silicon Oxycarbide Aerogels for High-Temperature Thermal Insulation

NASA Technical Reports Server (NTRS)

Evans, Owen; Rhine, Wendell; Coutinho, Decio

2010-01-01

This work has shown that the use of SOC-A35 leads to aerogel materials containing a significant concentration of carbidic species and limited amorphous free carbon. Substitution of the divalent oxide species in silica with tetravalent carbidic carbon has directly led to materials that exhibit increased network viscosity, reduced sintering, and limited densification. The SiOC aerogels produced in this work have the highest carbide content of any dense or porous SiOC glass reported in the literature at that time, and exhibit tremendous long-term thermal stability.
Anisotropic contribution to the van der Waals and the Casimir-Polder energies for CO2 and CH4 molecules near surfaces and thin films

NASA Astrophysics Data System (ADS)

Thiyam, Priyadarshini; Parashar, Prachi; Shajesh, K. V.; Persson, Clas; Schaden, Martin; Brevik, Iver; Parsons, Drew F.; Milton, Kimball A.; Malyi, Oleksandr I.; Boström, Mathias

2015-11-01

In order to understand why carbon dioxide (CO2) and methane (CH4) molecules interact differently with surfaces, we investigate the Casimir-Polder energy of a linearly polarizable CO2 molecule and an isotropically polarizable CH4 molecule in front of an atomically thin gold film and an amorphous silica slab. We quantitatively analyze how the anisotropy in the polarizability of the molecule influences the van der Waals contribution to the binding energy of the molecule.
Ultrahigh Vacuum Studies of the Fundamental Interactions of Chemical Warfare Agents and Their Simulants with Amorphous Silica

DTIC Science & Technology

2015-07-14

Aldao, C. M. Monte Carlo Study of Thermal Desorption Curves of Water from Zeolite Type A. Langmuir 1996, 12, 36-39. (83) Gorte, R. J. Design Parameters...and Diffusion-Limited TPD of Water from Zeolite Linde 4A. Thermochimica Acta 1998, 319, 177-184. (85) Palmero, A.; Loffler, D. G. Kinetics of Water...Desorption from Pelletized 4A and 5A Zeolites . Thermochimica Acta 1990, 159, 171-176. (86) Dean, J. A. Lange’s Handbook of Chemistry; Fifteenth
Densification behavior, nanocrystallization, and mechanical properties of spark plasma sintered Fe-based bulk amorphous alloys

NASA Astrophysics Data System (ADS)

Singh, Ashish Kumar

Fe-based amorphous alloys are gaining increasing attention due to their exceptional wear and corrosion resistance for potential structural applications. Two major challenges that are hindering the commercialization of these amorphous alloys are difficulty in processing of bulk shapes (diameter > 10 mm) and lack of ductility. Spark plasma sintering (SPS) is evolving as a promising technique for processing bulk shapes of amorphous and nanocrystalline materials. The objective of this work is to investigate densification behavior, nanocrystallization, and mechanical properties of SPS sintered Fe-based amorphous alloys of composition Fe48Cr15Mo14Y2C15B6. SPS processing was performed in three distinct temperature ranges of amorphous alloys: (a) below glass transition temperature (Tg), (b) between Tg and crystallization temperature (Tx), and (c) above Tx. Punch displacement data obtained during SPS sintering was correlated with the SPS processing parameters such as temperature, pressure, and sintering time. Powder rearrangement, plastic deformation below T g, and viscous flow of the material between Tg and Tx were observed as the main densification stages during SPS sintering. Micro-scale temperature distributions at the point of contact and macro-scale temperature distribution throughout the sample during SPS of amorphous alloys were modeled. The bulk amorphous alloys are expected to undergo structural relaxation and nanocrystallization during SPS sintering. X-ray diffraction (XRD), small angle neutron scattering (SANS), and transmission electron microscopy (TEM) was performed to investigate the evolution of nanocrystallites in SPS sintered Fe-based bulk amorphous alloys. The SANS analysis showed significant scattering for the samples sintered in the supercooled region indicating local structural and compositional changes with the profuse nucleation of nano-clusters (~4 nm). Compression tests and microhardness were performed on the samples sintered at different temperatures ranging from 570 °C to 800 °C. Maximum compression strength (1.1+/-0.2 MPa) was obtained for the samples sintered in the supercooled region. Effects of crystallization on tribological behavior of sintered samples were also investigated where crystallization resulted in increase in wear resistance. Laser surface hardening of SPS sintered amorphous samples were performed. Depending on the processing parameters, the laser surface irradiation causes structural relaxation and nanocrystallization, resulting in surface hardening.
Computer Modeling of the Thermal Conductivity of Cometary Ice

NASA Technical Reports Server (NTRS)

Bunch, Theodore E.; Wilson, Michael A.; Pohorille, Andrew

1998-01-01

The main objective of this research was to estimate the thermal conductivity of cometry ices from computer simulations of model amorphous ices. This was divided into four specific tasks: (1) Generating samples of amorphous water ices at different microporosities; (2) Comparing the resulting molecular structures of the ices with experimental results, for those densities where data was available; (3) Calculating the thermal conductivities of liquid water and bulk amorphous ices and comparing these results with experimentally determined thermal conductivities; and (4) Investigating how the thermal conductivity of amorphous ice depends upon the microscopic porosity of the samples. The thermal conductivity was found to be only weakly dependent on the microstructure of the amorphous ice. In general, the amorphous ices were found to have thermal conductivities of the same order of magnitude as liquid water. This is in contradiction to recent experimental estimates of the thermal conductivity of amorphous ice, and it is suggested that the extremely low value obtained experimentally is due to larger-scale defects in the ice, such as cracks, but it is not an intrinsic property of the bulk amorphous ice.
The investigation of order–disorder transition process of ZSM-5 induced by spark plasma sintering

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

Wang, Liang; Wang, Lianjun, E-mail: wanglj@dhu.edu.cn; Jiang, Wan

2014-04-01

Based on the amorphization of zeolites, an order–disorder transition method was used to prepare silica glass via Spark Plasma Sintering (SPS). In order to get a better understanding about the mechanism of amorphization induced by SPS, the intermediate products in this process were prepared and characterized by different characterization techniques. X-ray diffraction and High-energy synchrotron X-ray scattering show a gradual transformation from ordered crystal to glass. Local structural changes in glass network including Si–O bond length, O–Si–O bond angle, size of rings, coordination were detected by Infrared spectroscopy and {sup 29}Si magic-angle spinning nuclear magnetic resonance (NMR) spectroscopy. Topologically ordered,more » amorphous material with a different intermediate-range structure can be obtained by precise control of intermediate process which can be expected to optimize and design material. - Graphical abstract: Low-density, ordered zeolites collapse to the rigid amorphous glass through spark plasma sintering. The intermediate-range structure formed in the process of order–disorder transition may give rise to specific property. - Highlights: • Order–disorder transition process of ZSM-5 induced by spark plasma sintering was investigated using several methods including XRD, High-energy synchrotron X-ray scattering, SAXS, IR, NMR, ect. • Order–disorder transition induced by SPS was compared with TIA and PIA. • Three stages has been divided during the whole process. • The collapse temperature range which may give rise to intermediate-range structure has been located.« less
Interactions between DPPC as a component of lung surfactant and amorphous silica nanoparticles investigated by HILIC-ESI-MS.

PubMed

Silina, Yuliya E; Welck, Jennifer; Kraegeloh, Annette; Koch, Marcus; Fink-Straube, Claudia

2016-09-01

This paper reports a rapid HILIC-ESI-MS assay to quantify dipalmitoylphosphatidylcholine (DPPC) as component of lung surfactant for nanosafety studies. The technique was used to investigate the concentration-dependent sorption of DPPC to two-sizes of amorphous SiO2 nanoparticles (SiO2-NPs) in a MeOH:H2O (50/50v/v) mixture and in cell culture medium. In MeOH:H2O (50/50v/v), the sorption of DPPC was positively correlated with the nanoparticles concentration. A substantial affinity of small amorphous SiO2-NPs (25nm) to DPPC standard solution compared to bigger SiO2-NPs (75nm) was not confirmed for biological specimens. After dispersion of SiO2-NPs in DPPC containing cell culture medium, the capacity of the SiO2-NPs to bind DPPC was reduced in comparison to a mixture of MeOH:H2O (50/50v/v) regardless from the nanoparticles size. Furthermore, HILIC-ESI-MS revealed that A549 cells internalized DPPC during growth in serum containing medium complemented with DPPC. This finding was in a good agreement with the potential of alveolar type II cells to recycle surfactant components. Binding of lipids present in the cell culture medium to amorphous SiO2-NPs was supported by means of HILIC-ESI-MS, TEM and ICP-MS independently. Copyright © 2016 Elsevier B.V. All rights reserved.
Possible silica gel in the Olive Fault, Naukluft Nappe Complex, Namibia: A geologic record of dynamic weakening in faults during continental orogenesis

NASA Astrophysics Data System (ADS)

Faber, C.; Rowe, C. D.; Miller, J. A.; Backeberg, N.; Sylvester, F.

2009-12-01

The apparently low frictional strength of faults during earthquake slip is not sufficiently well explained. Dynamic weakening has been observed in recent laboratory experiments at seismic slip rates, even if materials are strong at slow slip rates. Di Toro et al. (2004) performed experiments on crystalline rocks at slip rates of 1m/s and observed frictional strength drops to near zero. Examination of the slip surface revealed an amorophous silica had formed during fast slip and interpreted this as a solidified silica gel. If similar silica gel forms during earthquakes, and solidifies to amorphous silica, it would be expected to slowly crystallize over time. Ujiie et al (2007) reported a microcrystalline silica fault vein from the Shimanto Complex (Japan) which contains colloidal microspheres of silica, consistent with its origin as a silica gel. This vein may have been created during seismic slip, although other explanations are possible. No other natural examples of this potentially important coseismic weakening mechanism have been reported. To investigate whether silica gel actually forms during seismic slip, it will be necessary to discover and fully characterize additional natural examples. The Naukluft Nappe Complex in central Namibia is a foreland thrust stack at the distal southern margin of the Pan-African Damara Orogen (active at ~ 550Ma). A fault vein of microcrystalline silica has been found in an intra-nappe thrust fault . The vein occurs as a mostly continuous, planar, 0.1-1.0cm-thick fault vein within dolomite breccias of the Olive Fault. There are no other veins of silica associated with the fault. The hanging wall and footwall are dolomite and calcareous shales, respectively. The layer is petrographically similar to the microcrystalline silica described by Ujiie et al. (2007). The silica layer is purple-blue to white in color cathodoluminescence, in contrast to the bright turquoise typical of quartz. Although X-ray diffraction spectra show only silica and minor dolomite in the fault vein, SEM revealed the presence of small grains of Ti-oxides which have not been observed in the host rock. The cathodoluminescence has also revealed primary textures in the dolomite breccias which are overprinted by recrystallization and invisible in transmitted light . Transmission Electron Microscopy will be used to determine whether colloidal silica particles are present. The possible finding of the solidified silica gel in the Olive Fault is significant because it may represent a new way to identify fault surfaces which have slipped seismically in the past. In particular, the presence of this unusual silica vein in a carbonate-dominated environment is consistent with the experiments of Di Toro et al (2004) who suggested that quartz need not be present in the source rocks in order to form silica gel. Di Toro, G. et al. (2004) Friction falls towards zero in quartz rock as slip velocity approaches seismic rates. Nature, 427, 436-439 Ujie, K. et al. (2007) Fluidization of granular material in a subduction thrust at seismogenic depths. EPSL, 259, 307-318
Unraveling the atomic structure of biogenic silica: evidence of the structural association of Al and Si in diatom frustules

NASA Astrophysics Data System (ADS)

Gehlen, M.; Beck, L.; Calas, G.; Flank, A.-M.; Van Bennekom, A. J.; Van Beusekom, J. E. E.

2002-05-01

We used X-ray absorption spectroscopy at the Al K-edge to investigate the atomic structure of biogenic silica and to assess the effect of Al on its crystal chemistry. Our study provides the first direct evidence for a structural association of Al and Si in biogenic silica. In samples of cultured diatoms, Al is present exclusively in fourfold coordination. The location and relative intensity of X-ray absorption near-edge structure (XANES) features suggests the structural insertion of tetrahedral Al inside the silica framework synthesized by the organism. In diatom samples collected in the marine environment, Al is present in mixed six- and fourfold coordination. The relative intensity of XANES structures indicates the coexistence of structural Al with a clay component, which most likely reflects sample contamination by adhering mineral particles. Extended X-ray absorption fine structure spectroscopy has been used to get Al-O distances in biogenic silica of cultured diatoms, confirming a tetrahedral coordination. Because of its effect on solubility and reaction kinetics of biogenic silica, the structural association between Al and biogenic silica at the stage of biosynthesis has consequences for the use of sedimentary biogenic silica as an indicator of past environmental conditions.
Formation, structural and optical characterization of neodymium doped-zinc soda lime silica based glass

NASA Astrophysics Data System (ADS)

Zamratul, M. I. M.; Zaidan, A. W.; Khamirul, A. M.; Nurzilla, M.; Halim, S. A.

New glass system of neodymium - doped zinc soda lime silica glass has been synthesized for the first time by melt-quenching of glass waste soda lime silica (SLS) with zinc oxide (ZnO) as precursor glass and Nd2O3 as dopant. In order to examine the effect of Nd3+ on the structural and optical properties, the prepared sample of structure [(ZnO)0.5(SLS)0.5](Nd2O3)x (x = 0, 1, 2, 3, 4 and 5 wt%) was characterized through X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, UV-Vis spectroscopy (UV-Vis) and the photoluminescence (PL). XRD pattern justifies the amorphous nature of synthesized glasses. FTIR spectroscopy has been used to observe the structural evolution of ZnO4 and SiO4 groups. The UV-Vis-NIR absorption spectra reveals seven peaks centered at excitation of electron from ground state 4I9/2 to 4D3/2 + 4D5/2 (∼360 nm), 2G9/2 + 2D3/2 + 2P3/2(∼470 nm), 2K13/2 + 4G7/2 + 4G9/2 (∼523 nm), 4G5/2 + 2G7/2 (∼583 nm), 4F9/2 (∼678 nm), 4S3/2 + 4F7/2 (∼748 nm) and 4F5/2 + 2H9/2 (∼801 nm). PL spectra under the excitation of 800 nm display four emission bands centered at 531 nm, 598 nm, 637 nm and 671 nm corresponding to 4G7/2 → 4I9/2, (4G7/2 → 4I11/2, 4G5/2 → 4I9/2), (4G5/2 → 4I11/2) and (4G7/2 → 4I13/2, 4G5/2 → 4I11/2) respectively.
Amorphization of Indomethacin by Co-Grinding with Neusilin US2: amorphization kinetics, physical stability and mechanism.

PubMed

Bahl, Deepak; Bogner, Robin H

2006-10-01

To quantify the effects of the ratio of indomethacin to Neusilin US2 and the processing humidity on the amorphization kinetics, stability and nature of the interaction. A porcelain jar mill with zirconia balls was used to affect conversion of the physical mixtures (48 g) of indomethacin and Neusilin US2 (in the ratios 1:1 to 1:5) to amorphous states at room temperature (25 degrees C) employing either 0% RH or 75% RH. The percent crystallinity in the samples was determined from ATR-FTIR scans chemometrically. The physical stability of these co-ground amorphous powders was evaluated at 40 degrees C/75% RH and 40 degrees C/0% RH. The lower the ratio of indomethacin to Neusilin US2, the faster is the amorphization during co-grinding. Higher humidity facilitates amorphization with a more pronounced effect at the lower ratio of indomethacin to Neusilin US2. There is further amorphization of some of the partially amorphized samples on storage at 40 degrees C/75% RH for 3 months. Hydrogen bonding and surface interaction between metal ions of Neusilin US2 and indomethacin can explain changes in the FTIR spectra. The processing humidity and the ratio of indomethacin to Neusilin US2 are important factors to be considered to affect amorphization during ball milling. Amorphous indomethacin can be stabilized by co-grinding with Neusilin US2.
Structural and Acidic Properties of Niobia-Silica and Niobia-Alumina Aerogels

DTIC Science & Technology

1991-05-06

some weak Bronsted acidity. The silica aerogel supported niobia samples also had strong Lewis acidity as well as strong iv Bronsted acidity which was...NS25w or the silica aerogel supported niobia because of the formation of a distorted octahedral niobia-rigid silica interface. Isomerization of 1...67 2.1.2 Silica Aerogel .......................................................... 70 2.1.3 Alumina

Imaging of Crystalline and Amorphous Surface Regions Using Time-of-Flight Secondary-Ion Mass Spectrometry (ToF-SIMS): Application to Pharmaceutical Materials.

PubMed

Iuraş, Andreea; Scurr, David J; Boissier, Catherine; Nicholas, Mark L; Roberts, Clive J; Alexander, Morgan R

2016-04-05

The structure of a material, in particular the extremes of crystalline and amorphous forms, significantly impacts material performance in numerous sectors such as semiconductors, energy storage, and pharmaceutical products, which are investigated in this paper. To characterize the spatial distribution for crystalline-amorphous forms at the uppermost molecular surface layer, we performed time-of-flight secondary-ion mass spectroscopy (ToF-SIMS) measurements for quench-cooled amorphous and recrystallized samples of the drugs indomethacin, felodipine, and acetaminophen. Polarized light microscopy was used to localize crystallinity induced in the samples under controlled conditions. Principal component analysis was used to identify the subtle changes in the ToF-SIMS spectra indicative of the amorphous and crystalline forms for each drug. The indicators of amorphous and crystalline surfaces were common in type across the three drugs, and could be explained in general terms of crystal packing and intermolecular bonding, leading to intramolecular bond scission in the formation of secondary ions. Less intramolecular scission occurred in the amorphous form, resulting in a greater intensity of molecular and dimer secondary ions. To test the generality of amorphous-crystalline differentiation using ToF-SIMS, a different recrystallization method was investigated where acetaminophen single crystals were recrystallized from supersaturated solutions. The findings indicated that the ability to assign the crystalline/amorphous state of the sample using ToF-SIMS was insensitive to the recrystallization method. This demonstrates that ToF-SIMS is capable of detecting and mapping ordered crystalline and disordered amorphous molecular materials forms at micron spatial resolution in the uppermost surface of a material.
Multiscale Computer Simulation of Tensile and Compressive Strain in Polymer- Coated Silica Aerogels

NASA Technical Reports Server (NTRS)

Good, Brian

2009-01-01

While the low thermal conductivities of silica aerogels have made them of interest to the aerospace community as lightweight thermal insulation, the application of conformal polymer coatings to these gels increases their strength significantly, making them potentially useful as structural materials as well. In this work we perform multiscale computer simulations to investigate the tensile and compressive strain behavior of silica and polymer-coated silica aerogels. Aerogels are made up of clusters of interconnected particles of amorphous silica of less than bulk density. We simulate gel nanostructure using a Diffusion Limited Cluster Aggregation (DLCA) procedure, which produces aggregates that exhibit fractal dimensions similar to those observed in real aerogels. We have previously found that model gels obtained via DLCA exhibited stress-strain curves characteristic of the experimentally observed brittle failure. However, the strain energetics near the expected point of failure were not consistent with such failure. This shortcoming may be due to the fact that the DLCA process produces model gels that are lacking in closed-loop substructures, compared with real gels. Our model gels therefore contain an excess of dangling strands, which tend to unravel under tensile strain, producing non-brittle failure. To address this problem, we have incorporated a modification to the DLCA algorithm that specifically produces closed loops in the model gels. We obtain the strain energetics of interparticle connections via atomistic molecular statics, and abstract the collective energy of the atomic bonds into a Morse potential scaled to describe gel particle interactions. Polymer coatings are similarly described. We apply repeated small uniaxial strains to DLCA clusters, and allow relaxation of the center eighty percent of the cluster between strains. The simulations produce energetics and stress-strain curves for looped and nonlooped clusters, for a variety of densities and interaction parameters.
X-Ray Amorphous Phases in Terrestrial Analog Volcanic Sediments: Implications for Amorphous Phases in Gale Crater, Mars

NASA Technical Reports Server (NTRS)

Smith, R. J.; Horgan, B.; Rampe, E.; Dehouck, E.; Morris, R. V.

2017-01-01

X-ray diffraction (XRD) amorphous phases have been found as major components (approx.15-60 wt%) of all rock and soil samples measured by the CheMin XRD instrument in Gale Crater, Mars. The nature of these phases is not well understood and could be any combination of primary (e.g., glass) and secondary (e.g., allophane) phases. Amorphous phases form in abundance during surface weathering on Earth. Yet, these materials are poorly characterized, and it is not certain how properties like composition and structure change with formation environment. The presence of poorly crystalline phases can be inferred from XRD patterns by the appearance of a low angle rise (< or approx.10deg 2(theta)) or broad peaks in the background at low to moderate 2(theta) angles (amorphous humps). CheMin mineral abundances combined with bulk chemical composition measurements from the Alpha Particle X-ray Spectrometer (APXS) have been used to estimate the abundance and composition of the XRD amorphous materials in soil and rock samples on Mars. Here we apply a similar approach to a diverse suite of terrestrial samples - modern soils, glacial sediments, and paleosols - in order to determine how formation environment, climate, and diagenesis affect the abundance and composition of X-ray amorphous phases.
Reinforced silver-embedded silica matrix from the cheap silica source for the controlled release of silver ions

NASA Astrophysics Data System (ADS)

Hilonga, A.; Kim, J. K.; Sarawade, P. B.; Kim, H. T.

2009-07-01

In this study, a reinforced silver-embedded silica matrix was designed by utilizing the interaction between the [AlO 4] - tetrahedral and the Ag + in sol-gel process using sodium silicate as a silica precursor. The Ag + mole ratio in each sample was significantly varied to examine the influence of silver concentration on the properties of the final product. Aluminium ions were added to reinforce and improve the chemical durability of silver-embedded silica. A templated sample at Al/Ag = 1 atomic ratio was also synthesized to attempt a possibility of controlling porosity of the final product. Also, a sample neither embedded with silver nor templated was synthesized and characterized to serve as reference. The material at Al/Ag = 1 was found to have a desirable properties, compared to its counterparts, before and even after calcination up to 1000 °C. The results demonstrate that materials with desirable properties can be obtained by this unprecedented method while utilizing sodium silicate, which is relatively cheap, as a silica precursor. This may significantly boost the industrial production of the silver-embedded silicas for various applications.
Laboratory Testing of Silica Sol Grout in Coal Measure Mudstones.

PubMed

Pan, Dongjiang; Zhang, Nong; Xie, Zhengzheng; Feng, Xiaowei; Kong, Yong

2016-11-22

The effectiveness of silica sol grout on mudstones is reported in this paper. Using X-ray diffraction (XRD), the study investigates how the silica sol grout modifies mudstone mineralogy. Micropore sizes and mechanical properties of the mudstone before and after grouting with four different materials were determined with a surface area/porosity analyser and by uniaxial compression. Tests show that, after grouting, up to 50% of the mesopore volumes can be filled with grout, the dominant pore diameter decreases from 100 nm to 10 nm, and the sealing capacity is increased. Uniaxial compression tests of silica sol grouted samples shows that their elastic modulus is 21%-38% and their uniaxial compressive strength is 16%-54% of the non-grouted samples. Peak strain, however, is greater by 150%-270%. After grouting, the sample failure mode changes from brittle to ductile. This paper provides an experimental test of anti-seepage and strengthening properties of silica sol.
Occupational exposure assessment for crystalline silica dust: approach in Poland and worldwide.

PubMed

Maciejewska, Aleksandra

2008-01-01

Crystalline silica is a health hazard commonly encountered in work environment. Occupational exposure to crystalline silica dust concerns workers employed in such industries as mineral, fuel-energy, metal, chemical and construction industry. It is estimated that over 2 million workers in the European Union are exposed to crystalline silica. In Poland, over 50 thousand people work under conditions of silica dust exposure exceeding the occupational exposure limit. The assessment of occupational exposure to crystalline silica is a multi-phase process, primarily dependent on workplace measurements, quantitative analyses of samples, and comparison of results with respective standards. The present article summarizes the approaches to and methods used for assessment of exposure to crystalline silica as adopted in different countries in the EU and worldwide. It also compares the occupational limit values in force in almost 40 countries. Further, it points out the consequences resulting from the fact that IARC has regarded the two most common forms of crystalline silica: quartz and cristobalite as human carcinogens. The article includes an inter-country review of the methods used for air sample collection, dust concentration measurements, and determination of crystalline silica. The selection was based on the GESTIS database which lists the methods approved by the European Union for the measurements and tests regarding hazardous agents. Special attention has been paid to the methods of determining crystalline silica. The author attempts to analyze the influence of analytical techniques, sample preparation and the reference materials on determination results. Also the operating parameters of the method, including limit of detection, limit of quantification, and precision, have been compared.
Characterization of the adsorption of water vapor and chlorine on microcrystalline silica

NASA Technical Reports Server (NTRS)

Skiles, J. A.; Wightman, J. P.

1979-01-01

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.
Influence of persistent exchangeable oxygen on biogenic silica δ18O in deep sea cores

NASA Astrophysics Data System (ADS)

Menicucci, A. J.; Spero, H. J.

2016-12-01

The removal of exchangeable oxygen from biogenic opal prior to IRMS analysis is critical during sample preparation. Exchangeable oxygen is found in the form of hydroxyl and between defects within the amorphous silicate lattice structure. Typical analytical procedures utilize a variety of dehydroxylation methods to eliminate this exchangeable oxygen, including vacuum dehydroxylation and prefluorination. Such methods are generally considered sufficient for elimination of non-lattice bound oxygen that would obfuscate environmental oxygen isotopic signals contained within the silicate tetrahedra. δ18O data that are then empirically calibrated against modern hydrographic data, and applied down core in paleoceanographic applications. We have conducted a suite of experiments on purified marine opal samples using the new microfluorination method (Menicucci et al., 2013). Our data demonstrate that the amount of exchangeable oxygen in biogenic opal decreases as sample age/depth in core increases. These changes are not accounted for by current researchers. Further, our experimental data indicate that vacuum dehydroxylation does not eliminate all exchangeable oxygen, even after hydroxyl is undetectable. We have conducted experiments to quantify the amount of time necessary to ensure vacuum dehydroxylation has eliminated exchangeable oxygen so that opal samples are stable prior to δ18Odiatom analysis. Our experiments suggest that previously generated opal δ18O data may contain a variable down-core offset due to the presence of exchangeable, non-lattice bound oxygen sources. Our experiments indicate that diatom silica requires dehydroxylation for ≥ 44 hours at 1060oC to quantitatively remove all non-lattice bound oxygen. Further, this variable amount of exchangeable oxygen may be responsible for some of the disagreement between existing empirical calibrations based on core-top diatom frustule remains. Analysis of δ18Odiatom values after this long vacuum dehydroxylation time is necessary for quantitative comparisons of stable isotopic values across geologic time periods. Menicucci, A. J., et al. (2013). "Oxygen isotope analyses of biogenic opal and quartz using a novel microfluorination technique." Rapid Communications in Mass Spectrometry 27(16): 1873-1881
In vitro cell transformation induced by synthetic amorphous silica nanoparticles.

PubMed

Fontana, Caroline; Kirsch, Anaïs; Seidel, Carole; Marpeaux, Léa; Darne, Christian; Gaté, Laurent; Remy, Aurélie; Guichard, Yves

2017-11-01

Synthetic amorphous silica nanoparticles (SAS) are among the most widely produced and used nanomaterials, but little is known about their carcinogenic potential. This study aims to evaluate the ability of four different SAS, two precipitated, NM-200 and NM-201, and two pyrogenic, NM-202 and NM-203, to induce the transformation process. For this, we used the recently developed in vitro Bhas 42 cell transformation assay (CTA). The genome of the transgenic Bhas 42 cells contains several copies of the v-Ha-ras gene, making them particularly sensitive to tumor-promoter agents. The Bhas 42 CTA, which includes an initiation assay and a promotion assay, was validated in our laboratory using known soluble carcinogenic substances. Its suitability for particle-type substances was verified by using quartz Min-U-Sil 5 (Min-U-Sil) and diatomaceous earth (DE) microparticles. As expected given their known transforming properties, Min-U-Sil responded positively in the Bhas 42 CTA and DE responded negatively. Transformation assays were performed with SAS at concentrations ranging from 2μg/cm 2 to 80μg/cm 2 . Results showed that all SAS have the capacity to induce transformed foci, interestingly only in the promotion assay, suggesting a mode of action similar to tumor-promoter substances. NM-203 exhibited transforming activity at a lower concentration than the other SAS. In conclusion, this study showed for the first time the transforming potential of different SAS, which act as tumor-promoter substances in the Bhas 42 model of cell transformation. Copyright © 2017 Elsevier B.V. All rights reserved.
Glycine Polymerization on Oxide Minerals.

PubMed

Kitadai, Norio; Oonishi, Hiroyuki; Umemoto, Koichiro; Usui, Tomohiro; Fukushi, Keisuke; Nakashima, Satoru

2017-06-01

It has long been suggested that mineral surfaces played an important role in peptide bond formation on the primitive Earth. However, it remains unclear which mineral species was key to the prebiotic processes. This is because great discrepancies exist among the reported catalytic efficiencies of minerals for amino acid polymerizations, owing to mutually different experimental conditions. This study examined polymerization of glycine (Gly) on nine oxide minerals (amorphous silica, quartz, α-alumina and γ-alumina, anatase, rutile, hematite, magnetite, and forsterite) using identical preparation, heating, and analytical procedures. Results showed that a rutile surface is the most effective site for Gly polymerization in terms of both amounts and lengths of Gly polymers synthesized. The catalytic efficiency decreased as rutile > anatase > γ-alumina > forsterite > α- alumina > magnetite > hematite > quartz > amorphous silica. Based on reported molecular-level information for adsorption of Gly on these minerals, polymerization activation was inferred to have arisen from deprotonation of the NH 3 + group of adsorbed Gly to the nucleophilic NH 2 group, and from withdrawal of electron density from the carboxyl carbon to the surface metal ions. The orientation of adsorbed Gly on minerals is also a factor influencing the Gly reactivity. The examination of Gly-mineral interactions under identical experimental conditions has enabled the direct comparison of various minerals' catalytic efficiencies and has made discussion of polymerization mechanisms and their relative influences possible Further systematic investigations using the approach reported herein (which are expected to be fruitful) combined with future microscopic surface analyses will elucidate the role of minerals in the process of abiotic peptide bond formation.
Characterizing Particle Size Distributions of Crystalline Silica in Gold Mine Dust

PubMed Central

Chubb, Lauren G.; Cauda, Emanuele G.

2017-01-01

Dust containing crystalline silica is common in mining environments in the U.S. and around the world. The exposure to respirable crystalline silica remains an important occupational issue and it can lead to the development of silicosis and other respiratory diseases. Little has been done with regard to the characterization of the crystalline silica content of specific particle sizes of mine-generated dust. Such characterization could improve monitoring techniques and control technologies for crystalline silica, decreasing worker exposure to silica and preventing future incidence of silicosis. Three gold mine dust samples were aerosolized in a laboratory chamber. Particle size-specific samples were collected for gravimetric analysis and for quantification of silica using the Microorifice Uniform Deposit Impactor (MOUDI). Dust size distributions were characterized via aerodynamic and scanning mobility particle sizers (APS, SMPS) and gravimetrically via the MOUDI. Silica size distributions were constructed using gravimetric data from the MOUDI and proportional silica content corresponding to each size range of particles collected by the MOUDI, as determined via X-ray diffraction and infrared spectroscopic quantification of silica. Results indicate that silica does not comprise a uniform proportion of total dust across all particle sizes and that the size distributions of a given dust and its silica component are similar but not equivalent. Additional research characterizing the silica content of dusts from a variety of mine types and other occupational environments is necessary in order to ascertain trends that could be beneficial in developing better monitoring and control strategies. PMID:28217139
Fischer-Tropsch-Type Production of Organic Materials in the Solar Nebula: Studies Using Graphite Catalysts and Measuring the Trapping of Noble Gases

NASA Technical Reports Server (NTRS)

Nuth, Joseph A., III; Ferguson, Frank T.; Lucas, Christopher; Kimura, Yuki; Hohenberg, Charles

2009-01-01

The formation of abundant carbonaceous material in meteorites is a long standing problem and an important factor in the debate on the potential for the origin of life in other stellar systems. The Fischer-Tropsch-type (FTT) catalytic reduction of CO by hydrogen was once the preferred model for production of organic materials in the primitive solar nebula. We have demonstrated that many grain surfaces can catalyze both FTT and HB-type reactions, including amorphous iron and magnesium silicates, pure silica smokes as well as several minerals. Graphite is not a particularly good FTT catalyst, especially compared to iron powder or to amorphous iron silicate. However, like other silicates that we have studied, it gets better with exposure to CO. N2 and H2 over time: e.g., after formation of a macromolecular carbonaceous layer on the surfaces of the underlying gains. While amorphous iron silicates required only 1 or 2 experimental runs to achieve steady state reaction rates, graphite only achieved steady state after 6 or more experiments. We will present results showing the catalytic action of graphite grains increasing with increasing number of experiments and will also discuss the nature of the final "graphite" grains aster completion of our experiments.
Effect of resin infiltration on the thermal and mechanical properties of nano-sized silica-based thermal insulation.

PubMed

Lee, Jae Chun; Kim, Yun-Il; Lee, Dong-Hun; Kim, Won-Jun; Park, Sung; Lee, Dong Bok

2011-08-01

Several kinds of nano-sized silica-based thermal insulation were prepared by dry processing of mixtures consisting of fumed silica, ceramic fiber, and a SiC opacifier. Infiltration of phenolic resin solution into the insulation, followed by hot-pressing, was attempted to improve the mechanical strength of the insulation. More than 22% resin content was necessary to increase the strength of the insulation by a factor of two or more. The structural integrity of the resin-infiltrated samples could be maintained, even after resin burn-out, presumably due to reinforcement from ceramic fibers. For all temperature ranges and similar sample bulk density values, the thermal conductivities of the samples after resin burn-out were consistently higher than those of the samples obtained from the dry process. Mercury intrusion curves indicated that the median size of the nanopores formed by primary silica aggregates in the samples after resin burn-out is consistently larger than that of the sample without resin infiltration.
The effect of processing on the surface physical stability of amorphous solid dispersions.

PubMed

Yang, Ziyi; Nollenberger, Kathrin; Albers, Jessica; Moffat, Jonathan; Craig, Duncan; Qi, Sheng

2014-11-01

The focus of this study was to investigate the effect of processing on the surface crystallization of amorphous molecular dispersions and gain insight into the mechanisms underpinning this effect. The model systems, amorphous molecular dispersions of felodipine-EUDRAGIT® E PO, were processed both using spin coating (an ultra-fast solvent evaporation based method) and hot melt extrusion (HME) (a melting based method). Amorphous solid dispersions with drug loadings of 10-90% (w/w) were obtained by both processing methods. Samples were stored under 75% RH/room temperatures for up to 10months. Surface crystallization was observed shortly after preparation for the HME samples with high drug loadings (50-90%). Surface crystallization was characterized by powder X-ray diffraction (PXRD), ATR-FTIR spectroscopy and imaging techniques (SEM, AFM and localized thermal analysis). Spin coated molecular dispersions showed significantly higher surface physical stability than hot melt extruded samples. For both systems, the progress of the surface crystal growth followed zero order kinetics on aging. Drug enrichment at the surfaces of HME samples on aging was observed, which may contribute to surface crystallization of amorphous molecular dispersions. In conclusion it was found the amorphous molecular dispersions prepared by spin coating had a significantly higher surface physical stability than the corresponding HME samples, which may be attributed to the increased process-related apparent drug-polymer solubility and reduced molecular mobility due to the quenching effect caused by the rapid solvent evaporation in spin coating. Copyright © 2014 Elsevier B.V. All rights reserved.
Relative Abundances of Calcite and Silica in Fracture Coatings as a Possible Indicator of Evaporation in a Thick Unsaturated Zone, Yucca Mountain, Nevada

NASA Astrophysics Data System (ADS)

Marshall, B. D.; Moscati, R. J.

2005-12-01

Yucca Mountain, a ridge of shallowly dipping, Miocene-age volcanic rocks in southwest Nevada, is the proposed site for a nuclear waste repository to be constructed in the 500- to 700-m-thick unsaturated zone (UZ). At the proposed repository, the 300-m-thick Topopah Spring Tuff welded unit (TSw) is overlain by approximately 30 m of nonwelded tuffs (PTn); the Tiva Canyon Tuff welded unit (TCw) overlies the PTn with a range in thickness from 0 to approximately 130 m at the site. The amount of water percolation through the UZ is low and difficult to measure directly, but local seepage into mined tunnels has been observed in the TCw. Past water seepage in the welded tuffs is recorded by widespread, thin (0.3 cm) coatings of calcite and silica on fracture surfaces and within cavities. Abundances of calcite and silica in the coatings were determined by X-ray microfluorescence mapping and subsequent multispectral image analysis of over 200 samples. The images were classified into constituent phases including opal-chalcedony-quartz (secondary silica) and calcite. In the TCw samples, the median calcite/silica ratio is 8; in the TSw samples within 35 m below the PTn, median calcite/silica falls to 2, perhaps reflecting an increase in soluble silica from the presence of glass in the nonwelded tuffs. In the deeper parts of the TSw, median calcite/silica reaches 100 and many samples contain no detectable secondary silica phase. Evaporation and changing pCO2 control precipitation of calcite from water percolating downward in the UZ, but precipitation of opal requires only evaporation. Calcite/silica ratios, therefore, can constrain the relative importance of evaporation in the UZ. Although calcite/silica values scatter widely within the TSw, reflecting the spatial variability of gas and water flow, average calcite/silica ratios increase with stratigraphic depth, indicating less evaporation at the deeper levels of the UZ. Coupled with the much smaller calcite/silica ratios observed in coatings from the TCw, these data indicate that evaporation decreases with depth in the UZ. Evaporation at the repository horizon and in the overlying units is an important process that reduces the amount of seepage at the repository horizon.
Considerations on the quantitative analysis of apparent amorphicity of milled lactose by Raman spectroscopy.

PubMed

Pazesh, Samaneh; Lazorova, Lucia; Berggren, Jonas; Alderborn, Göran; Gråsjö, Johan

2016-09-10

The main purpose of the study was to evaluate various pre-processing and quantification approaches of Raman spectrum to quantify low level of amorphous content in milled lactose powder. To improve the quantification analysis, several spectral pre-processing methods were used to adjust background effects. The effects of spectral noise on the variation of determined amorphous content were also investigated theoretically by propagation of error analysis and were compared to the experimentally obtained values. Additionally, the applicability of calibration method with crystalline or amorphous domains in the estimation of amorphous content in milled lactose powder was discussed. Two straight baseline pre-processing methods gave the best and almost equal performance. By the succeeding quantification methods, PCA performed best, although the classical least square analysis (CLS) gave comparable results, while peak parameter analysis displayed to be inferior. The standard deviations of experimental determined percentage amorphous content were 0.94% and 0.25% for pure crystalline and pure amorphous samples respectively, which was very close to the standard deviation values from propagated spectral noise. The reasonable conformity between the milled samples spectra and synthesized spectra indicated representativeness of physical mixtures with crystalline or amorphous domains in the estimation of apparent amorphous content in milled lactose. Copyright © 2016 The Author(s). Published by Elsevier B.V. All rights reserved.
Devitrification of amorphous celecoxib.

PubMed

Gupta, Piyush; Bansal, Arvind K

2005-09-30

The purpose of this research was to analyze the devitrification of amorphous celecoxib (CEL) in the presence of different stressors (temperature, pressure, and/or humidity) encountered during processing of solid dosage forms. Amorphous CEL was prepared in situ in the analytical instruments, as well as in laboratory, by quench-cooling of melt process, and analyzed by dynamic mechanical thermal analysis, differential scanning calorimetry, microscopy, and Fourier-transform infrared spectroscopy. Amorphous CEL prepared in situ in the analytical instruments was resistant to crystallization under the influence of temperature and/or pressure, because of its protection from the external environment during preparation. These samples exhibited structural relaxation during annealing at 25 degrees C/0% relative humidity (RH) for 16 hours. Generation of amorphous CEL in the laboratory resulted in partially crystalline samples, because of exposure to environmental temperature and humidity, resulting in incomplete vitrification. Subjection to thermal stress favored crystallization of amorphous CEL into metastable polymorphic forms, which were not obtained by solvent recrystallization approach. Temperature and humidity were identified as the major factors promoting devitrification of amorphous CEL, leading to loss of solubility advantage. Exposure to International Conference on Harmonization-specified accelerated stability storage conditions (40 degrees C/75% RH) resulted in complete devitrification of amorphous CEL within 15 days. The phase-transformation process of amorphous CEL along the temperature scale was examined visually, as well as spectrally. This propensity for devitrification of amorphous CEL seemed to depend on the strength of differential molecular interactions between the amorphous and crystalline form.
Impact of storage induced outgassing organic contamination on laser induced damage of silica optics at 351 nm.

PubMed

Bien-Aimé, K; Belin, C; Gallais, L; Grua, P; Fargin, E; Néauport, J; Tovena-Pecault, I

2009-10-12

The impact of storage conditions on laser induced damage density at 351 nm on bare fused polished silica samples has been studied. Intentionally outgassing of polypropylene pieces on silica samples was done. We evidenced an important increase of laser induced damage density on contaminated samples demonstrating that storage could limit optics lifetime performances. Atomic Force Microscopy (AFM) and Gas Chromatography -Mass Spectrometry (GC-MS) have been used to identify the potential causes of this effect. It shows that a small quantity of organic contamination deposited on silica surface is responsible for this degradation. Various hypotheses are proposed to explain the damage mechanism. The more likely hypothesis is a coupling between surface defects of optics and organic contaminants.
Control-release microcapsule of famotidine loaded biomimetic synthesized mesoporous silica nanoparticles: Controlled release effect and enhanced stomach adhesion in vitro.

PubMed

Li, Jing; Wang, Hongyu; Yang, Baixue; Xu, Lu; Zheng, Nan; Chen, Hongtao; Li, Sanming

2016-01-01

In the present work, control-release microcapsule of famotidine (FMT) loaded biomimetic synthesized mesoporous silica nanoparticles (B-MSNs) was developed, and controlled release effect and stomach adhesion of this formulation in vitro were mainly investigated. B-MSN was previously synthesized and it was amorphous mesoporous nanoparticles with helical channels. Cytotoxicity of B-MSN was studied using human breast cancer cells (MCF-7) and the result indicated that cytotoxicity of B-MSN can be neglected. After loading FMT into B-MSN, specific surface area, pore volume and pore diameter of B-MSN were obviously reduced. In vitro dissolution test showed that B-MSN had the ability to slow down FMT release for 15 min. In order to prolong controlled release effect and remained the advantage of B-MSN (improve drug stability due to its rigid silica framework), the combined application of control-release microcapsule (using cellulose and hydroxypropyl methylcellulose K15M as excipients) with B-MSN was designed. It was obvious that newly designed formulation significantly controlled FMT release with Fickian diffusion mechanism and showed enhanced stomach adhesion in vitro, which has significant value in widening the application of B-MSN in formulation design. Copyright © 2015 Elsevier B.V. All rights reserved.
Preparation of Water Suspensions of Nanocalcite for Cultural Heritage Applications.

PubMed

Coltelli, Maria-Beatrice; Paolucci, Dario; Castelvetro, Valter; Bianchi, Sabrina; Mascha, Elisabeth; Panariello, Luca; Pesce, Cecilia; Weber, Johannes; Lazzeri, Andrea

2018-04-19

The consolidation of degraded carbonate stone used in ancient monuments is an important topic for European cultural heritage conservation. The products most frequently used as consolidants are based on tetraalkoxy- or alkylalkoxy-silanes (in particular tetraethyl-orthosilicate, TEOS), resulting in the formation of relatively stable amorphous silica or alkylated (hydrophobic) silica inside the stone pores. However, silica is not chemically compatible with carbonate stones; in this respect, nanocalcite may be a suitable alternative. The present work concerns the preparation of water suspensions of calcite nanoparticles (CCNPs) by controlled carbonation of slaked lime using a pilot-scale reactor. A simplified design of experiment was adopted for product optimization. Calcite nanoparticles of narrow size distribution averaging about 30 nm were successfully obtained, the concentration of the interfacial agent and the size of CaO being the most critical parameters. Primary nanoparticle aggregation causing flocculation could be substantially prevented by the addition of polymeric dispersants. Copolymer-based dispersants were produced in situ by controlled heterophase polymerisation mediated by an amphiphilic macro-RAFT (reversible addition-fragmentation transfer) agent. The stabilized CCNP aqueous dispersions were then applied on carbonate and silicate substrates; Scanning Electron Microscopy (SEM)analysis of cross-sections allowed the evaluation of pore penetration, interfacial binding, and bridging (gap-filling) properties of these novel consolidants.

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