磷氮阻燃腈纶结构性能及阻燃机理研究

研究了含磷酸二氢铵和脲复合阻燃剂的共混阻燃腈纶的结构和性能。研究表明，在纤维成形加工过程中，部分阻燃剂聚合生成聚磷酸铵和聚脲，阻燃剂以微粒状均匀分散并包埋在纤维内部；阻燃剂的加入使纤维高序区大分子间等距离排列的规整性和片状结构单元等距离平行排列的程度降低，热稳定性亦略有下降；但纤维的宏形态结构及物理机械性能没有明显变化；磷氮阻燃腈纶具有良好的阻燃性和阻燃耐久性，经碱洗２０次、水洗３０次后，阻燃剂的磷和氮的保留率分别高达８２．９％和８９．５％，纤维的ＬＯＩ值仍在２６％以上。     

Surface Pretreatments of Silicon Nitride for CVD Diamond Deposition

The efficiency of different surface pretreatments (four standard chemical etchings and four diamond powder abrasive procedures) on silicon nitride (Si₃N₄) substrates for chemical vapor deposition (CVD) of diamond has been systematically investigated. Blank Si₃N₄ samples were polished with colloidal silica (∼0.25 μm). Diamond nucleation and growth runs were conducted in a microwave plasma chemical vapor deposition apparatus for 10 min and 6 h, respectively. Superior results concerning nucleation density ( N _d∼ 10¹⁰ cm⁻² after 10 min), film uniformity, and grain size (below 2 μm after 6 h) were obtained for the mechanically microflawed samples, revealing that chemical etchings (hot and cold strong acids, molten base or CF₄ plasma) are not crucial for good CVD diamond quality on Si₃N₄.     

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.     

Sol-Gel Alumina Coating for Improved Cyclic Oxidation Resistance of Silicon Nitride

A 25 nm thick α-alumina layer was deposited on a turbine-grade silicon nitride by sol-gel dip coating and subsequent heat treatment in air at 1200°C. This layer had a nanometer grain structure. Silicon nitride protected by this thin layer showed a significant improvement in oxidation resistance over its uncoated counterpart after 200 cyclic exposures in air at 1250°C. The oxide layer grown on the coated silicon nitride also exhibited superior surface morphology, compared with the uncoated silicon nitride.     

Microstructure and Mechanical Properties of Hot-Pressed Silicon Carbide-Aluminum Nitride Compositions

A flexural strength of up to 1 GPa was achieved in SiC-AIN materials and is attributed to a dense, equiaxial grain structure of the 2H(δ) SiC-AIN solid solution, with a relatively uniform grain size of ∼ 1 μm. The strength was found to decrease with increasing grain size. While the β→α phase transformation and the formation of various metastable polytypes make microstructural control difficult in SiC materials, excellent control is facilitated in SiC-AIN materials as a result of the stable 2H solid solution. Several mechanisms of grain refinement during the β→ 2H transition were observed, most notably the direct formation of several 2H grains from a single β grain. In addition, grain growth is limited by the diffusion-controlled nature of the transition. These mechanisms could be utilized to achieve even higher strength values, with potentially higher reliability of the materials in structural applications.     

Li_20对AlN陶瓷低温烧结的影响

利用XRD,SEM和TEM研究了Li2O-CaF2-Y2O3体系在/AlN陶瓷低温烧结中的作用机理,研究发现,添加Li2O的/AlN陶瓷有着更低的收缩开始温度和更大的收缩率,这种收缩来自于含Li玻璃相与CaYAlO4液相的共同作用。在烧结过程中,Li2O不仅改变了AlN烧结过程中的相组成,而且改善了液相的性质。由于Li2O和Al2O3在l 100℃以下反应生成含Li玻璃相,使得AlN开始收缩的温度大为降低。在1 600℃以上,含Li玻璃相分解散失,有利于AlN晶界的纯化,同时,CaYAl3O7向CaYAlO4的转变以及液相CaYAlO4在烧结过程中稳定存在,保证了含Li玻璃相散失后AlN的持续收缩。     

Electrosyntheses and characterization of poly(5‐bromoindole) in boron trifluoride diethyl etherate

Poly(5‐bromoindole) (PBrI) films were synthesized electrochemically by direct oxidation of 5‐bromoindole in pure boron trifluoride diethyl etherate. The oxidation potential of 5‐bromoindole in this medium was measured to be only 0.97 V vs. saturated calomel electrode, which was lower than that determined in acetonitrile + 0.1 mol L^?1 Bu₄NBF₄ (1.08 V). PBrI films obtained from this medium showed good electrochemical behavior and good thermal stability. Structural studies showed that the polymerization of 5‐bromoindole ring occurred at 2,3 position. As‐formed PBrI films were thoroughly soluble in strong polar solvent dimethylsulfoxide and partly soluble in tetrahydrofuran. Fluorescent spectral studies indicated that PBrI was a good blue‐light emitter. The excitation and emission spectra of PBrI showed a significant shift to longer wavelength compared with that of the monomer, consistent with the greater extent of electron delocalization. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 539–547, 2006     

Lewis酸存在下的自由基共聚合——Ⅰ.GeCl_4与BCl_3存在下的乙酸乙烯酯与丙烯酸交替共聚

乙酸乙烯酯(VAc)与丙烯酸(AA)在GeCl_4及BCl_3存在下通过自由基聚合可得到交替共聚物。对GeCl_4体系,聚合反应速率正比于[引发剂]~(0.5)。当VAc/AA=1:1(mol比)时有最大反应速率。CCl_4对本聚合反应无链转移作用。通过紫外光谱分析可证实VAc及AA均与GeC\(?)生成络合物;ESR分析表明,络合AA自由基较未络合AA有较强的阳离子特性,交替共聚的原因可能与络合AA自由基及活化单体络合物二者有关。     

硼酚醛树脂在涂料中的应用

通过将硼酚醛树脂和环氧树脂进行混用,利用硼酚醛树脂优异的耐酸、碱腐蚀性能以及耐高温性能和环氧树脂可以常温固化成膜的特点,制备常温固化的耐高温防腐蚀涂料。     

Solubility of Si3N4 in Liquid SiO2

The nitrogen solubility in the SiO₂-rich liquid in the metastable binary SiO₂-Si₃N₄ system has been determined by analytical TEM to be 1%–4% of N/(O + N) at 1973–2223 K. Analysis of the near edge structure of the electron energy loss peak indicates that nitrogen is incorporated into the silicate network rather than being present as molecular N₂. A regular solution model with a positive enthalpy of mixing for the liquid was used to match the data for the metastable solubility of N in the presence of crystalline Si₃N₄ and to adjust the computed phase diagram. The solubility of Si₃N₄ in fused SiO₂ is far less than reported in liquid silicates also containing Al, Mg, and/or Y. Apparently, these cations act as modifiers that break anion bridges in the silicate network and, thereby, allow further incorporation of Si₃N₄ without prohibitive amounts of network cross-linking. Finally, indications emerged regarding the diffuse nature of the Si₃N₄-SiO₂ interface that leads to amorphous regions of higher N content.