Preparation and Structure of Silicon Oxycarbide Glasses Derived from Polysiloxane Precursors

Silicon oxycarbide phases with different O/Si ratios were prepared by pyrolysis of highly cross-linked polysiloxane precursors. Their structure was investigated using quantitative ²⁹ Si solid-state NMR and X-ray photoelectron spectroscopy (XPS). The prominent part played by the redistribution reactions on the ceramic yield, the composition of the oxycarbide phases and their structure was illustrated. In a large range of compositions the oxycarbide phases formed by pyrolysis at moderate temperature (<1000°C) may be described as a purely random arrangement of CSi₄ tetrahedra and Si–O–Si bridges.     

Sol-Gel Synthesis and Structure of Borosilicon Oxycarbide Glasses

Existing sol-gel polymerisation/pyrolysis routes employing two separate boron containing metal alkoxide precursors have been applied to form multi-component silicon oxycarbide glasses based on a borosilicon oxycarbide (B–Si–O–C) system. 29Si, and 11B magic angle spinning nuclear magnetic resonance (MAS-NMR) was used to characterize the atomic structure of the gels, glasses and glass ceramics. Structural changes such as glass formation and crystal nucleation were identified by X-ray diffraction (XRD). Transmission electron microscopy (TEM) provided images of crystal nucleation and growth.     

Silicon Oxycarbide Glasses

The first attempts to introduce carbon into glass date back to 1951. But up until recently, the use of carbon or carbide raw materials, and the oxidation, volatilization and decomposition that accompany high temperature melting, have limited the synthesis of true silicon oxycarbide glasses. Here, the term silicon-oxycarbide refers specifically to a carbon-containing silicate glass wherein oxygen and carbon atoms share bonds with silicon in the amorphous, network structure. Thus, there is a distinction between black glass, which contains only a second-phase dispersion of elemental carbon, and oxycarbide glasses which usually contain both network carbon and elemental carbon. In addition to exploring the unique properties and applications of these glasses, per se, they are also of interest for developing models of the residual amorphous phases in polymer-derived silicon-carbide and silicon-nitride ceramics.The application of sol/gel techniques to glass synthesis has significantly advanced the development and characterization of silicon oxycarbide glasses. In this approach, alkyl-substituted silicon alkoxides, which are molecular precursors containing oxygen and carbon functionalities on the silicon, can be hydrolyzed and condensed without decomposition or loss of the carbon functional group. A low-temperature (<1000°C) heat-treatment of the gel creates a glassy silicate material whose molecular structure consists of an oxygen/carbon anionic network. In addition, there is always a blackening of the material due to elemental carbon, which forms during pyrolysis and densification of the gel. The nature of the network carbon, and especially the distribution and form of the elemental carbon, are fundamental to the structure and properties of these novel materials. Their chemical and physical characteristics as revealed by NMR, Raman and TEM are discussed in the overview. In addition, the high temperature stability of these glasses (up to 1750°C), and the effect of hot-pressing, are described.It will be shown that the silicon oxycarbide network is stable up to 1000–1200°C. The network carbon is terminated with hydrogen (i.e., CH, =CH2 and –CH3), and with polyaromatic carbon (i.e., nC6Hx) wherein most of the elemental carbon resides. These glasses can be described as molecular composites of polyaromatic graphene-rings dispersed in a silicon oxycarbide network. After heating to temperatures in excess of 1000–1200°C, the oxycarbide network decomposes through the loss of hydrogen, and a two- or three-phase glass-ceramic consisting of nanocrystalline graphite, silicon carbide, and amorphous silica or cristobalite, is created. Some of the properties and applications of these glasses/glass-ceramics for coatings, composites and porous solids are summarized.     

Preparation of Silicon Oxycarbide Ceramic Films by Pyrolysis of Polymethyl- and Polyvinylsilsesquioxanes

The sol-gel reactions of methyl- and vinyltrimethoxysilane under controlled conditions provided the corresponding polysilsesquioxanes and flexible thin films on further condensation of the precursors. Silicon oxycarbides containing a large amount of free carbon 58 mol% and 90 mol% were obtained in high yields 90 wt% on pyrolyzing the precursors of polymethyl-and polyvinylsilsesquioxane at 1400°C under N₂ atmosphere, respectively. Moreover, pyrolytic polycondensation of polyvinylsilsesquioxane was found to give the silicon oxycarbide ceramic films without deformations and cracks. The composition and properties of films were investigated.     

Infiltration of SiO<Subscript>2</Subscript>/SiOC Nanocomposites by a Multiple Sol Infiltration-Pyrolysis Process

SiO₂ containing hybrid inorganic-organic nanocomposites prepared by the sol-gel method from silica nanoparticles, tetraethylorthosilicate and silanol terminated polydimethylsiloxane were used as precursors for obtaining porous SiO₂/SiOC nanocomposites by pyrolysis in nitrogen atmosphere. A tetraethylorthosilicate sol and a triethoxysilane/methyldiethoxysilane sol, prepared by the sol-gel method and investigated by FT-IR, were used for a multiple sol infiltration-pyrolysis process in vacuum as precursors for a secondary SiO₂ and SiOC glassy phase respectively. As the density and porosity of these materials depends on the starting precursor composition, the sol infiltration-pyrolysis process was carried out in order to decrease the porosity and increase the density of such materials. This process was monitored using the sample weight gain and by a non-destructive method for measuring of the E modulus on each cycle. The initial and final material was also characterized by means of Hg porosimetry and the three-point bend test, at room temperature, of the nanocomposites was also examined.     

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.     

Effect of vinyltriethoxysilane addition on the pyrolytic conversion of tetraethoxysilane based silica gel

The effect of vinyltriethoxysilane (VTES) addition on the pyrolytic conversion of tetraethoxysilane (TEOS) based silica gel had been studied. Thermogravimetric analysis coupled with mass spectroscopy was carried out to study the thermal decomposition behavior of precursor gels. The ceramic yield of precursor gels was decreased with the increase of the VTES content. ²⁹Si magic angle spinning nuclear magnetic resonance indicated that the incorporation of VTES into TEOS not only changed the composition and structure of precursor gels, but also increased carbon-enriched SiO _x C_4?x units of silicon oxycarbide ceramics during the pyrolysis conversion. The carbon content of SiOC ceramic was almost unchanged between 1,000 and 1,500 °C. However, the O/Si ratio of the silicon oxycarbide ceramic was reduced and the free carbon content was increased with the increasing molar ratios of VTES/TEOS. Moreover, the carbothermal reduction reaction led to the free carbon content decreased with the increase of the sintering temperature.     

Silicon oxycarbide glasses from gels

Silicon-oxycarbide glasses can be synthesized from modified silica gels through a pyrolysis process in inert atmosphere. A critical analysis of the literature suggests a close relationship between oxygen content in the gel precursors and the amount of carbon atoms covalently bonded to silicon atoms in the corresponding silicon-oxycarbide phase. The problem of the formation of a free carbon phase will be discussed and related to the amount of carbon in the starting gel. An example of successful synthesis of an almost pure carbon-rich oxycarbide phase will also be presented.     

FT-IR and Porosity Study of Si-B-C-O Materials Obtained from TEOS-TEB-PDMS Derived Gel Precursors

Mixed vitreous oxycarbide glasses containing silicon and boron were prepared by pyrolysis of hybrid precursors in N₂ at 1100°C. Four different precursors were synthesized through the sol-gel process using TEOS, TEB and PDMS. Poly-condensation between the Si(OH) groups, from the hydrolysed TEOS, and the PDMS was observed by FT-IR spectroscopy. Boron seems not to incorporate into the network until pyrolysis of the precursors that form the oxycarbides. The oxycarbides were porous made of spherical interconnected particles. The porosity and mean pore size of the glasses increased with increasing TEB content.     

Tailoring Silicon Oxycarbide Glasses for Oxidative Stability

BlackglasTM polysiloxane systems produce silicon oxycarbide glasses by pyrolysis in inert atmosphere. The silicon oxycarbides evidence oxidative degradation that limits their lifetime as composite matrices. The present study characterizes bonding rearrangements in the oxycarbide network accompanying increases in pyrolysis temperature. It also addresses the changes in susceptibility to oxidation due to variations in the distribution of Si bonded species obtained under different processing conditions. The study is carried out using 29Si nuclear magnetic resonance (NMR) spectroscopy and a design of experiments approach to model the oxidation behavior. The NMR results are compared with those obtained by thermogravimetric analysis (TGA). Samples pyrolyzed under inert conditions are compared to those pyrolyzed in reactive ammonia environments.     

Caractérisation de revêtements PVD dans le Système V-C-N-O et comparaison avec les propriétés de revêtements similaires obtenus par OMCVD

Vanadium nitride, carbide, carbonitride and oxycarbide coatings were produced on steel substrates, by reactive magnetron sputtering from a vanadium target or by chemical vapor deposition using vanadocene as an organometallic precursor. The composition and crystallographic structure of coatings were determined by different techniques. The mechanical characteristics of the coatings are highly dependent on both their composition and the deposition technique.     

Surface Chemistry and Structure of Silicon Oxycarbide Gels and Glasses

In this study, the surface chemistry and structure of methyl-substituted silica gels and porous oxycarbide glasses were investigated. FTIR was used to measure the relative concentration of Si−CH₃ and Si−OH as a function of the degree of methyl-substitution and the pyrolysis temperature. The gels and glasses were further heated, dehydrated or hydrated, in situ, within the FTIR spectrometer. In the temperature range of 800–850°C, high surface area oxycarbide glasses were created with no detectable surface hydroxyl groups. Oxycarbide glasses synthesized in argon at 700°C displayed a weak band for surface hydroxyl groups and reversible physisorption of water, while those synthesized at 850/900°C showed a complete absence of surface hydroxyl groups and the formation of vicinal silanols upon chemisorption of water. Isolated silanols were observed upon heat treatment in vacuum. Formation of aromatic carbon species was found to correlate with the decomposition of the methyl groups. The oxycarbide surface is quite stable to densification (presumably due to elemental carbon on the pore surfaces). In the absence of oxygen, porous silicon oxycarbide glass powders maintain surface areas >200 m²/g at 1200°C. However, oxidizing species in the atmosphere deplete the aromatic carbon species, and the glasses lose surface area.     

Structural and Microstructural Evolution During Pyrolysis of Hybrid Polydimethylsiloxane-Titania Nanocomposites

The evolution during pyrolysis of hybrid polydimethylsiloxane-titania nanocomposites has been studied as a function of the ratio between polysiloxane and titania phases. The xerogels, prepared by the sol–gel process starting from diethoxydimethylsilane and titanium isopropoxide, have been heated under argon atmosphere and the evolution with temperature has been followed by infrared and ²⁹Si solid state nuclear magnetic resonance spectroscopies, thermal analyses, X-ray diffraction, N₂ sorption measurements and scanning electron microscopy. Below 800C, the polymer-to-ceramic conversion takes place at different temperatures with changing the titania content. The stability of Si–C bonds in polydimethylsiloxane networks depends on the metal oxide amount. The high reactivity of titanium atoms towards the Si–C bonds produces Si–C bond cleavage with mild thermal treatments and in the case of 30 mol% TiO₂, leads to the ceramization of the hybrid nanocomposite at 500C. Decreasing the titania load, a shift towards higher temperatures to complete the polymer-to-ceramic conversion is observed. The structural rearrangement of the siloxane moiety produces mesoporous and microporous materials, depending on the composition; in the case of 10 and 20 mol% TiO₂ content, the samples present high specific surface area up to 1200C.The crystallization process begins at 1000C and the phase evolution depends on the composition. The phase analysis obtained from XRD spectra shows that different crystalline oxide and oxycarbide phases develop during the thermal process, as a function of the amount of available carbon, ultimately leading to the preferential crystallization of titanium carbide. Between 1000 and 1600C the amorphous silicon oxycarbide phase undergoes a continuous structural evolution caused by the decrease of carbon content in the phase, leading to almost pure silica at 1600C.     

Microstructural and Dielectric Characterization of Sol-Gel Derived Silicon Oxycarbide Glass Sheets

Thin (50—1000 m) silicon oxycarbide glass sheets were synthesized by the pyrolysis of gel sheets obtained from a methyl-modified silica sol containing colloidal silica under inert atmosphere between 900 and 1450°C. The microstructure of these glass sheets was investigated with the help of high resolution scanning and transmission electron microscopy (HR-SEM and HR-TEM), X-ray diffraction and Raman spectroscopy and their dielectric properties were determined. The surface morphology as observed with HR-SEM did not exhibit a notable temperature dependence. HR-TEM studies showed that the glass sheets sintered up to 1200°C are amorphous, whereas those sintered at 1450°C contain uniformly dispersed crystallites of SiC and graphite. X-ray diffraction studies were found in agreement with the HR-TEM results. Raman spectroscopy showed that free carbon is present as an amorphous phase till a temperature of 1000°C, whereas at temperatures 1200°C, the presence of graphitic carbon was observed. Silicon oxycarbide glass sheets heat treated at temperatures up to 1200°C, showed a dielectric constant between 4.1 ± 0.11 and 4.6 ± 0.15 in the frequency range from 75 kHz to 5 MHz, with corresponding losses between 0.0008 and 0.1100. Such silicon oxycarbide glass sheets sintered at 1200°C could find an application as substrates for electronic packaging.     

具有碱催化活性的有序氮氧化硅MCM-41介孔分子筛的制备与性能研究

以介孔氧化硅MCM-41为氮化前驱体, 以纯的氨气为氮源, 通过调节氮化工艺参数, 制备出了氮含量高达23.01 wt%、比表面积高达665.4 m²•g^－1、平均孔径为2.5 nm的氮氧化硅有序介孔分子筛材料. 采用CNH元素分析、N₂吸附- 脱附分析、小角XRD、高分辨透射电镜(HRTEM)、红外光谱以及²⁹Si 固体核磁共振谱(MAS NMR)等技术对材料的结构进行系统的研究. 并且通过苯甲醛和丙二腈的缩合反应研究了该类材料的碱催化活性. 研究表明, 在30 ℃反应3 h后苯甲醛的转化率达到99.9%.     

BaTiO3纳米晶的制备和结构

ＢａＴｉＯ_３纳米晶的制备和结构方佑龄，赵文宽，邹化民，王仁卉（武汉大学化学系，武汉大学物理系，武汉，４３００７２）关键词钛酸钡纳米晶，过氧化物，制备，结构ＢａＴｉＯ３具有高介电常数及优异的铁电、压电性能，是一种重要的电子陶瓷材料，因此，对其纳米晶的?..     

The method of flash vacuum pyrolysis,preparative applications and analytical studies

Flash vacuum pyrolysis has been used to prepare a variety of differently substituted derivatives of the benzocyclobutene ring system starting with simple precursors. An analytical gas flow reactor is described which simulates reaction conditions of flash vacuum pyrolysis experiments. This reactor allows to optimise reaction conditions and to obtain structure reactivity correlations for thermolytic gas phase reactions.     

Effect of polydispersity on the crystallization kinetics of suspensions of colloidal hard spheres when approaching the glass transition

We present a comprehensive study of the solidification scenario in suspensions of colloidal hard spheres for three polydispersities between 4.8% and 5.8%, over a range of volume fractions from near freezing to near the glass transition. From these results, we identify four stages in the crystallization process: (i) an induction stage where large numbers of precursor structures are observed, (ii) a conversion stage as precursors are converted to close packed structures, (iii) a nucleation stage, and (iv) a ripening stage. It is found that the behavior is qualitatively different for volume fractions below or above the melting volume fraction. The main effect of increasing polydispersity is to increase the duration of the induction stage, due to the requirement for local fractionation of particles of larger or smaller than average size. Near the glass transition, the nucleation process is entirely frustrated, and the sample is locked into a compressed crystal precursor structure. Interestingly, neither polydispersity nor volume fraction significantly influences the precursor stage, suggesting that the crystal precursors are present in all solidifying samples. We speculate that these precursors are related to the dynamical heterogeneities observed in a number of dynamical studies.     

Quantitative analysis of silicon-oxynitride films by EPMA

Thin films of silicon oxynitride with diverse compositions were prepared by de-magnetron sputtering of silicon, utilising oxygen and nitrogen gas flows and the sputtering power to vary the composition. In order to investigate the composition of these films, a method of analysis by electron probe micro analysis with energy dispersive detection was developed and the figures of merit were compared to the wavelength dispersive method used by other authors. The precision and repeatability of the results are evaluated and the accuracy is checked by comparison with Rutherford backscattering and nuclear reaction analysis. Energy dispersive X-ray spectrometry was proven to be applicable to analyse silicon oxynitride films of any composition yielding quantitative results for nitrogen and oxygen as well as silicon. Besides the good analytical performance, electron probe micro analysis with energy dispersive X-ray spectrometry has turned out to be a non-destructive, quick, easy to use and cost effective tool for the routine analysis of light elements in thin films.