High char‐yielding poly[acrylonitrile‐co‐(itaconic acid)‐co‐(methyl acrylate)]: synthesis and properties

Polyacrylonitrile terpolymers of various compositions consisting of acrylonitrile (AN), itaconic acid (IA) and methyl acrylate (MA) were synthesized by solution polymerization in dimethylsulfoxide. Increase in concentration of either IA or MA retarded the overall polymerization rate and the polymer molecular weight. The system consisting of AN + MA and varying IA concentration was more prone to retardation in comparison with the system composed of AN + IA with variable MA concentration. The retardation factors were quantified. Minor quantities of MA boost the reactivity of IA in the terpolymer system. The terpolymer was richer in MA vis‐à‐vis the feed. The thermal characteristics of the terpolymer were examined as a function of its composition. In contrast to the copolymer of AN and IA requiring 1–1.5 mol% IA, the terpolymer required an IA content of approximately 2.5 mol% for optimum thermal stability. The polymer with 90 mol% AN, 2.5 mol% IA and 7.5 mol% MA exhibited reasonably good char‐forming characteristics and thermal stability. The overall crystallinity and crystallite size of the polymers were found to decrease on incorporation of the comonomers. The ‘aromatization index’ of the copolymer increased with the temperature of pyrolysis through re‐organization of the tetrahydropyridine ladder structure. Copyright © 2005 Society of Chemical Industry     

Manufacture of carbon fibers from polyacrylonitrile precursors treated with CoSO4

Free‐radical solution copolymerization of itaconic acid and acrylonitrile was carried out in DMSO using azodiisobutyronitrile as an initiator, changing the feed rate of itaconic acid. The resulting polymerization solution was spun to form polyacrylonitrile (PAN) precursors of carbon fibers. The precursors were treated with a CoSO₄ aqueous solution on‐line. The structure and properties of untreated and treated PAN precursors and the resultant carbon fibers were characterized by SEM and TEM, a stabilization process, etc. It is suggested that CoSO₄ acts as a catalyst in the formation of a ladder structure and reduces the temperature of cyclization, and the carbon fibers developed from treated PAN fibers showed improvement in the tensile strength and the Young's modulus. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 153–158, 2002     

尿素对以硝酸铝和葡萄糖为原料合成氮化铝粉末反应过程中相变及反应速率的影响

以硝酸铝(Al(NO3)3·9H2O)和葡萄糖(C6H12O6·H2O)为原料,利用碳热还原法制备氮化铝粉末,研究了尿素对前驱物的制备及前驱物氮化反应的影响,研究发现添加尿素合成的前驱物和未添加尿素合成的前驱物在氮化反应过程中相变和反应速率存在较大差异。在没有添加尿素合成的前驱物的氮化反应过程中,出现了γ-Al2O3、α-Al2O3、AlON和AIN相,该前驱物的反应速率慢,完全氮化需要在1600℃下才能完成。对于添加尿素合成的前驱物而言,在其氮化反应过程中仅出现了γ-Al2O3和AIN相,没有α-Al2O3和AlON的生成,AIN直接由γ-Al2O3氮化生成,该前驱物的氮化反应速率快,氮化反应温度低,在1400℃下即可实现完全氮化。分析讨论了两种前驱物的氮化反应速率不同的主要原因,并利用XRD、SEM等分析方法对粉末进行了表征。     

Low-pressure pyrolysis studies of a new phosphorus precursor: Tertiarybutylbis(dimethylamino)phosphine

The low pressure decomposition of tertiarybutylbis(dimethylamino) phosphine, (t-Bu)P(NMe₂)₂, (TBBDMAP), has been studied on quartz and deposited GaP and InP surfaces. This new phosphorus precursor has been found to pyrolyze on quartz surfaces at much lower temperatures than the related compounds tertiarybutylphosphine, (t-Bu)PH₂, (TBP) and tris(dimethylamino)phosphorus, P(NMe₂)₃, (TDMAP). In contrast to the results obtained for TDMAP, GaP and InP surfaces decrease the decomposition temperature of TBBDMAP only slightly. The TBBDMAP reaction products were dimethylamine, methylmethyleneimine, and isobutylene, consistent with previous pyrolysis studies of TBP and TDMAP.     

Silicon Nitride Derived from an Organometallic Polymeric Precursor: Preparation and Characterization

Partially crystalline Si₃N₄, with nanosized crystals and a specific surface area greater than 200 m²/g, is obtained by pyrolysis of a commercially available vinylic polysilane in a stream of anhydrous NH₃ to 1000°C. This polymer does not contain N initially. Crystallization to high-purity α-Si₃N₄ proceeds with additional heating above 1400°C under N₂. The changes in crystallinity, powder morphology, infrared spectra, and elemental compositions, for samples annealed from 1000° to 1600°C under N₂, are consistent with an amorphous-to-crystalline transformation. Although macroscopic consolidation and local densification occur at 1400°C, volatilization and accompanying weight loss limit bulk densification. The effect of temperature on specific surface area is examined and related to the sintering process. These results are applicable to pyrolysis, decomposition, and crystallization studies of ceramics synthesized by polymeric precursor routes.     

正交试验法在PAN原丝纺丝工艺中的应用

利用正交设计方法确定了PAN湿法纺丝过程中影响原丝性能最主要的因素。结果表明 :以计量泵转速、凝固浴温度、负拉伸以及蒸汽拉伸倍数作为考察对象 ,影响原丝性能的最显著因素是蒸汽拉伸倍数 ,其次是负拉伸。以负拉伸、第二拉伸、第三拉伸以及蒸汽拉伸的倍数作为考察对象 ,影响原丝性能最显著的是蒸汽拉伸倍数 ,负拉伸几乎没有影响。利用正交实验结果 ,适当调节蒸汽拉伸倍数 ,制得强度为 6.5～ 7.0cN/dtex ,线密度为 1.1～ 1.3dtex的原丝     

二甲基亚砜一步法碳纤维用聚丙烯腈原丝生产工艺

叙述了二甲基亚砜一步法（高转化）高强碳纤维用聚丙烯腈原丝生产的工艺流程。着重讨论了聚合、纺丝的工艺控制。以及工艺控制对聚丙烯腈原丝和最终碳纤维性能的影响。按此工艺生产的聚丙烯腈原丝的质量完全符合高强碳纤维生产的需要。     

Effect of hydrocarbons precursors on the formation of carbon nanotubes in chemical vapor deposition

High-temperature decomposition of hydrocarbons may lead to the formation of carbon deposits. However in our present studies, we found that the morphology of carbon deposits over MgO supported Fe catalyst during chemical vapor deposition (CVD) process was closely related to the thermodynamic properties and chemical structures of hydrocarbon precursors. Six kinds of hydrocarbons (methane, hexane, cyclohexane, benzene, naphthalene and anthracene) were used as carbon precursors in this study. Methane which has a pretty simple composition and is more chemically stable was favorable for the formation of high-purity single walled carbon nanotubes (SWNTs). For high-molecular weight hydrocarbons, it was found that the chemical structures rather than thermodynamic properties of carbon precursors would play an important role in nanotube formation. Specifically, the CVD processes of aromatic molecules such as benzene, naphthalene and anthracene inclined to the growth of SWNTs. While the cases of aliphatic and cyclic hydrocarbon molecules seemed a little more complicated. Based on different pyrolytic behaviors of carbon precursors and formation mechanism of SWNTs and multi-walled carbon nanotubes (MWNTs), a possible explanation of the difference in CVD products was also proposed.     

Variable temperature13C MAS NMR of KFe2Mn(CO)12 in the solid state and as aCatalyst precursor on a carbon support

Variable temperature¹³C MAS NMR spectra are reported for¹³CO-enriched KFe₂Mn(CO)₁₂ as a solid and also as dispersed clusters on a carbon support. The spectrum of KFe₂Mn(CO)₁₂ at 300 K agrees with the proposed structure for this cluster and shows that the cluster is static. Two bridging carbonyl resonances are clearly resolved and, by comparison with¹³C MAS NMR spectra of Mn₂(CO)₁₀ and Fe₂(CO)₉, all terminal resonances for the cluster can be assigned. When the cluster is supported on carbon, two broad resonances are observed at room temperature which are assignable to KFe₂Mn(CO)₁₂ and a decomposition product, Mn₂(CO)₁₀. The carbonyl ligands in both supported clusters are completely averaged, and KFe₂Mn(CO)₁₂ on the carbon surface demonstrates fluxional behavior similar to that observed for the cluster in solution. For this fluxional process, activation energies of 0.6 kcal/mol and 0.5 kcal/mol are estimated for carbon-supported KFe₂Mn(CO)₁₂ and Mn₂(CO)₁₀, respectively.     

Evolution of chemistry and morphology during the carbonization and combustion of rice husk

Both fine carbon/silica and pure silica powders can be obtained by carbonization and combustion of rice husk under non-isothermal conditions, and the products can be used for preparation of high-quality ceramic materials. Studies on the morphology, chemical and physical characteristics of products were carried out by N₂-adsorptionmeter, SEM, XRD, FTIR, ICP-MS and EA. Results indicate that decreasing the heating rate increased the specific surface area, pore volume and pore diameter. At a heating rate of 5 °C/min, the specific surface areas of both the carbon/silica and pure silica powders were 261 and 235 m²/g, and the average pore diameters were 2.2 and 5.4 nm, respectively. The products obtained from various heating rates were all amorphous. Thermogravimetric analysis was employed to study the reaction characteristics during carbonization or combustion, indicating that decomposition process of rice husk could be divided into three temperature zones. This results of the study can also provide the important information on the recovery of biomass material from rice husk.