Study on thermal decomposition processes of polysiloxane polymers—From polymer to nanosized silicon carbide

The objective of this study is to determine experimentally the usefulness of different polysiloxanes as precursors for bulk ceramic products. Such resins are an alternative for currently commercially used polycarbosilanes. Four types of polysiloxanes were used. The polymers differed in C/Si molar ratio. Thermogravimetric measurements of polymers were made to determine curing and heat treatment conditions. Ceramic yield (Y_c) after heat treatment over the temperature range from 20 to 1700 °C was determined. Structure, microstructure and phase composition of ceramic products obtained from the polymers were investigated. It was found that during thermal decomposition of polymers in the temperature range from 20 to 1000 °C amorphous inorganic Si–C–O ceramics were formed. When the temperature exceeded 1500 °C nanosized 3C and 2H types of silicon carbide crystallized from the resin precursors with C/Si molar ratio higher than 1. On the contrary, heat treatment of polymer with C/Si molar ratio close to 1 did not lead to the formation of nanocrystalline silicon carbide.     

Mechanism of structural networking in hydrogels based on silicon and titanium glycerolates

Formation of organic/inorganic hydrogels based on silicon- and titanium-glycerol precursors synthesized by transesterification of alkoxy derivatives in excess of glycerol was investigated. The precursors in excess of glycerol and obtained gels were studied by chemical and physical methods including gelation kinetics, IR spectroscopy, XRD, dynamic and electrophoretic light scattering, mechanical deformation, which disclosed the basic difference in the gelation mechanism and structure of network in the hydrogels. Due to this difference, the gelation time of silicon- and titanium-glycerol precursors depended on pH or electrolyte addition in an opposite way. In the wide pH range, silicon-glycerol hydrogel was a polymeric single-phase system formed by the polymeric network homogeneously swollen in liquid water/glycerol medium. Flory-Rehner theory applied to the elastic modulus of these gels gave 40-180 monomer base units in the subchains of the network depending on water content in the gel. The mechanism of networking was three-dimensional polycondensation promoted by the electrically charged functional groups attached to the flexible polymeric chains. Electrolyte solutions provided the gelation according to Hofmeister series. Titanium-glycerol hydrogels were heterogeneous colloid systems at pH>1.5 and single-phase polymeric gels at lower pH. Electrolyte solutions provided the gelation according to Schultze-Hardy rule.     

Gravimetric determination of free carbon and silicon carbide in silica fume

Silica fume is formed as a by-product in the manufacture of silicon from quartzite. This paper describes an analytical method for the determination of free carbon and silicon carbide in silica fume. The silicon carbide was determined after removal of free carbon, amorphous silica, crystalline silica, graphite and silicon from the fume. The free carbon content was found to vary from 2 to 8% while the silicon carbide content ranged from 1 to 5%. X-ray diffraction, thermal analysis, scanning electron microscopy and Fourier Transform infrared spectroscopy were used to validate the steps used in the analytical procedure. The purpose of determining the free carbon and silicon carbide content of the fume is to help understand the efficiency of the reduction process and mechanism of the reaction.     

Sol–gel processing at increased temperatures: the formation of polyester nanocomposites

Polyester nanocomposites were prepared using sol–gel precursors, prehydrolyzed sols, or nanoparticles in polyester formulations. The different inorganic components were introduced in the early stages of the esterification reaction and a typical polymerization temperature program was applied leading to temperatures up to 240 °C at low pressures. The structural and physical properties of the final materials depend on the applied method for the introduction of the sol–gel materials. Silicon atoms were incorporated into the polyester chain if silicon tetraalkoxide was used as precursor. The silicon atoms represent branching points in the polymer structure. Prehydrolyzed sols that were prepared under acidic conditions were another source of silicon and formed larger inorganic aggregates in the polymer matrix. Nanoparticles prepared via the Stöber process were the third inorganic species in polyester formation. All three processing pathways produced different kinds of materials depending on the type of silica incorporated in the polyester networks but also with regard to the nanoscale structure of the materials. Both, composition and structure have a major influence on the final polyester nanocomposite properties. Model reactions between silicon tetraalkoxides and diols or diacids using the temperature program for the polyester formation showed that exchange reactions of the alkoxides and the alcohols or acids can occur and the obtained products can carry out side reactions in the polyester formation. The final materials show a homogeneous distribution of the silicon containing moieties in the polyester matrix. The viscosities and the branching degrees of the polymers changed dramatically compared to the pristine polymers by incorporation of the sol–gel precursors.     

Synthesis of pharmacologically active hydrogels based on combined silicon and titanium polyolates

The target synthesis of new biologically active hydrogels based on combined silicon and titanium polyolates was carried out. The optimum conditions for hydrogel formation and their composition were determined. The type of hydrogels and mechanisms of gelation depend on the nature of polyols: gels based on combined silicon and titanium polyethylene glycolates are polymeric and formed via the polycondensation mechanism, whereas gels based on combined silicon and titanium glycerolates are colloidal and formed via the coagulation-condensation mechanism. The combined hydrogels based on silicon dimethyl glycerolates and titanium tetraglycerolate exhibit enhanced transcutaneous, wound healing, and regenerating activity.     

Applications of Inorganic Polymeric Materials II: Polysilanes

Polysilanes which cover one of the most attractive and challenging fields, are high molecular weight polymers with inorganic elements in their backbone. These materials have silicon atoms in their main chain and exhibit unique properties resulting from the easy delocalization of sigma electrons in the Si─Si bonds. There are many technical uses as well as applications of these materials such as precursors of silicon carbide ceramics; a strengthening agent in porous ceramic; imaging materials in microlithography; photoiniting in radical reactions; and photoconducting, conducting, and semiconducting which are due to the unusual mobility of sigma electrons. In this work, the main structural features, properties, and some other important and recent applications of polysilanes are discussed.     

Nanoparticle formation using a plasma expansion process

We describe a process in which nanosize particles with u narrow size distribution are generated by expanding a thermal plasma carrying vapor-phase precursors through a nozzle. The plasma temperature and velocity profiles are characterized by enthalpy probe measurements. by calorimetric energy balances. and by a model of the nozzle flow. Aerosol samples are extracted from the flow downstream of the nozzle by means of a capillary probe interfaced to a two-stage ejection diluter. The diluted aerosol is directed to a scanning electrical mobility spectrometer (SEMS) which provides on-line size distributions down to particle diameters of 4 nmt. We have generated silicon, carbon, and silicon carbide particles with number mean diameters of about 10 not or less, and we have obtained some correlations between the product and the operating conditions. Inspection of the size distributions obtained in the experiments, together with the modeling results, suggests that under our conditions silicon carbide formation is initiated by nucleation of extremely small silicon particles from supersaturated silicon vapor, followed by chemical reactions at the particle surfaces involving carbon-containing species from the gas phase.     

Structure of hybrid organic–inorganic sols for the preparation of hydrothermally stable membranes

A procedure for the preparation of hybrid sols for the synthesis of organic–inorganic microporous materials and thin film membranes is reported. We describe silane reactivity and sol structure for acid-catalysed colloidal sols from mixtures of either tetraethylorthosilicate (TEOS) and methyltriethoxysilane (MTES), or bis(triethoxysilyl)ethane (BTESE) and MTES. Early-stage hydrolysis and condensation rates of the individual silane precursors were followed with ²⁹Si liquid NMR and structural characteristics of more developed sols were studied with Dynamic Light Scattering. Condensation was found to proceed at more or less similar rates for the different precursors. Homogeneously mixed hybrid colloids can therefore be formed from precursor mixtures. The conditions of preparation under which clear sols with low viscosity could be formed from BTESE/MTES were determined. These sols were synthesised at moderate water/silane and acid/silane ratios and could be applied for the coating of defect-free microporous membranes for molecular separations under hydrothermal conditions.     

聚有机硅倍半氧烷热解研究进展

国防航空工业的发展需求高性能陶瓷,尤其是纳米陶瓷。聚有机硅倍半氧烷可作为前驱体,通过热解制备陶瓷。该方法操作简便,易于控制。本文综述了国外有关聚有机硅倍半氧烷热解理论与应用研究近况,并对这一领域的发展进行了展望。     

Composition and thermal stability of SiO2-based hybrid materials TEOS-MTEOS system

Hybrid materials with different amounts of organics permanently bound on the inorganic network obtained in the TEOS-MTEOS (tetraethoxysilan-methyltriethoxysilan) system are used for obtaining coatings with different optical and mechanical properties. To study the thermal stability of the mentioned materials, compositions with different molar ratios of the precursors were prepared. The influence of the solvent and water amounts on the gelation process was also investigated. The gels obtained were characterised by IR spectrometry and their decomposition temperatures were determined by DTA/TG. Thermal stability of the gels is rather influenced by their composition than the conditions of the gelation process. This revised version was published online in July 2006 with corrections to the Cover Date.     

Epoxide Opening versus Silica Condensation during Sol–Gel Hybrid Biomaterial Synthesis

Hybrid organic–inorganic solids represent an important class of engineering materials, usually prepared by sol–gel processes by cross‐reaction between organic and inorganic precursors. The choice of the two components and control of the reaction conditions (especially pH value) allow the synthesis of hybrid materials with novel properties and functionalities. 3‐Glycidoxypropyltrimethoxysilane (GPTMS) is one of the most commonly used organic silanes for hybrid‐material fabrication. Herein, the reactivity of GPTMS in water at different pH values (pH 2–11) was deeply investigated for the first time by solution‐state multinuclear NMR spectroscopic and mass spectrometric analysis. The extent of the different and competing reactions that take place as a function of the pH value was elucidated. The NMR spectroscopic and mass spectrometric data clearly indicate that the pH value determines the kinetics of epoxide hydrolysis versus silicon condensation. Under slighly acidic conditions, the epoxy‐ring hydrolysis is kinetically more favourable than the formation of the silica network. In contrast, under basic conditions, silicon condensation is the main reaction that takes place. Full characterisation of the formed intermediates was carried out by using NMR spectroscopic and mass spectrometric analysis. These results indicate that strict control of the pH values allows tuning of the reactivity of the organic and inorganic moities, thus laying the foundations for the design and synthesis of sol–gel hybrid biomaterials with tuneable properties.     

Production of porous ceramic materials using nanodisperse SiC powder

Porous ceramic materials were produced by hot pressing of a nanocrystalline (19 nm) silicon carbide powder synthesized by a hybrid method that combined the sol–gel processing of a finely divided and chemically reactive SiO₂–C system and the carbothermic synthesis at moderate (1400°C) temperature in a vacuum. It was studied how such characteristics as density, porosity, sizes of crystallites and aggregates of SiC particles, specific surface area, and compressive strength depend on pressing temperature (1400, 1500, 1600, and 1700°C).     

Sol-Gel and Ultrafine Particle Formation via Dielectric Tuning of Inorganic Salt-Alcohol-Water Solutions

Under some conditions, inorganic salts can be as good precursors for sol-gel-type processing as those obtained from expensive metalloorganic precursors such as alkoxides. In this work, the formation of monodispersed hydrous zirconia microsphere particles (particularly nanosized) and gels was achieved in solutions of zirconyl chloride dissolved in alcohol-water mixed solvents. The dielectric property of the mixed alcohol-water solvent directly affects the nucleation and growth of zirconia clusters/particles in homogeneous solutions. A lower dielectric constant of mixed solvent corresponds to a lower solubility of inorganic solute and, thus, a shorter induction period for nucleation as well as higher solid particle growth kinetics. Dynamic light scattering (DLS) was used to monitor the homogeneous nucleation and growth processes, while final particles and gels were studied by scanning electron microscopy (SEM) and high-temperature X-ray diffraction (HTXRD). The sol-gel processes in the mixed solvent system can be adjusted using the processing parameters, including the initial inorganic salt concentration (C), alcohol/aqueous medium volume ratio of the mixed solution (RH), incubation temperature (T), incubation time (t), concentration of hydroxypropyl cellulose (HPC), and ammonia neutralization. Monodispersed submicron and nanoscale (<100 nm) zirconia microspheres/powders were successfully synthesized under conditions of high RH (5) and using HPC (molecular weight of 100,000, 2.0x10(-3) g/cm(3)) and ammonia neutralization. Initial salt concentration affects the particle size significantly. Gel materials were obtained under conditions of low RH (1.0). Microstructure and transparency of gels changed significantly from low (0.05 M) to high (0.2 M) concentration of the metal salt. We have also demonstrated that monodispersed particle production can be achieved not only at low temperatures (<100 degrees C) but also at room temperature using an inorganic salt precursor. Copyright 2000 Academic Press.     

Study on the applications of SiC thin films to MEMS techniques through a fabrication process of cantilevers

We have tried to find the most suitable conditions for the deposition process of silicon carbide thin films as a material for MEMS techniques. We have also studied its application to semiconductor processes. To do this, we have tried to fabricate several dimensions of cantilevers with these silicon carbide thin films. High quality silicon carbide thin films are grown by metal-organic chemical vapor deposition (MOCVD). This process employs single molecular precursors such as diethylmethylsilane (DEMS), 1,3-disilabutane (DSB) at a pressure of 1 × 10⁻³ Pa and a growth temperature in the range of 700–1000 °C. Two fabrication methods are tested for initial fabrication of cantilevers. First, deposit SiC thin films on Si based atomic force microscopy (AFM) cantilevers. Second, used the lift-off process. To get three-dimensional cantilever-shaped SiC thin films, moreover, we chemically etched silicon substrate with strong alkaline solution such as TMAH at 80 °C. In addition, a high resolution of probe tips on the cantilevers was achieved using electron-beam deposition in a carbon atmosphere.     

A novel sacrificial interlayer-based method for the preparation of silicon carbide membranes

A novel method is presented based on the use of sacrificial interlayers for the preparation of nanoporous silicon carbide membranes. It involves periodic and alternate coatings of polystyrene sacrificial interlayers and silicon carbide pre-ceramic layers on the top of slip-casted tubular silicon carbide supports. Membranes prepared by this technique exhibit single gas ideal separation factors of helium and hydrogen over argon in the ranges 176–465 and 101–258, respectively, with permeances that are typically two to three times higher than those of silicon carbide membranes prepared previously by the more conventional techniques. Mixed-gas experiments with the same membranes indicate separation factors as high as 117 for an equimolar H₂/CH₄ mixture. We speculate that the improved membrane characteristics are due to the sacrificial interlayers filling the pores in the underlying structure and preventing their blockage by the pre-ceramic polymer. The new method has good promise for application to the preparation of a variety of other inorganic microporous membranes.     

邻苯二酚在合成合硅方钠石分子筛大单晶中的螯合效应

通过对合成全硅方钠石（Si-SOD)溶胶的液体^29Si NMR、IR光谱、紫外可见光谱,及其晶化产物的^13C MAS CP NMR3和^29Si NMR的研究表明,邻苯二酚在的反应混合物中能和硅物 生反应而生成硅－本二酚螯合物,该螯合物在水热条件下是亚稳态的,它能缓慢释放出生成分子筛所需要的硅种,使反应体系中的晶核始终处于数量较少状态,从而有利于晶体的缓慢长大。     

Crystallization and thermoreversible gelation of poly(butylene terephthalate)–epoxy mixtures

The thermoreversible gelation of solutions of poly(butylene terephthalate) (PBT) and a liquid diglycidyl ether of bisphenol-A epoxy has been investigated. The morphology of the gels and the conditions under which they form have been characterized by optical microscopy, thermal analysis, and x-ray scattering. Gels were found to form under two different conditions and with different morphologies. Gels formed after a considerable delay when homogenous PBT-epoxy solutions were cooled to slightly below the dissolution temperature of crystalline PBT. These gels contained large, irregular PBT spherulites and smaller birefringent interspherulitic matter. The melting of these gels and the onset of macroscopic flow coincided with the melting of the interspherulitic matter, and occurred before the melting of the large spherulites. Thermoreversible gels formed very quickly when PBT-epoxy solutions were self-nucleated by heating a dispersion of crystalline PBT in epoxy slightly and briefly above the dissolution temperature and then cooling. These gels displayed only a weak background birefringence and were molten when the weak birefringence disappeared. In both cases, gelation occurred by the formation of a three-dimensional PBT network in the epoxy liquid, and the nodes of the network were crystalline PBT particles. $ 1994 John Wiley & Sons, Inc.     

Nanocomposite Gels: New Advanced Functional Soft Materials

Summary: Nanocomposite gels (NC gels) consisting of poly(N-alkylacrylamides) and exfoliated inorganic clay were prepared by in-situ, free-radical polymerization at high yield under mild conditions (near ambient temperature, without stirring). Various shapes and different surface forms of NC gels were readily obtained using corresponding vessels and templates, since NC gels were always mechanically tough. The view that polymer/clay networks are formed in NC gels was supported by dynamic viscoelastic and swelling measurements. The entirely different mechanical properties of NC gels, compared with conventional, chemically-crosslinked hydrogels (OR gels), are discussed on the basis of their network structure. In addition to functions previously reported, NC gels exhibit further interesting characteristics, such as inherent incombustibility, good thermal conductivity, large heat capacity, they can be readily colored and fabricated as foams. NC gels can be utilized as environmentally-friendly, soft materials from the viewpoints of resources and waste, as their primary component is water.     

TiO2-Based Porous Materials Obtained from Gels, in Different Experimental Conditions

The gels which are precursors of TiO₂ porous materials are prepared by the controlled hydrolysis-condensation of titanium isopropoxide by polymeric method. In the present work, a study of the influence of different experimental conditions (water/alkoxide ratio, solvent/alkoxide ratio and temperature) on the structure and texture of the polymeric gels obtained with the same type of alkoxide has been investigated. The structural and textural modifications for the unsupported materials have been detected using DTA/TGA, XRD, specific surface area and pore size computerized measurements. The optical properties of the supported materials deposited on silicon wafers have been investigated using ellipsometric method. Supported and unsupported porous materials with different structure and texture have been obtained depending on different experimental and thermal treatment conditions.     

Morphology and dispersion control of titania–silica monolith with macro–meso pore system

Macroporous gels with bicontinuous morphology in micrometer range were prepared in a titania?Csilica system containing 5 and 7.6 mass?% titania using tetraethoxysilane and four kinds of Ti precursors, two titanium alkoxides, titanium chloride and titanium sulfate, under coexistence of poly(ethylene glycol) (PEG) with an average molecular weight of 20,000. In all the systems with different Ti precursors, the addition of PEG induced phase separation, and the macroporous morphology was formed when the transitional structure of phase separation was frozen-in by sol?Cgel transition of inorganic components. However, we can see large differences in phase separation tendency and Ti dispersion in silica network depending on the Ti precursors used. When titanium alkoxides were added into pure silica sol?Cgel system, phase separation tendency largely decreased, so that low temperature reaction was necessary for macropore formation. When we used titanium salts, on the other hand, phase separation tendency does not change much from pure silica system. The difference has been tentatively attributed to the difference in the mixing level of Ti in silica network. Although titania tended to aggregate when titanium alkoxides were used as precursors, Ti could be well dispersed in silica gel matrix when acetylacetone was added in the alkoxide system or when titanium salts were used as Ti precursors.