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At least 523 records · Page 29Linked to original sources
PubMed2006

First isolation of individual silicate platelets from clay exfoliation and their unique self-assembly into fibrous arrays.

Thin silicate platelets in a dimension of approximately 80 x 80 x 1 nm(3) are isolated for the first time by a newly developed process involving one-step exfoliation of natural montmorillonite clay and toluene/aqueous NaOH extraction. The platelets are observed to be polygon shape by transmission electron microscopy (TEM) and round bent-leaf shape by dynamic force microscopy (DFM). Individual platelets possessing high-aspect-ratio dimension and ionic character are able to self-assemble into microscale fiber bundles after water evaporation. The self-stacking mechanism indicated strong face-to-face ionic charge stacking propensity in triggering a vertical growth. Regularity of fibrous bundles in an average 5 microm length has been observed.

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PubMed2005

Modeling gas adsorption and transport in small-pore titanium silicates.

Engelhard titanium silicate, ETS-4, is a promising new adsorbent for size-selective separation of mixtures of small gases, a leading industrially important example of which is methane-nitrogen separation. Single component equilibrium and kinetics of oxygen, nitrogen, and methane adsorption in Na-ETS-4 and cation-exchanged Sr-ETS-4, measured in an earlier study over a wide range of temperatures and pressures, are analyzed in this study. The adsorbent crystals were synthesized and pelletized under pressure (without any binder), thus giving rise to a bidispersed pore structure with controlling resistance in the micropores. Change in equilibrium and kinetics of adsorption of the aforementioned gases in Sr-ETS-4 due to pore shrinkage with progressively increasing dehydration temperature has also been investigated. Differential uptakes have been measured at various levels of adsorbate loading, which has allowed the elucidation of the nature of concentration dependence of micropore diffusivity. Both homogeneous and heterogeneous models are examined on the equilibrium data, while a bidispersed pore diffusion model is able to capture the differential uptakes very well. On the basis of chemical potential gradient as the driving force for diffusion, the impact of isotherm models on the concentration dependence of micropore diffusivity is also analyzed. It is shown that pore tailoring at the molecular scale by dehydration can improve the kinetic selectivity of nitrogen over methane in Sr-ETS-4 to a promising level. The models investigated are evaluated to identify essential details necessary to reliably simulate a methane-nitrogen separation process using the promising new Sr-ETS-4 adsorbent.

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PubMed2005

Phase separation in class II organically modified silicate films as probed by phase-imaging atomic force microscopy.

Phase imaging tapping mode atomic force microscopy has been used to examine the presence and extent of phase separation in organically modified silicate films. A total of seven films were prepared using two different synthetic routes (cohydrolysis/condensation and separate hydrolysis/condensation) with three different organoalkoxysilanes and tetraethoxysilane. Films made from separately hydrolyzed sols were rougher and had larger phase separated domains compared to films prepared from cohydrolyzed sols. Likewise, films prepared from sols containing organoalkoxysilanes with nonpolar bulky substituents, such as ethyl and isobutyl, were significantly rougher and more phase separated relative to those prepared from a more miscible nitrile alkoxysilane.

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PubMed2005

Micropore to macropore structure-designed silicas with regulated condensation of silicic acid nanoparticles.

A new preparation method for porous silica particles was developed using activated silica sols which are called nano-silica solutions in this paper. Several kinds of organic and inorganic acids are employed to neutralize diluted sodium silicate solutions to form the nano-silica solutions: formic acid, acetic acid, propionic acid, oxalic acid, succinic acid, dl-malic acid, citric acid, and tricarballylic acid as carboxylic acids, and sulfuric acid and hydrochloric acid as inorganic acids. The effect of salts in the nano-silica solution is also studied. The products were investigated using a field emission scanning electron microscope, an X-ray diffractometer, the nitrogen adsorption technique, and a mercury porosimeter. Microporous silicas were produced when carboxylic acids were applied; the formation of micropores was influenced by the pH of the nano-silica solutions and molecular sizes of the carboxylic acids. Addition of a salt in a citric acid solution increased the mesopore volume. Macropores were formed when inorganic acids including salts were applied; the salt nanoparticles which were crystallized in silica spheres acted as templates. The anion types and salt concentrations in the nano-silica solutions affected the aggregation condition of silica nanoparticles, following the Schulze-Hardy rule.

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PubMed1998

Behaviour of photopolymerized silicate-glass-fibre-reinforced dimethacrylate composites subjected to hydrothermal ageing: part I. Steady-state sorption characteristics.

Steady-state water sorption due to hydrothermal ageing (37 degrees C) was determined via gravimetric methods for both an unreinforced dimethacrylate copolymer network and for composites of the copolymer reinforced with two different silicate yarn products - S2-glass(R) and quartz. The copolymer sorbed 4.9+/-0.3 wt%, and the composites sorbed 0.5-2.5 wt%. For the two types of composites, two different positive linear correlations were established between the sorption gain and the copolymer content in the composites. In the case of the S2-glass(R) composites, the sorption gain was fully explained in terms of sorption in the copolymer; and normalization of these data by the mass fraction of copolymer yielded a constant sorption value matching that of the unreinforced copolymer. After normalizing the data for the quartz composites, an additional positive correlation was established between the water gain (per unit weight of copolymer) and the linear density of interfacial surface area. For both types of composites the sorption response was stable over a three-month ageing period.

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PubMed1997

Bioactivity of sol-gel derived organically modified silicates: part i: in vitro examination.

Bioactivity was investigated for several organically modified silicates (Ormosils) prepared through sol-gel processes. Ca(II)-free samples were biocompatible only, but Ca(II)containing samples were bioactive and deposited apatite during immersion in a simulated body fluid. The ease of silanol (Si-OH) group formation on the ormosils was considered a predominant factor controlling the bioactivity, while the effect of dissolved Ca(II) ions to increase the degree of supersaturation in the simulated body fluid is secondary.

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PubMed2002

Cell adhesion and proliferation on biomimetic calcium-phosphate coatings produced by a sodium silicate gel methodology.

The present study describes a methodology to produce bioactive coatings on the surface of starch based biodegradable polymers or other polymeric biomaterials. As an alternative to the more typical bioactive glass percursors, a sodium silicate gel is being employed as a nucleating agent, for inducing the formation of a calcium-phosphate (Ca-P) layer. The method has the advantage of being able to coat efficiently both compact materials and porous 3D architectures aimed at being used on tissue replacement applications and as bone tissue engineering scaffolds. This treatment is also very effective in reducing the incubation periods, being possible to observe the formation of an apatite-like layer, only after 6 h of immersion in a simulated body fluid (SBF). The influence of the SBF concentration on the formation of the apatite coating was also studied. The apatite coatings formed under different conditions were analyzed and compared in terms of morphology, chemical composition and structure. After the first days of SBF immersion, the apatite-like films exhibit the typical cauliflower like morphology. With increasing immersion times, these films exhibited a partially amorphous nature and the Ca/P ratios became very closer to the value attributed to hydroxyapatite (1.67). The obtained results are very promising for pre-calcifying bone tissue engineering scaffolds. Therefore, in order to study cell behavior and response to these apatite coatings, adhesion, morphology, and proliferation of a human osteoblast cell line (SaOS-2) was also analyzed after being cultured in the coatings formed after 15 days of immersion in SBF. Results indicate a good correlation between crystallinity of the apatite like coatings formed in these conditions and respective cell spreading and morphology. In general, higher cell proliferation was observed for higher crystalline Ca-P coatings.

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PubMed2001

Evidence for mantle metasomatism by hydrous silicic melts derived from subducted oceanic crust.

The low concentrations of niobium, tantalum and titanium observed in island-arc basalts are thought to result from modification of the sub-arc mantle by a metasomatic agent, deficient in these elements, that originates from within the subducted oceanic crust. Whether this agent is an hydrous fluid or a silica-rich melt has been discussed using mainly a trace-element approach and related to variable thermal regimes of subduction zones. Melting of basalt in the absence of fluid both requires high temperatures and yields melt compositions unlike those found in most modern or Mesozoic island arcs. Thus, metasomatism by fluids has been thought to be the most common situation. Here, however, we show that the melting of basalt under both H2O-added and low-temperature conditions can yield extremely alkali-rich silicic liquids, the alkali content of which increases with pressure. These liquids are deficient in titanium and in the elements niobium and tantalum and are virtually identical to glasses preserved in mantle xenoliths found in subduction zones and to veins found in exhumed metamorphic terranes of fossil convergent zones. We also found that the interaction between such liquids and mantle olivine produces modal mineralogies that are identical to those observed in metasomatized Alpine-type peridotites. We therefore suggest that mantle metasomatism by slab-derived melt is a more common process than previously thought.

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PubMed2005

Breaking of Henry's law for noble gas and CO2 solubility in silicate melt under pressure.

Degassing of the Earth is still poorly understood, as is the large scatter in He/Ar ratios observed in mid-ocean ridge basalts. A possible explanation for such observations is that vesiculation occurs at great depths with noble-gas solubilities different from those measured at 1 bar (ref. 1). Here we develop a hard-sphere model for noble-gas solubility and find that, owing to melt compaction, solubility may decrease by several orders of magnitude when pressure increases, an effect subtly overbalanced by the compression of the fluid phase. Our results satisfactorily explain recent experimental data on argon solubility in silicate melts, where argon concentration increases almost linearly with pressure, then levels off at pressures of 50-100 kbar (refs 2-5). We also model vesiculation during magma ascent at ridges and find that noble-gas partitioning between melt and CO2 vesicles at depth differs significantly from that at low pressure. Starting at 10 kbar (approximately 35 km depth), several stages of vesiculation occur followed by vesicle loss, which explains the broad variability of He-Ar concentration data in mid-ocean ridge basalts. 'Popping rocks', exceptional samples with high vesicularity, may represent fully vesiculated ridge magma, whereas common samples would simply have lost such vesicles.

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PubMed2006

Aluminium control of argon solubility in silicate melts under pressure.

Understanding of the crystal chemistry of the Earth's deep mantle has evolved rapidly recently with the gradual acceptance of the importance of the effect of minor elements such as aluminium on the properties of major phases such as perovskite. In the early Earth, during its formation and segregation into rocky mantle and iron-rich core, it is likely that silicate liquids played a large part in the transport of volatiles to or from the deep interior. The importance of aluminium on solubility mechanisms at high pressure has so far received little attention, even though aluminium has long been recognized as exerting strong control on liquid structures at ambient conditions. Here we present constraints on the solubility of argon in aluminosilicate melt compositions up to 25 GPa and 3,000 K, using a laser-heated diamond-anvil cell. The argon contents reach a maximum that persists to pressures as high as 17 GPa (up to 500 km deep in an early magma ocean), well above that expected on the basis of Al-free melt experiments. A distinct drop in argon solubility observed over a narrow pressure range correlates well with the expected void loss in the melt structure predicted by recent molecular dynamics simulations. These results provide a process for noble gas sequestration in the mantle at various depths in a cooling magma ocean. The concept of shallow partial melting as a unique process for extracting noble gases from the early Earth, thereby defining the initial atmospheric abundance, may therefore be oversimplified.

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PubMed2001

Redirect the assembly of hexagonal MCM-41 into cubic MCM-48 from sodium silicate without the use of an organic structure modifier.

In contrast to earlier methods requiring the presence of organic modifiers for the preparation of cubic MCM-48 mesostructures from low cost sodium silicate, we show that this three dimensional framework structure can be readily assembled in the absence of co-surfactants simply by using the overall SiO2/OH- ratio as means of controlling the surfactant packing parameter.

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PubMed2002

Microwave assisted template removal of siliceous porous materials.

Organic templates of meso- and macro-porous siliceous materials can be completely removed within minutes by microwave digestion, resulting in highly ordered inorganic frameworks with higher surface areas, larger pore volumes, lower structural shrinkage and richer silanol groups compared with those from conventional template removal methods.

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PubMed2002

Porous nanocomposites of zirconium dioxide and silicate.

Highly porous nanocomposites of zirconium dioxide and silicate are synthesised in an aqueous system from an inorganic salt of zirconium; the nanacomposites, with tailorable pore structures, exhibit superior performance as catalyst supports.

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