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.     

莫来石晶种对反应烧结ZrO2/莫来石复相陶瓷显微结构的影响

通过显微结构观察研究了莫来石晶种对反应烧结ZrO2/莫来石复相陶瓷显微结构的影响。研究结果表明：与不含晶种试样相比，添加Ma(d50=1.87μm)和Mb(d50=0.83μm)晶种试样的显微结构比较均匀，莫来石晶粒多呈等轴状，且大小均一，晶内型ZrO2和封闭气孔较少。添加晶种对莫来石晶粒有明显细化作用。但晶种添加量和晶种颗粒尺寸对反应生成莫来石的晶粒尺寸无明显影响。采用溶胶－凝胶法制备的莫来石晶种（Mc)使试样中长出了一定量的长柱状的莫来石晶粒。     

高性能PAN原丝计算机仿真与信息管理系统开发

以聚丙烯腈（PAN）原丝实际生产过程为研究对象。以溶液聚合和湿法纺丝为基础。模拟PAN原丝纺制条件，设计开发了一套PAN原丝计算机仿真与信息管理系统。基于Windows视窗编程技术，利用VB和Access数据库。该系统将信息管理，工艺制订，性能预测，在线帮助等功能融为一体，界面友好，操作方便。利用该系统对现场生产过程进行仿真研究，仿真结果和实际测试结果比较表明，系统仿真精度误差小于5%，应用效果良好。     

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.     

Mullitization of Diphasic Aluminosilicate Gels

Recent studies have shown that the mullitization of diphasic aluminosilicate matrices comprising transitional alumina and amorphous silica occurs via a nucleation and growth process. Nucleation is preceded by a temperature-dependent incubation period. Following this incubation period, rapid nucleation of mullite occurs, producing about 1.8 × 10¹¹ nuclei/cm³, which remains constant throughout the rest of the transformation. Both incubation and mullite growth are thermally activated processes with apparent activation energies of 987 ± 63 and 1070 ± 200 kJ/mol, respectively. The growth rate of mullite grains under isothermal conditions is time dependent. An interpretation of these results is proposed on the basis of the nucleation and growth concepts of LaMer and Dinegar which supports the concept that the growth rate of mullite grains is controlled by the dissolution of transitional alumina into the amorphous matrix.     

Characterization and Sintering Behavior of Alkoxide-Derived Aluminosilicate Powders

Submicrometer SiO₂-Al₂O₃ powders with compositions of 46.5 to 76.6 wt% Al₂O₃ were prepared by hydrolysis of mixed alkoxides. Phase change, mullite composition, and particle size of powders with heating were analyzed by DTA, XRD, IR, BET, and TEM. As-produced amorphous powders partially transformed to mullite and Al-Si spinel at around 980°C. The compositions of mullite produced at 1400° and 1550°C were richer in Al₂O₃ than the compositions of stable mullite solid solutions predicted from the phase diagram of the SiO₂-Al₂O₃ system. Particle size decreased with increasing Al₂O₃ content. The sintered densities depended upon the amount of SiO₂-rich glassy phase formed during sintering and the green density expressed as a function of particle size.     

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.     

前驱体热解法制备Al2O3的物相转变及其合成

本文着重考查了Al2O3的前驱体一碳酸铝铵沉淀的形成过程及煅烧过程物相变化，发现可通过调节反应条件和加入合适的表面活性剂，来控制碳酸铝铵晶核的形成及晶体的生长速度，有效地阻止了Al2O3的团聚，并在温度1150摄氏度下制备出分散的Al2O3，其平均粒径为－2um，比表面为－3m^2/g。     

Electrical conductivity and redox stability of La2Mo2−xWxO9 materials

A series of compounds La₂Mo_2−xW_xO₉ (x = 0-2) were synthesized using a freeze-dried precursor method at relatively low temperatures (673-823 K). These materials were characterised by thermogravimetric and differential thermal analysis (TG/DTA), differential scanning calorimetric (DSC), X-ray diffraction (XRD), and transmission electron microscopy (TEM) and dilatometric measurements. Oxygen stoichiometry was evaluated by coulometric titration and thermogravimetric analysis at 873-1273 K. The ionic and electronic conductivities of these materials were analysed by impedance spectroscopy and a Hebb-Wagner ion-blocking method under moderately reducing conditions. The presence of W⁶⁺ leads to an increase of the stability range (about 10⁻¹⁶ Pa for La₂Mo_0.5W_1.5O₉ at 1073 K) and prevents oxygen loss and amorphisation. Within the stability range, the electronic conductivity increases gradually as the temperature increases and as the oxygen partial pressure reduces. This indicates that the electronic transport is mainly n-type as a result of the oxygen-content decreasing in the molybdate lattice. Further reduction of the oxygen partial pressure gave rise to the decomposition of La₂Mo_2−xW_xO₉, leading to the formation of new phases with molybdenum in lower oxidation states, which further enhances the electronic conductivity. The results of the coulometric titration and the thermogravimetric studies under a dry 5% H₂/Ar flow suggest that tungsten doped lanthanum molybdate materials can be used as electrolyte only at low temperature and under moderate reducing conditions.