Novel non-hydrolytic sol-gel route to metal oxides

Monolithic alumina and aluminosilicate gels have been prepared using a novel sol-gel process based on the non-hydrolytic condensation reaction between a metal halide and a metal alkoxide. XRD indicated that the alumina gel remained amorphous at 750°C; solid state ²⁷Al NMR indicated the presence in the dried gel and in the amorphous calcined sample of a large amount of pentacoordinated aluminum atoms. A study of the sol formation using liquid state ²⁷Al NMR suggested that the gel structure was reminiscent of the oligomeric structure of the chloroisopropoxide precursors. Differential thermal analysis and XRD indicated that the aluminosilicate gels were converted to mullite below 1000°C, suggesting a high degree of homogeneity in these precursors.     

Porous silicon oxycarbide glasses from organically modified silica gels of high surface area

High surface area alkyl-substituted silica aerogels and xerogels were successfully prepared by sol-gel processing and supercritical drying. The gels were further heat treated in inert atmosphere to temperatures as high as 1000°C. Surface areas and pore structure of the gels and gels pyrolyzed at high temperatures were determined by multipoint BET surface area measurement. The aerogels and xerogels exhibited surface areas of about 1100 m²/g. No significant effect of pH was found on the surface areas of gels in the two step sol-gel process, but gels of low pH showed smaller pore diameter and higher density. Xerogels showed smaller surface area, pore size, and pore volume compared to aerogels. Upon pyrolyzing in inert atmosphere, the surface areas of all the gels decreased with temperature as a result of collapse of micropores and shrinkage of mesopores. Unlike pure silica gel, which loses almost all surface area and densifies at 1000°C, the advantage of the alkyl-substituted gels is that they maintained a high surface area of 400 m²/g at 1000°C.Also with the Department of Agronomy.     

Thermal Evolution of Hybrid Organic-Inorganic Gels Derived from Reaction of 1,4 Butanediol with Tetraethoxysilane

Transparent monolithic discs of organic-inorganic hybrid gels have been prepared by hydrolysis-condensation reactions of tetraethyl orthosilicate with 1,4 butanediol. The gels and glasses have been characterized by infrared spectroscopy and ²⁹Si MAS NMR. The characterization of the gels by infrared spectroscopy showed the incorporation of carbonaceous groups in the polymeric structure and Si–C bonding in the glasses. Pyrolysis of the gels has been studied using thermal analysis. It showed that the pyrolysis of the gels occurs in two temperature domains. The first is below 400°C due to condensation reactions and second is in the temperature range 450–550°C due to decomposition of carbonaceous groups and crosslinking. Pyrolysis of the gels at 1000°C resulted in X-ray amorphous, hard black glasses similar to oxycarbide glasses obtained by pyrolysis of siloxanes. On further heat treatment to 1400–1600°C, development of cristobalite structure and crystalline silicon carbide is observed in the otherwise amorphous black mass. The pyrolysed materials have been found to exhibit good resistance towards oxidation at 1000°C.     

Structural Development of Single Phase (Type I) Mullite Gels

Single phase (type I) mullite gels were prepared by sol-gel techniques starting from alkoxides (Al-butylate, tetraethylorthosilicate) and alkoxides plus nitrates (tetraethylorthosilicate, Al(NO₃)₃·9H₂O). After drying at 150°C the aluminosilicate gels are non-crystalline and remain so up to 900°C. Above 900°C the gels transform into Al₂O₃-rich mullite plus a coexisting SiO₂ phase. Structural studies on temperature-dependent dehydroxylation and condensation of the gels were carried out by large angle X-ray scattering, by infrared spectroscopy and by²⁹ Si NMR spectroscopy. Heat-treatment (<150°C) of dried gels first causes removal of the H₂O and organic residuals weakly bound at the open pore surfaces of the gels while the stronger, structurally bound OH groups are not affected. At temperatures <600°C OH groups are released and recombine to molecular H₂O. If the temperature does not exceed 800°C the newly formed H₂O is trapped in closed nanopores of the gel-network. Corresponding electron microscopical investigations reveal agglomerates of 10 nm sized primary particles virtually unaffected by the heat-treatment below 900°C. NMR investigation provided a new structural model on type and distribution of coordination polyhedra in aluminium silicate gel networks. Unlike Si, which according to ²⁹Si NMR is always 4-fold coordinated with O, ²⁷Al NMR spectroscopy revealed that Al cordination is more complex and is influenced by thermal treatment. Al occurs six-fold (octahedrally) and four-fold (tetrahedrally) coordinated. A third ²⁷Al NMR signal which has been attributed to five-fold-coordinated Al in the literature increased in intensity with the heat-treatment. A comparison of NMR data of the gels with those of mullite suggests that tetrahedra triclusters (3 tetrahedra having one oxygen atom in common) occur as major structural units in aluminium silicate gels rather than five-fold-coordinated Al. Triclusters of tetrahedra may compensate the excess negative charge in the network caused by Si⁴⁺ Al³⁺ substitution. The charge compensation model is supported by aluminosilicate gels doped with network modifiers (e.g., Na⁺). Since equimolar addition of Na⁺ compensates Si⁴⁺ Al³⁺ substitution the formation of triclusters is no longer required which actually can be deduced from²⁷ Al NMR studies.     

Phase Formation in Gels of the Apatite-Anorthite System

Phase formation in heat-treated composites containing anorthite gel and fluorapatite has been investigated. For the sol-gel synthesis TEOS, Al(NO3)3·9H2 O, Ca(NO3)2·4H2O, (NH4)3PO4·3H2O, NH4F and CaF2 were used as precursors. The gel mixtures were treated from 200 to 1250°C. It was found that the gels remain in an amorphous state up to 900°C. From X-ray diffraction structural analysis of anorthite gel-glasses heat treated at 600°C and 800°C it was found that a shift of the first maximum occurred from 1.85 to 1.77 Å, which could be interpreted as a transformation of the gel-glass structure with increasing temperature. During the heat treatment of the mixed gels from the apatite-anorthite system it was found that fluorapatite is present as a major crystal phase at 950°C. At 1250°C anorthite and gehlenite are the major crystalline phases.     

Preparation and Characterization of Highly Proton-Conductive Composites Composed of Phosphoric Acid-Doped Silica Gel and Styrene-Ethylene-Butylene-Styrene Elastomer

Highly proton-conductive elastic composites have been successfully prepared from H₃PO₄-doped silica gel and a styrene-ethylene-butylene-styrene (SEBS) block elastic copolymer. Ionic conductivities of the composites depended on the concentration of H₃PO₄ and the heat treatment temperature of the H₃PO₄-doped silica gel. It was found that H₃PO₄ added is present mainly as free orthophosphoric acid in the silica gel. The composite composed of H₃PO₄-doped silica gel with a molar ratio of H₃PO₄/SiO₂ = 0.5 heat-treated at temperatures below 200°C and SEBS elastomer in 5 mass% showed a high conductivity of 10^–5 S cm^–1 at 25°C in an dry N₂ atmosphere. The water adsorption during a storage in 25% relative humidity at room temperature for 1 day enhanced the ionic conductivities of composites by about one order of magnitude. Lower conductivities obtained in the composite with the H₃PO₄-doped silica gel heat-treated at 250°C for 1 h were due to the formation of crystalline Si₃(PO₄)₄. The temperature dependence of conductivity of the composites was the Vogel-Tamman-Fulcher type, indicating that proton was transferred through a liquidlike phase formed in micropores of the H₃PO₄-doped silica gels. The temperature dependence of the modulus of the composite was similar to that of the SEBS elastomer. The thermoplastically deforming temperature of the composite was around 100°C, which was higher by 30°C than that of the SEBS elastomer.     

Synthesis and swelling behavior of thermosensitive hydrogels based on N-substituted acrylamides and sodium acrylate

A series of hydrogels based on N-isopropylacrylamide, sodium acrylate, and N-tert-butylacrylamide were synthesized by free radical polymerization in a mixture of dioxane and water with tetra(ethylene glycol) diacrylate as the crosslinker and benzoyl peroxide as the initiator. The swelling behavior including the swelling rate of the crosslinked gels in water was studied with gravimetric method. The swelling ratio of the gel (0.1 mol% crosslinking) can reach 420 g/g at 20 °C and such a gel can release 96% of the water absorbed at 40 °C. The lower critical swelling temperature (LCST) of the copolymers can be adjusted by changing the chemical composition of the polymers. Such crosslinked gels can be potentially used as thermosensitive superabsorbent because of their high water uptake and thermal sensitivity.     

Gelation of Aluminosilicate Systems Under Different Chemical Conditions

Optically clear aluminosilicate gels of different chemical compositions (0–0.9 mole ratios of total Al/(Si + Al)) were prepared directly from solutions of inorganic aluminum salts, tetraethoxysilane, water and alcohol without the time-consuming sol forming. However, in these gels only 0–75% of total Al content was incorporated by chemical bonding into the gel network depending on the compositions of gels and the preparation conditions. The incorporation of aluminum atoms into the gel framework and the structure of wet gels were investigated by chemical analysis, ²⁷Al magic angle spinning nuclear magnetic resonance, and small angle X-ray scattering. The present method may be most favourable for the preparation of aluminosilicate gels with 0.30–0.70 mole ratios of total Al/(Si + Al). At lower Al content acidic catalysis is required. Above 0.70 mole ratio homogeneous gels cannot be obtained by this method. The highest aluminum incorporation in homogeneous gel structures of various mole ratios of total Al/(Si + Al) was 0.53 mole ratio of bonded Al/(Si + Al) in contradiction to 0.1 mole ratio of Al/(Si + Al) achieved by traditional melting process of glass.     

Highly fluorinated graphite prepared from graphite fluoride formed using BF3 catalyst

Fluorinated graphites (CF_0.47) were obtained by reaction at room temperature of fluorine gas with graphite in the presence of boron trifluoride and hydrogen fluoride as catalysts. Their thermal treatments under fluorine at temperatures up to 600 °C lead to a progressive increase of the fluorine level resulting in an highly fluorinated graphite (CF_1.02). Whatever the fluorination level, a stage one fluorine-graphite intercalation compound is obtained. The sp² carbon hybridization is maintained for treatment temperature below 300 °C and two types of structure coexist for T_T in the range 350-550 °C. Finally, above 550 °C, carbon hybridization is sp³.The resulting materials were studied by ¹¹B, ¹H, and ¹⁹F NMR and EPR at different experimental temperatures giving informations about the intercalated fluoride species, the temperature of their removal from the host fluorocarbon matrix, as well as their mobility.     

Room Temperature Synthesis and Characterization of Hybrid Materials of Polymethylhydrosiloxane Modified by Hydroxide Organic Compounds

New monolithic and transparent hybrid gels were obtained by reaction at room temperature of polymethylhydrosiloxane (PMHS) with 1,3,5-trihydroxybenzene (DO_1,3,5) and 2-hydroxybenzoic acid (DO₂), in tetrahydrofuran, using hexachloroplatinic acid (H₂PtCl₆·6H₂O) as catalyst. The products have been characterized by infrared and ²⁹Si MAS-NMR spectroscopy. The results show that the organic compounds have reacted with the PMHS, leading to monolithic and transparent gels in which organic-inorganic bridges were formed. An appropriate thermal treatment procedure was determined from TGA and DTA curves recorded on the hybrid gel powder after drying at 70 °C. The morphology and structure of the materials obtained were studied by scanning electronic microscopy (SEM) and X-ray powder diffraction (XRD).     

Sol-gel prepared copper doped SiO2 glasses

SiO₂ glasses doped with nano-sized copper particles were prepared through sol-gel method. Samples with nominal composition xCu–(1–x)SiO₂ (x=0.02, 0.05, 0.1, 0.2, 0.4) were prepared by hydrolyzing tetraethylorthosilicate with various amounts of Cu(NO₃)₂. The dried gels were heat treated at 400, 500, 600, 700°C for 10 hrs under flowing 5% H₂-95% N₂ mixture gas to reduce Cu⁺² ions to metallic copper. The amorphous nature of the SiO₂ matrix was confirmed by powder X-ray diffraction. The size of particulate copper metal, which was determined by transmission electron microscopy, increases with the temperature of heat treatment and the copper content. The local structure of SiO₂ matrix was probed by FTIR. The silica matrix has no major structural change for gels heat treated at different temperatures and with different copper contents.     

Preparation of titania colloids by thermal hydrolysis of urea and densification behavior of the collid-derived monolithic titania gels

Hydrous titania colloids with different sizes and shapes were prepared from urea-containing TiCl₄ solutions by controlled thermal hydrolysis of urea. Very small colloidal particles (Sw=280–290 m²/g) with anatase structure were precipitated from aqueous HCl solutions of [TiCl₄] <1.0 mol/dm³ and [urea] >16.6 mol/dm³. Sols containing such colloids could be converted to translucent monolithic gels. A decrease in urea concentration ([urea]=8.3 mol/dm³) caused the production of aggregated rutile-type particles with a large aspect ratio, from which only titania powder was obtained. Heating of a monolithic gel above 500°C resulted in the accelerated densification of the gel. A highly densified titania with 96% of theoretical density was produced from the monolithic gel after heating at 700°C for 6 h.     

Pore size and liquid impregnation of microporous aluminosilicate gels and glasses

Optically clear monolithic (OCM) gels of microporous aluminosilicates have been prepared by slow hydrolysis-polycondensation of alkoxides. Subsequent heating induces transformations into OCM microporous glasses. The surface area (∼610 m²/g after drying at 300°C) and the pore volume (∼0.35 cc/g at 300°C) decrease monotonously with increasing annealing temperature. However, after heat treatment at 600°C under air (glass state) the monoliths are still microporous. Modifications of the xerogel pore distribution by an impregnation process and metal aggregate formation with pyrolysis are studied by N₂ adsorption-desorption analysis and small-angle X-ray scattering (SAXS). The microporous structure becomes mesoporous. A model of microporous impregnation in the gel or glass state is proposed.     

Characterization of Alumina Gel Catalysts by Emanation Thermal Analysis (ETA)

Alumina gels made from the metal alkoxide is known to have high catalyst activity for the selective reduction of NO _x by hydrocarbons. It is also reported that the fine structure of the gels effects the activity. In this study, the effect of the preparation method on the fine structure and catalyst activity of the gels was investigated. Monolithic gels were obtained by hydrolysis of Al(sec-C₄H₉O)₃. The wet gels were dried at 90°C (xerogels), supercritically dried (aerogels), or dried after immersion in an ethanol solution of methyltrimethoxysilane (modified xerogels). The changes in the microstructure during heating were discussed using the results of TG-DTA, ETA and N₂ adsorption. The ETA curves show the ²²⁰Rn-release rate, E, of the samples, previously labelled with ²²⁸Th and ²²⁴Ra, during heating. The decrease in E of the xerogel at temperatures higher than 400°C indicates a gradual decrease in the surface area and porosity. A remarkable decrease in the BET surface area of the xerogel was found after heat-treating at 500°C. On the other hand, constant E of the aerogels and modified xerogels above 450°C suggests high thermal stability. The pore radii, estimated by BJH method, and the catalyst activities at 500°C of the aerogels and the modified xerogels were higher than those of the xerogels. The temperature range in which the alumina gels are applicable as catalysts was determined.     

Adhesive effect of low-density polyethylene gels on polyethylene moldings

Adhesive effect of low density polyethylene (LDPE) gels in organic solvents such as decalin, tetralin, ando-dichlorobenzene on high density polyethylene (HDPE) moldings has been investigated by shearing tests, electron microscopy, and DSC measurements. When heated at 110°C for 2 h, all of the gels showed strong adhesive strengths around 30 kg/cm², which is sufficiently strong for practical uses. It has been found that the adhesive strength increases with the heating temperature and that the temperature at which the heated gel begins to exhibit the adhesive effect depends upon solvents and is about 30° lower than that of the HDPE gels.     

Formation of functional phosphosilicate gels from phytic acid and tetraethyl orthosilicate

Phosphosilicate gels with high phosphorus content (P mol% > Si mol%) have been prepared using phytic acid as the phosphorus precursor, with tetraethyl orthosilicate (TEOS). It is shown that the structure of phytic acid is maintained in both the sols and those gels dried at a low temperature (i.e. ≤120 °C). Solid state ²⁹Si and ³¹P NMR suggest that the gel network is primarily based on tetrahedral silicon and that phosphorus is not chemically incorporated into the silicate network at this point. X-ray diffraction shows the gel to be amorphous at low temperatures. After heat treatment at higher temperatures (i.e. up to 450 °C), P–O–Si linkages are formed and the silicon coordination changes from tetrahedral to octahedral. At the same time, the gel crystallizes. Even after this partial calcination, ³¹P NMR shows that a large fraction of phytic acid remains in the network. The function of phytic acid as chelating agent is also maintained in the gels dried at 120 °C such that its ability to absorb Ca²⁺ from aqueous solution is preserved.     

Sol-Gel Synthesis of Humidity-Sensitive P2O5-SiO2 Amorphous Films

The sol-gel synthesis of silicophosphate gels using phosphoryl chloride and tetraethoxysilane as molecular precursors is reported and discussed. Gel-derived glasses and films having the molar compositions 10P₂O₅ · 90SiO₂ and 30P₂O₅ · 70SiO₂ have been obtained. The structure of the dried gels as well as the structural modifications that occurs during the transformations in gel-derived glasses are analyzed by Fourier transform infrared spectroscopy (FTIR). It has been found that the evidence of the P—O—Si linkages begins to appear only on the FTIR spectra of the bulk gels heat treated up to 400°C while they are well resolved on the FTIR spectra of the bulk gel samples heated up to 1000°C indicating that at this temperature the transformation in the corresponding gel-derived glasses occurs. The humidity sensitive properties of the gel-films have been evaluated by electrochemical impedance spectroscopy (EIS). The phosphorous content as well as the temperature of the heat treatments strongly affect the sensitivity to RH of the gel-derived films.     

The Effect of Precursor Chemistry on the Crystallisation and Densification of Sol-Gel Derived Mullite Gels and Powders

Stoichiometric and silica-rich mullite gels and powders were prepared using four different sol-gel methods. Thermal analysis, X-ray powder diffraction and dilatometry techniques were used to investigate the thermal decomposition, crystallisation and sintering of these mullite precursor gels. The method of preparation, by controlled hydrolysis of various mixtures of tetraethylorthosilicate, aluminium sec-butoxide and aluminium nitrate, affected the texture of the gels, producing single-phase or diphasic samples.The crystallisation sequence of the gels depended on the composition and method of preparation. Single phase mullite crystallised from homogeneous gels at 980°C, while diphasic gels initially formed of a mixture of -Al₂O₃ spinel and mullite, or simple -Al₂O₃ spinel, which subsequently transformed to mullite at 1260°C.Dilatometry and density measurement were used to investigate the sintering of compacts formed by pressing powders prepared from gels precalcined at 500°C. Varying the heating rates from 2 to 10°C min^-1 had little effect on the densification to 1500°C. However, the densification rate was sensitive to the degree of crystallinity and the amount and type of phases present at the sintering temperature. The presence of -Al₂O₃ spinel in the structure initially promoted densification, but the sintering rate was reduced considerably after mullite crystallised. Diphasic materials, especially those with an excess amount of silica in the original gel, sintered to higher densities due to the presence of excess silica promoting densification by viscous phase sintering.     

Enthalpies of Dilution of Aqueous Solutions of HCl, MgCl2}, CaCl2, and BaCl2 at 300, 325, and 350°C

Dilution enthalpies, measured using isothermal flow calorimetry, are reported for aqueous solutions of BaCl₂ at 300°C and 11.0 MPa, MgCl₂, CaCl₂, and BaCl₂ at 325°C and 14.8 MPa, and at 350°C and 17.6 MPa. Previously collected dilution enthalpies for aqueous solutions of MgCl₂ and CaCl₂ at 300°C and 10.3 MPa and for aqueous solutions of HCl at 250, 275, and 300°C at 10.3 MPa and 320°C at 12.8 MPa were included with the new data at 300°C and 11.0 MPa and at 350°C and 17.6 MPa when fitting the Pitzer parameters. The concentration range of the chloride solutions was 0.5 to 0.02 molal. Parameters for the Pitzer excess Gibbs ion–interaction equation were determined from the fits of the experimental heat data. Equilibrium constants, enthalpy changes, entropy changes, and heat-capacity changes for the association of alkaline earth metal ions and H⁺ with chloride ion were estimated from the heat data. For all systems, the enthalpy and entropy changes are positive and show accelerating increases with temperature. The resulting equilibrium constants show significant, but smaller, increases with temperature.     

Silica Gels and Gel Glasses Containing Silver and Platinum Metal Particles

Silica gels containing between 0.05 and 20.0 mol% Ag2O and between 0.1 and 1.0 mol% PtO2 have been synthesized using TEOS, C2H5OH, H2O, HNO3, HCl, AgNO3 and PtCl4 as precursors. The gels obtained with Ag2O are colorless, while the gels containing PtO2 are yellow. The gels have been heat treated in the 25–1000°C temperature range. The processes of structural evolution of gels have been studied by means of IR-spectroscopy, X-ray diffraction analysis, transmission electron microscopy (TEM) and transmission electron microdiffraction (TEMD). It has been established that the temperature of gel to gel-glass transition decreases when the Ag2O content of the gels increases. The same tendency was established for the gel to gel-glass transition in the SiO2-PtO2 system.Special attention was paid to the formation of silver and platinum metallic particles in amorphous materials. The microstructure of the gels has been observed and the sizes of the metal particles were determined to be from 3 to 25 nm.The crystallization processes in the gels heat treated at 1000–1200°C have been examined and besides the silver and platinum particles -cristobalite was formed.It has been shown that nanocomposite materials containing ultrafine silver and platinum particles in SiO2 amorphous or polycrystalline matrixes can be obtained.