Branched polysilanes from tetrafunctional monomers

Tetrafunctional silicon monomers have been incorporated into soluble branched polysilanes. Tetrakis(chlorodimethylsilyl)silane has been homopolymerized to form an irregular branched polymer which may contain some spiro and some bicyclic units. This polymer shows weak absorption at 300 nm, the region of the linear polysilane chains. It emits broadly in the region from 400 to 500 nm. The copolymers of tetrakis(chlorodimethylsilyl)silane with dichlorodimethylsilane are also soluble and in the presence of l ge amount of the tetrakis monomer emit in the region from 400 to 500 nm. By contrast, copolymers with phenyltrichlorosilane emit strongly at 450 to 650 nm, due to the phenylsilane hyperbranched structure. Small amounts of tetrachlorosilane can be incorporated into soluble polysilanes. Incorporation of =Si=units into polymers withn-hexyl substituents is very inefficient but leads to minor changes in emission spectra. Incorporation into polymers with phenyl substituents affects luminescence and increases molecular weights and broadens polydispersities. Reaction with dimethyldichlorosilane provides soluble low molecular weight oligomers and polymers. Polymers prepared with a small proportion of tetrachlorosilane show absorption and emission typical for linear polymers. Polymers synthesized with higher proportion of tetrachlorosilanes emit broadly at 400 to 500 nm, indicating the presence of Si clusters. The silicon clusters entrapped into soluble polymers are very easily oxidized as seen by the siloxane peaks in²⁹Si NMR spectra and they should be treated under complete exclusion of oxygen.     

Chemically Cross-linked Polysilanes as Stable Polymer Precursors for Conversion to Silicon Carbide

Cross-linked polysilanes were prepared by the co-polymerization of Me₂SiCl₂ or PhMeSiCl₂ with varying amounts of divinylbenzene (2–15% by weight) using molten sodium as the dehalogenating agent. All the cross-linked polysilanes were stable to air and could be processed thermally for conversion to silicon carbide. Polymers containing from 5–15% of the cross-linking agent underwent a uniform shrinkage during thermal treatment (1500 °C) to afford β-SiC in good yields. The ceramic was characterized by a variety of techniques including Raman and infrared spectroscopy, powder XRD, as well as Scanning Electron Microscopy (SEM). Dedicated to Prof. C. W. Allen in recognition of his outstanding contributions to inorganic polymers. Deceased in a tragic car accident in July 2004.     

New ways to polysilanes

New cyclosilanes with substituents, which are functional groups, open the possibility of forming new polycyclic silanes in an aimed synthesis. This is possible on five- and six-membered rings. Also, mixed systems with different ring sizes were prepared. The UV spectra are discussed. An annelid dicycle Si₁₀Me₁₈ was also prepared. With this compound a radical anion can be formed. New aspects of the electrochemical synthesis of polysilanes are presented and a chlorine stable anode is proposed for the first time. The polymerization reaction of hydrogen-containing methyldisilanes is discussed. This reaction yields polysilanes with a general composition (SiMeH) _n and a ceramic yield over 88%. The reaction is very different from the known reaction of monosilanes. Disilanes react faster and to high polymers. Two reaction mechanisms seem to be working simultaneously, i.e., a mechanism as postulated in monosilanes and a disproportionation reaction. These mechanisms are discussed.     

Enhancing the thermal insulation properties of polymer-derived SiCN(O) ceramic aerogels with a polysilazane-precursor design

In this study, we investigated the tunable porous structure of SiCN(O)-derived ceramic aerogels by changing the molecular structure of the polysilazanes from linear to branched. We also studied the effect of molecular structure on the thermal insulation properties of ceramic aerogels. As the percentage of branched molecular structure in the polysilazane precursor increased, the internal microscopic pore structure of the aerogels changed from macroporous to mesoporous. The specific surface areas and pore volumes of the ceramic aerogels prepared with different precursors increased after pyrolysis at 1000 °C, ranging from 3.7 to 255.9 m²/g and 0.01–0.36 cm³/g, respectively. The corresponding thermal conductivities increased slightly as the aerogels contracted after pyrolysis. The low thermal conductivity (0.046 W/(m·K) at minimum) can be attributed to the decrease in pore size caused by adjusting the precursor structure, which limits the thermal conduction of gas in the porous aerogel materials.     

New ways to polysilanes

New cyclosilanes with substituents, which are functional groups, open the possibility of forming new polycyclic silanes in an aimed synthesis. This is possible on five- and six-membered rings. Also, mixed systems with different ring sizes were prepared. The UV spectra are discussed. An annelid dicycle Si₁₀Me₁₈ was also prepared. With this compound a radical anion can be formed. New aspects of the electrochemical synthesis of polysilanes are presented and a chlorine stable anode is proposed for the first time. The polymerization reaction of hydrogen-containing methyldisilanes is discussed. This reaction yields polysilanes with a general composition (SiMeH) _n and a ceramic yield over 88%. The reaction is very different from the known reaction of monosilanes. Disilanes react faster and to high polymers. Two reaction mechanisms seem to be working simultaneously, i.e., a mechanism as postulated in monosilanes and a disproportionation reaction. These mechanisms are discussed.     

Laser synthesis of silicon carbonitride nanopowders; structure and thermal stability

Si₃N₄/SiC nanocomposite materials are of great interest for structural applications at high temperature. In silicon nitride based ceramics, the small size and the spherical shape of the grains constituting the material are two important parameters in favour of high temperature deformation. Therefore, SiCN nano-sized powders are real candidates as starting materials to elaborate dense Si₃N₄/SiC nanocomposites exhibiting the microstructure required for ductility at high temperature. SiCN nanopowders with different chemical compositions and characteristics can be prepared by CO₂ laser pyrolysis of organosilicon precursors. Laser pyrolysis of gaseous precursors is able to produce partly crystallised SiCN nanoparticles exhibiting a reasonable thermal stability and suitable for elaboration of ceramic materials. In order to reduce the cost and to improve the safety of the process, an aerosol generated from a liquid precursor, hexamethyldisilazane (HMDS), has also been used to synthesised SiCN nanopowders. However, in this latter case the powders obtained exhibit a high weight loss during heat treatment at high temperature. Therefore, in this study the effects of various synthesis parameters (chemical nature of the precursor and laser power) on the degree of crystallisation and on the thermal stability of nanopowders are investigated. Characteristics of powders such as chemical composition, morphology, structure and thermal stability are reported. A correlation between the synthesis conditions of powders and their thermal stability is established, and the synthesis parameters enabling improvement of thermal stability are determined.     

Role of the hydrotalcite-type precursor on the properties of CPO catalysts

New active and stable nano-structured catalysts obtained from hydrotalcite-type precursors (HT) have been synthesised as catalytic materials for the partial oxidation of methane. The prepared hydrotalcitic precursors containing carbonates or silicates as interlayer anions were calcined and the latter give rise to new mixed oxide and silicates phases. The calcined and reduced catalysts formed by mixed oxide and silicate phases were tested for the catalytic partial oxidation of methane (CPO). Finally, the role of the amount of the active metal and the amount of the excess of silicates inserted as anion were investigated.     

Excitation and Detection Energy Dependence of the Fluorescence of Polysilanes in Dilute Solutions

Excitation energy dependence of the fluorescence spectra and detection energy dependence of the fluorescence excitation spectra have been investigated for symmetrically and unsymmetrically substituted polyalkylsilanes in dilute solutions at different temperatures. The fluorescence maximum measured as a function of the excitation energy and the excitation maximum obtained at different detection energies at temperatures above the thermochromic transition temperature for the former polysilanes vary almost in the same way as those of the latter polysilanes. It is inferred from the spectroscopic data that the distribution and arrangement of the segment lengths of symmetrically substituted polysilanes above the transition temperature resemble those of unsymmetrically substituted polysilanes.     

Effect of the Chiral Center Position of an Optically Active Terminal Group on the Induction of Optical Activity in Polysilanes

Summary Polysilanes with an optically active alkoxy group, i.e., (S)-(+)-2-butoxy, (R)-(-)-2-butoxy, (S)-(-)-2-methyl-1-butoxy, and (S)-(+)-3,7-dimethyl-1-octoxy, at the terminal positions, the chiral carbon centers of which were located at the α, β, and γ positions relative to the oxygen, respectively, were prepared, and the effect of the position of chiral center of the terminal optically active group on the induction of optical activity in polysilanes was investigated. The circular dichroism (CD) spectra of these polymers showed positive Cotton signals around 340 nm at temperatures below -20 °C, but the intensities were small, indicating that the optically active groups at the terminal positions have some ability, albeit small, to induce optical activity to the polysilanes. Further, the optically active (S)-(+)-2-butoxy and (R)-(-)-2-butoxy groups did not control the helical sense direction of the polymers, despite the different chiral stimuli from the 2-butoxy groups introduced to the terminal positions. To control the helical structure of polysilanes by the use of optically active terminal groups, appropriate optically active groups are required.     

Ceramic Coatings and Glass Additives for Improved SiC‐Based Filters for Molten Iron Filtration

Reticulated silicon carbide (SiC) ceramic filters are prepared with modified coatings in an attempt to improve mechanical properties of the sintered filter. Two classes of coatings are used: mixtures of non‐SiC ceramic and sintering aid and mixtures of SiC and glass. Various candidate ceramics, sintering aids, and glasses are screened. The most promising coatings are determined to be silica with 5 wt% bismuth oxide and SiC with ≤10 wt% Spruce Pine Batch glass. Filters with these coatings are prepared and subjected to mechanical abuse. Both coatings improve the ruggedness of the filter relative to the standard uncoated SiC type. Filters with <10 wt% glass additive were subjected to molten metal impingement and filtration of liquid gray iron at 1510°C. Those with 5 wt% glass or more softened during filtration. Those with 2.5 wt% glass or less survived without failure.     

Preparation of self-healing Cf/SiBCN(O) composite using a novel polyborosilazane

In this study, novel polyborosilazane-derived SiBCN(O) ceramic was used as self-healing component in self-healing C_f/SiBCN(O) composite, which was prepared by polymer infiltration and pyrolysis (PIP) process. Molecular-level structure design of boron-containing ceramic precursors was utilized to achieve uniform dispersion of boron-containing self-healing components in prepared composites. No elemental diffusion was observed at the interface of ceramic matrix and carbon fibers, which resulted in stable SiBCN(O) structure. In addition, boron was uniformly distributed in C_f/SiBCN(O) composite ceramic matrix, which was beneficial for self-healing of cracks. Cracks and indentations were able to heal at high temperatures in air. The best crack-healing behavior occurred in air atmosphere at 1000 °C, with nearly complete crack healing. This excellent self-healing behavior was achieved because silicon and boron atoms in SiBCN(O) ceramic reacted with available oxygen at high temperatures to form SiO₂(l), B₂O₃(l), and B₂O₃·xSiO₂ liquid phases, which effectively filled cracks. In general, as-prepared C_f/SiBCN(O) composite exhibited excellent self-healing properties and shows great application potential in high-temperature environment applications such as aviation, aerospace, and nuclear power.     

Rapid, low temperature microwave synthesis of novel carbon nanotube-silicon carbide composite

Single wall carbon nanotubes (SWNTs) incorporated into ceramic matrices are known to impart enhanced mechanical, thermal and electrical properties to the composites formed. Current procedures for their synthesis face challenges, such as, the non-uniform dispersion of the SWNTs and their damage during high temperature processing in a reactive environment. These have led to poor interfacial matrix to SWNT adhesion and the ineffective utilization of the unique properties of the nanotubes. Here we report a rapid, low temperature microwave-induced reaction to create a novel nanoscale silicon carbide (SiC)-SWNT composite. The reaction, which was completed in 10 min, involves the decomposition of chloro-trimethylsilane and the simultaneous nucleation of nanoscale SiC spheres on the SWNT bundles. The bulk composite is a branched tree-like structure comprised of three-dimensionally arrayed SiC-SWNTs. The uniqueness of this approach lies in the formation of a ceramic directly on the SWNTs, rather than physical mixing, or the growth of nanotubes in a ceramic matrix.     

Investigation of the morphological changes promoted by heating of Si–C–O ceramics derived from a phenyl-rich hybrid polymer. Effect of Ni in the polymeric precursor

This study focuses on the structural and morphological changes promoted by heating of silicon oxycarbide ceramics obtained from hybrid polymeric precursors based on poly(methylsiloxane) and divinylbenzene, with or without nickel acetate, by pyrolysis under Ar at different temperatures. The increase of the temperature from 950 to 1500 °C promoted the densification and crystallization of SiC and graphite nanodomains in the ceramic bulk with or without Ni, as identified by HRTEM. Moreover, the Ni-containing precursor led to the formation of ultra-long amorphous nanowires on the surface and voids in the ceramic body obtained at 1500 °C. These nanowires presented different sizes and morphologies, but similar compositions, basically composed by silicon and oxygen, with the presence of carbon at their external layers. The growth mechanism and the nature of the nanowires are also proposed. The addition of nickel acetate in the polymeric precursor induced the formation of nanowires with different morphologies in the Si–O–C system.     

陶瓷前驱体聚硅氮烷的应用研究进展（二）

综述了陶瓷前驱体聚硅氮烷在制备陶瓷基复合材料、超高温材料、催化剂、多孔材料、粘接陶瓷、3D打印材料、三维陶瓷微结构材料,电脑芯片的多层连接技术、锂电池阳极上的应用研究进展。     

Adsorbed O2 on the Graphite‐Induced Growth of Ultra‐Long Single‐Crystalline 6H–SiC Nanowires

Large‐scale ultra‐long 6H–SiC nanowires were in situ synthesized on the as‐prepared SiC–Si ceramic substrate using graphite as the carbon source and substrate as the silicon source via improving the adsorbed O₂ content on the graphite precursors using milling technology. The as‐grown nanowires were typical single crystal of hexagonal 6H–SiC with diameters of 50–100 nm and lengths of up to several millimeters (or even centimeters). Vapor‐solid mechanism was proposed for the growth mode of the as‐grown ultra‐long 6H–SiC nanowires. This study not only provided new insight into the growth mode for in situ synthesizing 6H–SiC nanowires on silicon‐based ceramics, but also suggested a new design methodology for synthesizing ultra‐long nanowires.     

多孔石英基体上CVD法沉积氮化硅涂层的工艺、结构与性能研究

以甲硅烷(20％甲硅烷+80％氢气)和氨气作为反应前驱体,选择孔隙率为20％左右的多孔石英陶瓷基体,采用CVD法在多孔石英基体表面制备了氮化硅涂层.研究了沉积反应温度、反应压力、反应气体配比以及沉积时间等工艺参数对附着力的影响,确定了CVD法制备氮化硅涂层的最佳工艺参数,通过对所得涂层及复合材料进行抗弯强度和介电性能的表征,探讨了氮化硅涂层对多孔石英基体力学性能和介电性能的影响.     

用作陶瓷先驱体的可溶性聚硅烷的合成与表征

以甲基氢二氯硅烷、二甲基二氯硅烷为原料，利用均聚和共聚的方法，合成了几种不同组成的可溶性聚硅烷，研究了反应条件对可溶性聚硅烷产率的影响，并用IR、XRD对产物进行了表征。结果表明：甲基氢二氯硅烷在反应体系中的比例越高，可溶聚硅烷的产率越高，增加反应时间和降低反应温度可提高可溶聚硅烷的产率。     

Direktsynthesen,Modifizierungen und Anwendungsmöglichkeiten von Poly(carbosilanen)

„One-Pot”︁ Syntheses, Modifications and Applicabilities of Poly(carbosilanes) The modification of poly(carbosilanes) and the investigation of their application as binding agents and sintering additives in the production of pressurelessly sintered SiC-bulks as well as their effectiveness as precursors for SiC-fibers is of considerable interest. The synthesis of suitable compounds considers the variation of the carbosilane bridge, the following reactions of functional groups, the backbone branching at silicon and carbon atoms, and the insertion of heteroelements, especially boron and titanium. Different synthetic routes were used for the preparation of modified phenyl-containing poly(carbosilanes). The pyrolytic method, developed by YAJIMA and coworkers, transformed the methyl-containing poly(silanes) into poly(carbosilanes). The addition of polyborodiphenylsiloxane gave products with boron in the molecular sceleton. The development of a one step synthesis in analogy to the Wurtz-polycondensation leads to a series of methylene- and phenylethylene-bridged oligomeric compounds. Furthermore, branched and the heteroelements boron- and titanium-containing poly(carbosilanes) were obtained. The substitution of the functional phenyl groups leads to halogenated and alkyl-, alkenyl-, as well as alkynyl-substituted oligomers. Modified poly(carbosilanes) with unsaturated functional groups or SiH were prepared via Grignard-coupling. Beside benzylidene the units diphenylmethylene, p-xylylene and p-phenylene were used as carbosilane bridges. Directly synthesized copolymers were applicable as binding agents and sintering additives for the production of pressurelessly sintered SiC-bulks. Ethynyl-substituted poly(carbosilanes) were used as precursors for the production of oxygen-free SiC-fibers.     

Pressureless synthesis of fully dense and crack-free SiOC bulk ceramics via photo-crosslinking and pyrolysis of a polysiloxane

This paper presents the pressureless preparation of fully dense and crack-free SiOC ceramics via direct photo-crosslinking and pyrolysis of a polysiloxane. Elemental analysis revealed the presence of high levels of carbon in the SiOC ceramics. Thus, the samples showed the highest content (78-86 mol%) of segregated “free” carbon reported so far. XRD investigations indicated that the materials prepared at 1100 °C were X-ray amorphous, whereas the sample prepared at 1400 °C contained a turbostratic graphite-like phase and silicon carbide as crystalline phases, as additionally confirmed by TEM and Raman spectroscopy. Vickers hardness was measured to be 5.5-8.6 GPa. The dc resistivity of the prepared material at 1100 °C was 0.35 Ω m, whereas the ceramic pyrolyzed at 1400 °C showed a value of 0.14 Ω m; both values are much lower than those of other known SiOC materials. This latter feature was attributed to the presence of a percolating carbon network in the ceramic.     

Mechanical properties and microstructure of biomorphic silicon carbide ceramics fabricated from wood precursors

Silicon carbide-based, environment friendly, biomorphic ceramics have been fabricated by the pyrolysis and infiltration of natural wood (maple and mahogany) precursors. This technology provides an eco-friendly route to advanced ceramic materials. These biomorphic silicon carbide ceramics have tailorable properties and behave like silicon carbide based materials manufactured by conventional approaches. The elastic moduli and fracture toughness of biomorphic ceramics strongly depend on the properties of starting wood preforms and the degree of molten silicon infiltration. Mechanical properties of silicon carbide ceramics fabricated from maple wood precursors indicate flexural strengths of 344±58 MPa at room temperature and 230±36 MPa at 1350 °C. Room temperature fracture toughness of the maple based material is 2.6±0.2 MPa√m while the mahogany precursor derived ceramics show a fracture toughness of 2.0±0.2 MPa√m. The fracture toughness and the strength increase as the density of final material increases. Fractographic characterization indicates the failure origins to be pores and chipped pockets of silicon.