Production mechanism of polyzirconocarbo- silane using zirconium(IV)acetylacetonate and its conversion of the polymer into inorganic materials

The reaction of polycarbosilane with zirconium(IV)acetylacetonate proceeded at 573 K in nitrogen atmosphere by the condensation reaction of the Si–H bonds in polycarbosilane and the ligands of zirconium(IV)acetylacetonate accompanied by the evolution of acetylacetone, and then the molecular weight increased by the cross-linking reaction with a formation of Si–Zr bond. The obtained polyzirconocarbosilane showed higher ceramic yield than the polycarbosilane. Zirconium contained in the pyrolysed polyzirconocarbosilane was furthermore found to have the effect of inhibiting crystalline grain growth of -type SiC up to high temperature, so Si–Zr–C–O fibre, which was obtained by the use of polyzirconocarbosilane as precursor, showed high tensile strength up to high temperature.     

29Si MAS-NMR investigation of the conversion process of a polytitanocarbosilane into SiC-TiC ceramics

A polytitanocarbosilane has been prepared from polycarbosilane and titanium n-butoxide.²⁹Si MAS-NMR was used to characterize the various steps of the conversion process of the polymer into the final ceramic. The reaction of titanium butoxide with polycarbosilane introduces oxygen into the polymer that seems to play an important role in the pyrolysis process. In the first stage up to 1000 ° C, the study reveals the cleavage of Si-C bonds and the formation of SiC_4-xO_x units. In the second stage, above 1000 ° C, the number of Si-O bonds decreases, probably due to a carbothermal reduction process. At 1500 ° C, the product can be described as a mixture of crystalline SiC and TiC with no excess carbon.     

Synthesis of a polytitanocarbosilane and its conversion into inorganic compounds

The novel polytitanocarbosilane, formed by the cross-linking of polycarbosilane with titanium tetra-alkoxide, was synthesized to examine the process of converting a multielement organometallic polymer into an inorganic compound. The chemical structure of this polymer was investigated by the techniques of infra-red spectroscopy (IR), gel permeation chromatography (GPC), number average molecular weight measurements and²⁹Si nuclear magnetic resonance (NMR) measurements. The pyrolysis products in N₂ gas at 1400° C and 1700° C were the microcrystalline and crystalline states of silicon carbide and titanium carbide, respectively.     

Development of a new continuous Si-Ti-C-O fibre using an organometallic polymer precursor

A polytitanocarbosilane, which is useful as the precursor polymer for ceramic fibre, was synthesized using polydimethylsilane, polyborodiphenylsiloxane and titanium tetraisopropoxide. The polytitanocarbosilane was melt-spun and using the continuous heat-treatment process from the polymer fibre to ceramic fibre, flexible Si-Ti-C-O fibre was produced. The density, tensile strength and Young's modulus of this amorphous ceramic fibre were found to be 2.35 g cm^–3, 3.0±0.2 and 220±10 GPa, respectively. The Si-Ti-C-O fibre retained its high tensile strength to higher temperatures (about 1200° C). The specific resistance of this ceramic fibre covered a wide range of 10⁷ to 10^–1cm. This ceramic fibre is considered to be useful as reinforcement fibre for composites.     

The crystallographic properties of PbTiO3 thin films fabricated by chemical vapour deposition

Lead titanate, PbTiO₃, is a well-known material having remarkable ferroelectric, piezoelectric and pyroelectric properties. Thin films of lead titanate have been successfully fabricated by chemical vapour deposition on a titanium substrate. Layers deposited on the titanium substrate using PbO vapour and O₂ gas grow along the (1 0 1) preferred orientation. The maximum dielectric constant and loss tangent of PbTiO₃ thin film deposited on a titanium substrate are about 90 and 0.02, respectively. The electrical resistivity of the PbTiO₃ is about 10⁹cm. The deposition rates of PbTiO₃ deposited on the titanium substrate were 10 to 15 mh^–1. A titanium dioxide interlayer formed between the PbTi0₃ film and titanium substrate materials. It might improve the adhesion of the film.     

The molecular weight distribution of polymerized iso-butylsilane and γ-methacryloxypropylsilane in aqueous solutions

The condensation of iso-butyltrimethoxysilane and -methacryloxypropyltrimethoxysilane (-MPS) in aqueous solutions has been studied. The silanes were hydrolysed in acidic solutions followed by adjustment of the pH of the solutions to allow condensation at different pH conditions. The molecular weights of the polymer mixtures obtained were determined by using gel permeation chromatography (GPC) with a light scattering detector. The GPC results suggest that the polybutylsilsesquioxanes differ in molecular weight distribution to the polymethacryloxypropylsilsesquioxanes. In general, polymers with the highest molecular weight were obtained in mild alkaline conditions. Strongly acidic as well as strongly alkaline conditions gave low molecular weight oligomers. The effect of fluoride ions on polymer molecular weight was also investigated. The polymers from the hydrolysis and condensation of iso-butylsilane and -MPS were monodisperse when the condensation was catalysed by fluoride ion. The molecular weights of the polymers were lower than those from the analogous base-catalysed reactions and the molecular weights increased with an increase in fluoride concentration.     

A study of the oxidation curing mechanism of polycarbosilane fibre by solid-state high-resolution nuclear magnetic resonance

The chemical structure of oxidation-cured polycarbosilane fibres has been studied by IR and chemical analysis, but its structure has not been identified in detail. In this work, the molecular structure was examined by chemical analysis, and solid state¹³C and²⁹Si nuclear magnetic resonance (NMR) spectroscopy. Si-O-Si, Si-O-C(I) and Si-O-C(II) bonds were formed by the oxidation curing process. The six chemical bonds (Si-C, Si-H, Si-Si, Si-O-Si, Si-O-C(I) and Si-O-C(II)) in oxidation-cured polycarbosilane were determined quantitatively, and the chemical structural model was shown. Solid state²⁹Si resolution NMR spectroscopy has proved to be a powerful tool for investigating the curing mechanism of oxidation-cured polycarbosilane fibres.     

Synthesis of continuous silicon carbide fibre

The structure of polycarbosilane is represented by three structural elements, but their quantification is difficult. Polycarbosilanes were synthesized by three methods and the respective molecular structures were examined by measurements of the molecular weight and the intrinsic viscosity, infrared, ultraviolet,¹H-,¹³C- and²⁹Si-NMR spectral measurements, and chemical analysis. The three structural elements (SiC₄, SiC₃H, SiC _x Si_4–x ) in the polycarbosilane molecule were determined quantitatively. By the comparison between¹H-NMR spectral data and calculation assuming a linear chain structure, the number of linkages in the unit consisting of ten silicon atoms was estimated to be 3 to 4. This result is in agreement with the result from the intrinsic viscosity; it was found that the shape of the polycarbosilane molecule is planar.     

Synthesis of thermosetting copolymer of polycarbosilane and perhydropolysilazane

A copolymer of polycarbosilane and perhydropolysilazane was obtained by reacting polycarbosilane with titanium n-butoxide and perhydropolysilazane. Titanium n-butoxide and perhydropolysilazane were essential for the polymer to show a thermosetting property. The thermosetting copolymers were converted into silicon carbide-based ceramics by pyrolysis in a stream of nitrogen to 1000 °C with about 80 wt% ceramic yield. The main phase of the pyrolysis product at 1500 °C in nitrogen was small crystallite -SiC. Elemental carbon, based on rule-of-mixtures composition, in the final ceramics could be reduced by varying the ratio of polycarbosilane/perhydropolysilazane. The copolymer was dry spun and pyrolysed to produce ceramic fibre. Pyrolysis in nitrogen to 1500 °C yielded a silicon carbide-based fibre with low oxygen and low elemental carbon content. A tensile strength of 1.8 GPa and an elastic modulus of 220 GPa were obtained for the fibre which ranged from 10–12 m in diameter. Crystallization to -Si₃N₄, -SiC, and -Si₃N₄ proceeded on annealing in nitrogen at 1700 °C for 1 h.     

Influence of molecular weight on the mechanical performance of a thermoplastic glassy polyimide

Mechanical testing of an advanced thermoplastic polyimide (LaRC^TM-SI) with known variations in molecular weight was performed over a range of temperatures below the glass transition temperature. The physical characterization, elastic properties and notched tensile strength were all determined as a function of molecular weight and test temperature. It was shown that notched tensile strength is a strong function of both temperature and molecular weight, whereas stiffness is only a strong function of temperature. A critical molecular weight (M _c) was observed to occur at a weight-average molecular weight (M _w) of 22000 g/mol below which, the notched tensile strength decreases rapidly. This critical molecular weight transition is temperature-independent. Furthermore, inelastic analysis showed that low molecular weight materials tended to fail in a brittle manner, whereas high molecular weight materials exhibited ductile failure. The microstructural images supported these findings.     

Influence of carbide formation on the strength of carbon fibres on which silicon and titanium have been deposited

Silicon or titanium was deposited on the filaments of carbon fibres by chemical vapour depositions and the reactions between the deposited silicon or titanium and the carbon fibres were investigated below 1300° C. Between the silicon and the carbon fibres, -SiC layers formed at rates of 1.5 to 3 nm in 3 h at 1300° C. These rates were 10^–4 times that of the TiC formation by the reaction of titanium with carbon fibre. Furthermore, the effect of the reaction on fibre strength was investigated. By reaction with silicon, the carbon fibre at a carbonized stage decreased in strength at the beginning of the reaction, but afterwards it recovered to the original level. The carbon fibre at a graphitized stage maintained its original strength after heat treatment for several hours at 1300° C. With the TiC-coated carbon fibres, the carbon fibres decreased in strength following the relation _m d ^–1/2, where d is the thickness of the TiC layer.     

聚碳硅烷的分子量分布与可纺性研究

阐述了聚碳烷的合成及其分子量分布，讨论了高低分子含量对聚碳硅烷熔点及可纺性的影响，而且提出了分子量分布的控制标准与方法。     

非水沉淀法制备纳米氧化钛及其光催化性能研究

采用非水沉淀工艺制备了锐钛矿型纳米氧化钛(TiO₂)。在冰醋酸的催化作用下, 钛酸丁酯在乙醇中发生非水解反应。冰醋酸的引入增加了钛酸丁酯中Ti-O键和C-O键的极性, 进而促进其在溶剂乙醇中发生非水解脱醚缩聚反应形成Ti-O-Ti键合。经过80℃回流24 h, Ti-O-Ti键重排形成锐钛矿型纳米TiO₂。其粒径为5~20 nm; 比表面积为169.4 m²/g。非水沉淀法制备的纳米氧化钛分散性良好, 光催化性能优异。紫外光照2 h, 纳米氧化钛对甲基橙的降解率达99.81%, 具有良好的污水处理应用前景。     

Ceramic fibres from polymer precursors

Following the first synthesis of silicon carbide fibres from polycarbosilane, the formation of ceramic fibres by the pyrolysis of organometallic polymers has recently begun to attract considerable attention. Si_xN_yC_z, Si-Ti-C-O and Si-N-O fibres have been synthesized by the pyrolysis pf polysilazane, polytitanocarbosilane and the nitridation of polycarbosilane, respectively. These ceramic fibres are promising as the reinforcement in composites. Here, a review is given of organometallic polymers as precursors for ceramic fibres, conversion processes from polymer to ceramic and the mechanical properties of ceramic fibres.     

Combustion synthesis of titanium carbide: Theory and experiment

The combustion synthesis of titanium carbide from elemental powders has been theoretically and experimentally studied as a model system for self -propagating high temperature synthesis (SHS) of refractory compounds. Calculations of the adiabatic temperature of combustion of graphite and titanium powders to form TiC _x have been made to show the effects of stoichiometry, dilution and the initial temperature of the reactants. Experimental observations on the stability of the combustion front, combined with theoretical predictions, lead to an estimated activation energy of 117 kJ mol^–1 for the process. This value is at least a factor of about four too low to correspond to a diffusion-controlled process. The combustion of graphite and titanium powders was accompanied by the evolution of gases whose primary constituent was found to be hydrogen. This observation was attributed to the reaction of adsorbed moisture with titanium powder. The titanium carbide phase resulting from the combustion of compacted mixed powders of the elements was highly porous ( 50% porosity). It can be obtained in high density (5% porosity) when pressure is applied during the combustion process.     

Synthesis of continuous silicon carbide fibre

The polycarbosilane (PC-470) synthesized by thermal decomposition of polydimethylsilane was melt-spun. The conversion process of the fibre into silicon carbide fibre was investigated by chemical analysis, TG-DTA and infra-red spectrum analysis, and measurements of the mechanical properties and densities. The conversion process of polycarbosilane (PC-TMS) synthesized by Fritz was examined and compared with the conversion process of PC-470. It is shown that the process is divided into three stages; condensation at the first stage, thermal decomposition at the second stage and crystallization at the third stage. The mechanical properties and density of the SiC fibre obtained by heattreatment were affected by the molecular weight and structure of the polycarbosilane of the starting material.     

Fine SrTiO3 and Sr(Mg0.4Ti0.6)O3–δperovskite ceramic powders prepared by a sol-precipitation process

Fine and Sr(Mg_0.4Ti_0.6)O_3– powders were prepared by a sol-precipitation method. Tetraisopropyl titanate was used as a starting material, which firstly chelated with the acetic acid to form a water-soluble titanyl precursor. This precursor was then precipitated in a strong NaOH solution, to which, a nitrate solution of the required ratio of was also added. By properly controlling reaction conditions, high crystalline undoped and Mg-doped strontium titanates with the dominating perovskite structures could be obtained directly at 80 °C. Owing to the chelating reaction of tetraisopropyl titanate with the acetic acid, the problem of the premature hydrolysis of titanium precursor was circumvented. The rates of the hydrolysis and condensation of titanyl acylate were also diminished. The final powder obtained had a uniform particle size of 40–60 nm. The formation mechanisms of and Sr(Mg_0.4Ti_0.6)O_3– were also discussed. This study indicated that in the entire sol-precipitation process, the mixing of cations was homogeneous and the diffusion of alkaline earth cations into titanium particles occurred all at atomic level, which allowed the realization of the optimized solid-solubility in the complex oxide system. This method could be exploited for the preparation of other doped titanates.     

Homogeneous (co)precipitation of inorganic salts for synthesis of monodispersed barium titanate particles

Various processes of coprecipitation or crystallization of inorganicsalts of barium and titanium from homogeneous solutions were studiedin this work. In particular, barium hydroxide and barium chloridesalt as well as titanium tetrachloride were used as the startingmaterials for dielectric-tuning homogeneous precipitation in mixedsolvents of isopropanol and water. Hydroxypropylcellulose was used asa steric dispersant. Evaluations of size, shape, and composition ofsynthesized particles were made using scanning electron microscopy,high-temperature X-ray diffractometry, and differential thermalanalysis. Results show that salt concentration, pH, and reaction timeare important in determining the morphology and composition of thefinal powder. The titania particles from dielectric-tuningprecipitation are perfect microspheres with narrow size distribution(near monodispersed), while the particles from barium salts areflake-like, irregular in shape and size. Instead of particlescontaining uniform compositions of barium and titanium compounds,dielectric-tuning coprecipitation yielded powders of two separatedphases, i.e., monodispersed titania microspheres (1 m) coated onbarium chloride salt flakes. Titanium-rich barium titanate wasobtained after calcination of coprecipitated powders. However,preliminary results show that the titania particles obtained bydielectric-tuning precipitation can be hydrothermally converted toBaTiO₃ particles that are fully crystallized after calcination above950°C.     

Synthesis of acrylate functional telechelic poly(lactic acid) oligomer by transesterification

The controlled synthesis of low molecular weight (Mn from 700 to 10 000 g/mol) poly(lactic acid) (PLA) telechelic oligomers end-capped with acrylate groups by a one-step reaction was investigated. A transesterification reaction was carried out in solution with a Lewis acid titanium catalyst using a high molecular weight PLA and a low molar mass diacrylate. End-functionalization was demonstrated by proton NMR spectroscopy which was also used for quantitative analysis and number average molecular weight determination using the ratio between the acrylic chain ends to the main groups of poly(D,L-lactic acid). The formation of low molar mass oligomers from high molecular weight poly(lactic acid) was verified by gel permeation chromatography. Matrix-assisted laser desorption ionization time-of-flight mass spectrometry showed that the above oligomerization was accompanied by the formation of cyclic compounds. By these means the feasability of a simple transesterification for a controlled synthesis of telechelic oligomers with molecular mass being a function of the added amount of diacrylate has been demonstrated. The glass transition temperatures of the elaborated oligomers varied from –35 to –5 °C. Subsequent thermal crosslinking was performed using benzoyl peroxide which enabled the formation of amorphous networks with Tgs close to the body temperature of 40 °C. Upon storage in a humid atmosphere the initially fairly hard and brittle networks became, due to hydrolysis, progressively more flexible thus demonstrating the potential biodegradability of these materials.     

Synthesis and characterization of cyclopentadithiophene-based low bandgap copolymers for all-polymer solar cells

Three conjugated copolymers based on cyclopentadithiophene (CPDT) units, namely, poly{4,4-bis(2-ethylhexyl)cyclopenta[2,1-b:3,4-b′]dithiophene-2,6-diyl-alt-2,1,3-benzothiadiazole-4,7-diyl} (P1), Poly{4,4-bis(2-ethylhexyl)cyclopeanta[2,1-b:3,4-b′]dithiophene-2,6-diyl-alt-2,1,3-benzoselenadiazole-4,7-diyl} (P2) and Poly{4,4-bis(2-ethylhexyl)cyclopenta[2,1-b:3,4-b′]dithiophene-2,6-diyl-alt-N,N′-bis(2-ethylhexyl)-3,4,9,10-perylene diimide-1,7-diyl} (P3) have been synthesized via Stille coupling reaction. The polymers were characterized by ¹H NMR spectroscopy, gel permeation chromatography (GPC), UV–vis absorption spectroscopy, and cyclic voltammetry. These new polymers exhibit broad and strong absorption between 500 and 800 nm. The highest occupied molecular orbital energy levels of polymers vary between ?4.98 and ?5.27 eV and the lowest unoccupied molecular orbital energy levels range from ?3.43 to ?3.70 eV. By employing P1 and P2 as electron donors (D) and P3 as electron acceptor (A), all-polymer solar cells with bulk heterojunction structure have been fabricated. Preliminary results indicate that these devices show higher open circuit voltage (V _OC ) in comparison with the traditional polymer/fullerene systems of P1 and P2 blended with the acceptor (6,6)-phenyl C₆₁-butyric acid methyl ester (PCBM).