Effects of hydrolysis of precursor on the structures and properties of polymer-derived SiBN ceramic fibers

In this paper, polyborosilazane precursor was synthesied from HMDZ, HSiCl₃, BCl₃ and CH₃NH₂ using a multistep method. By controlling the storage conditions, parts of the polyborosilazane fibers were hydrolyzed. FT-IR, NMR, XRD, TEM and monofilament tensile strength test were employed to study the effects of hydrolysis of precursor on the structures and properties of polymer-derived SiBN ceramic fibers. FT-IR and NMR results indicate that Si-N group in PBSZ reacts with H₂O to form Si-O-Si group. After pyrolysis reaction at 1400℃, Si-O-Si group will finally transformed into highly ordered cristobalite and β-quartz, resulting in formation of the wrinkled surface of the obtained SiBN ceramic fiber. The strip-like defects on fiber surface, according to monofilament tensile strength test, had a significant effect on mechanical property of the obtained SiBN ceramic fiber and caused no increase in fiber tensile strength of hydrolytic polyborosilazane fiber before and after pyrolytic process.     

Synthesis of highly efficient,structurally improved Li4SiO4 sorbents for high-temperature CO2 capture

Li₄SiO₄ sorbents for high-temperature CO₂ removal have drawn extensive attention owing to their potential application in carbon capture and storage (CCS). The major challenge in the application lies in the poor CO₂ capture performance under realistic conditions of low CO₂ concentrations, owing to the dense structure and poor porosity. In this work, Li₄SiO₄ sorbents were prepared with porous micromorphologies and large contact areas using a variety of organometallic Li-precursors, achieving fast CO₂ sorption kinetics, high capacity and excellent cyclic stability at a low CO₂ concentration (15?vol%). It was found that a high conversion of ~?74% was maintained for pure Li₄SiO₄ even after 100 sorption/desorption cycles. Moreover, by doping with Na₂CO₃ to reduce the CO₂ diffusion resistance, the conversion of the sorbent was further enhanced to 93.2%. The enhancement mechanism of alkali carbonate have been proven here to be ascribed to the formation of the eutectic melt of Li/Na carbonates, the existence and function of which has been confirmed in this study.     

Characteristics of polycarbosilanes produced under different synthetic conditions and their influence on SiC fibers: Part I

SiC fibers can be obtained by the spinning, curing, and heat treatment of polycarbosilane (PCS); however, the properties of the PCS precursor must be considered to set the correct spinning conditions. Although many studies have focused on the synthesis conditions, the characterization (in particular, the structural characteristics) of PCS fibers, and the polymer itself has limitations. In this study, PCS was prepared in two steps, and the growth of the polymer with respect to the reaction conditions was analyzed. We found that PCS is formed and grown by the rearrangement and subsequent condensation reactions of polydimethylsilane (PDMS). Further, fiber formation was affected by the reaction temperature, time, and pressure. Three types of PCS were obtained under different synthetic conditions, and they were all characterized. Regardless of the structural similarity of the PCS fibers (based on the spectroscopic analysis), the polymers showed different thermal and rheological properties. Our findings will be important in improving the production of PCS fibers (and subsequent SiC fibers) with finely controlled properties.     

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。     

共沉淀法制备锰锌软磁铁氧体前躯体共沉过程中钙、镁深度脱除的热力学分析

通过对Fe(Ⅱ)-Mn(Ⅱ)-Zn(Ⅱ)-Ca(Ⅱ)-Mg(Ⅱ)-NH3-NH4HCO3-H2O体系的热力学分析，得到各金属离子浓度与pH的关系，从而确定共沉法制备锰锌软磁铁氧体前躯体共沉过程中钙、镁深度脱除的共沉区域。热力学分析结果表明，溶液中钙、镁的含量随着体系pH的增大而降低，在相同条件下镁的溶解度大于钙的溶解度。为减少进入共沉粉中的钙、镁含量，需要保证在铁、锰、锌共沉完全的基础上降低体系的pH。当溶液中[C]T=0．1mol／L，[N]T=1．0mol／L时，pH控制在6．23～6．50之间可以大大降低进入共沉粉中的钙、镁含量。确定共沉过程钙，镁深度脱除的共沉区域，对于生产高纯锰锌软磁铁氧体前躯体具有重要的指导意义。     

Eight mole percent yttria stabilized zirconia powders by organic precursor route

An organic precursor-mixing route has been developed for preparation of 8 mol% yttria stabilized zirconia (8YSZ) ceramics. Polymeric salt of succinic acid with yttrium and zirconium has been prepared separately by treating sodium succinate with yttrium chloride and zirconyl chloride followed by washing with water and drying at 120 °C. Thorough mixing of the two salts in stoichiometric proportions by planetary ball milling followed by calcination at 850 °C resulted in a precursor powder containing nanocrystalline (∼40 nm) monoclinic zirconia, tetragonal YSZ, cubic YSZ and yttria. Compacts prepared after deagglomeration of powder by planetary ball milling produce 8YSZ ceramics having density 99.3% TD on sintering at 1550 °C for 2 h.     

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.