新型硅氮烷先驱体的合成和表征

采用ＭｅＳｉＨＣｌ２和ＭｅＳｉＶｉＣｌ２共氨解方法制备出了流动性好的含Ｓｉ－Ｈ和Ｓｉ－Ｖｉ的低分子硅氮烷。结果表明，Ｈ２ＨｔＣｌ６（脱水）和ＤＣＰ是合适的硅氢化交联催化剂和双键交联的引发剂，交联产物在程序控温的管式炉中裂解，得到了高的陶瓷产率。     

STUDY FOR MECHANICAL ALLOYING OF Fe─M BY MOSSBAUER SPECTROSCOPY

将Ｆｅ－Ｍ（Ｍ＝Ｃ５ＳｉＯ２Ａｌ２Ｏ３）混合物在Ａｒ中高能球磨５６ｇ后测量Ｍｏｓｂａｕｅｒ谱，结果表明，（Ｆｅ）２－（ＳｉＯ２）１仍为Ｆｅ和ＳｉＯ２的机械混合物：（Ｆｅ）６－（Ｃ）３已完全合金化，生成两种Ｆｅ３Ｃ；（Ｆｅ）２－（Ａｌ２Ｏ３）１则成为Ｆｅ（７３％），尖晶石型的ＦｅＡｌ２Ｏ４）２２％），ｑｑｎｔＦｅ的团聚族（５％）和Ａｌ２Ｏ３的混合物。     

1,3-戊二烯阳离子聚合引发体系(CH3)3SiCl/EtAlCl2的研究

研究了阳离子引发体系Ｍｅ３ＳｉＣｌ（ＴＭＳＣｌ）ＥｔＡｌＣＬ２在正己烷中引发的１,３－戊二烯（ＰＤ）聚合反应。研究结果表明,在ＥｔＡｌＣｌ２引发的ＰＤ聚合反应中引入ＴＭＳＣｌ后大幅主提高了聚合物产率,同时使聚合反应速率明显提高,在「ＴＭＳＣｌ」／「ＥｔＡｌＣｌ２２」＝０－１范围内,ＴＭＳＣｌ／ＥｔＡｌＣｌ２体系制备的聚合物分子量高于ＥｔＡｌＣｌ２引发制备的聚合物,这些结果表明Ｍｅ３ＳｉＣｌ／ＥｔＡ     

三价铈离子在氯硅酸镁钙中的晶体学格位研究

首次合成了发射蓝紫光的Ｃｅ＾３＋激活的氯硅酸镁钙ＣａｇＭｇ（ＳｉＯ４）４Ｃｌ２：Ｃｅ＾３＋新荧光粉,利用Ｃｅ＾３＋的光谱结果和Ｖａｎ Ｕｉｔｅｒｔ经验公式,结合对ＣａｇＭｇ（ＳｉＯ４）４Ｃｌ２晶体的结构研究,判断出ＣａｇＭｇ（ＳｉＯ４）４Ｃｌ２：Ｃｅ＾３＋中存在两种性质稍有差异的Ｃｅ＾３＋发光中心,这两种发光中心均占据其质中八配位的钙格位。     

(Si-,Al-)陶瓷化木材的化学方法

以 ＡｌＣｌ３．６Ｈ２Ｏ为原料,制备高盐基度碱式氯化铝 Ａｌ２（ＯＨ）ｎＣｌ６－ｎ,作为催化剂及网络形成剂参与陶瓷前驱体中ＴＥＯＳ、ＧＰＴＭＳ的水解、缩聚反应．将其注入木材并热处理,得到高性能的（ＡＩ－, Ｓｉ－）陶瓷化木材     

碳纤维增强C—SiC梯度基复合材料研究

采用ＣＶＩ工艺均热法共沉积技术制备了碳纤维增强Ｃ－ＳｉＣ梯度基复合材料。Ｃ和ＳｉＣ的原料氛分别是Ｃ２Ｈ２ｔ ＣＨ３ＳｉＣｌ３，Ａｒ和Ｈ２分别是载流和稀释气体。基体微观结构的变化通过控制原料气体的成分配比藜得。测试了材料的力学性能、抗氧化性能和摩擦磨损性能。利用金相技术、电子探针成分分析技术、ＴＥＭ和ＳＥＭ技术观察和分析了材料的微观结构。试验结果表明，这种材料的组织结构特点是：在微观上是梯度的，即围     

超高真空CVD生长的Si1—xGex合金组分变化与表面偏析现象

系统分析了利用超高真空ＣＶＤ技术在Ｓｉ衬底上外延Ｓｉ－ｘＧｅｘ合金的体内组分分布情况和Ｇｅ的表面偏析现象。用ＳＩＭＳ对Ｓｉ和Ｇｅ的组分作了深度剖析。在生长过程中,组分均匀,在表面Ｇｅ浓度减小,Ｓｉ浓度没有明显变化。在不经ＨＦ酸清洗和在ＨＦ酸中去掉表面自然氧化层的两种情况下,用ＸＰＳ分别对外延层表面进行了定量分析,得到Ｇｅ的表面偏析与表面自然氧化相关的结论。     

气相反应法合成超细粉末过程中的r~＊叶和晶型的研究

本文以ＳｉＣｌ４－ＮＨ３、ＳｉＣｌ４－Ｏ２、ＳｉＣｌ４－Ｎ２－Ｈ２、ＴｉＣｌ４－ＮＨ３－Ｈ２、ＴｉＣｌ４－Ｎ２－Ｈ２、ＴｉＣｌ４－Ｏ２、ＡｌＣｌ３－Ｏ２等为体系，运用均匀成核理论，研究了平衡常数Ｋｐ、过饱和比Ｓ及临界核半径，ｒ＊等因素对气相反应法中超细粉末的形成及粉末结构状态的影响．结果表明，当２ｒ＊大于某物质的晶格常数时，用气相反应法得到的该物质的超细粉末一般为晶体粉末，反之则得到无定形粉末．     

添加Al_2O_3对SiC板粒／Y－TZP复合材料力学性能的影响

本文以ＳｉＣ板粒、ＺｒＯＣｌ２－８Ｈ２Ｏ、ＡｌＣｌ３和Ｙ（ＭＯ）３为原料，利用共沉淀和热压烧结工艺，制备ＳｉＣ板粒／Ｙ－ＴＺＰ和（含Ａｌ２Ｏ３）ＳｉＣ板粒／Ｙ－ＴＺＰ复合材料．测试了材料的室温和高温力学性能．研究了添加Ａｌ２Ｏ３对ＳｉＣ板粒／Ｙ－ＴＺＯ复合材料的影响．结果表明，ＳｉＣ板粒／Ｙ－ＴＺＰ复合材料与Ｙ－ＴＺＰ陶瓷相比，其室温强度和韧性出现明显下降，高温强度也没有改善；而在ＳｉＣ板粒与Ｙ－ＴＺＰ复合的基础上，添加Ａｌ２Ｏ３可明显提高材料的强度和断裂韧性，同时，材料的高温强度也获得显著改善．     

碳化硅和氧化铝陶瓷的热等静压氮化

通过对无压烧结、热压烧结和热等静压烧结ＳＩＣ陶瓷以及热压烧结的ＳｉＣ粒子补强Ａｌ２Ｏ３基复相陶瓷（ＳｉＣｐ－Ａｌ２Ｏ３）和ＳｉＣ粒子与ＳｉＣ晶须共同增强的Ａｌ２Ｏ３基复合材料（ＳｉＣｐ－ＳｉＣｗ－Ａｌ２Ｏ３）在氮气氛中进行高温氮化处理，成功地实现了这些材料的开口气孔表面裂纹的愈合。研究表明：热等静压氯化工艺可以显著提高ＳｉＣ和Ａｌ２Ｏ３陶瓷的抗弯强度，对断裂韧性也有较大的改善作用。对于热等静压烧结ＳｉＣ陶瓷，在１８５０℃和２００ＭＰａ氮气压力下氯化处理１小时后，其抗弯强度和断裂韧性分别由５８２ＭＰａ和５．７ＭＰａ·ｍ１／２提高到９０７ＭＰａ和８．４ＭＰａ·ｍ１／２；对于热压烧结的ＳｉＣｐ－Ａｌ２Ｏ３复相陶瓷和ＳｉＣｐ－ＳｉＣｗ－Ａｌ２Ｏ３复合材料，在１７００℃和１５０ＭＰａ氮气压力下氮化处理１小时后，其室温抗弯强度分别由４６０和７０５ＭＰａ提高到８９５和１０３３ＭＰａ。     

Near-infrared combination and overtone bands of the CH2 sequence in CH2X2, CH2XCHX2, and CH3(CH2)5CH3 and their characteristic frequency zones

We characterized near-infrared spectra of the CH2 sequence in CH2X2 (X=halogen), CH2ClCHCl2, and CH3(CH2)5CH3. Each near-infrared absorption in the region from 3500 to 10,000 cm-1 is consistently assigned to one of the five different combination or overtone groups, in the order of increasing frequency, of the {[v(CH)]+[delta(CH)]} (A), {[v(CH)]+[2delta(CH)]} (B), [2v(CH)] (C), {[2v(CH)]+[delta(CH)]} (D), and [3v(CH)] (E) types, where v(CH) and delta(CH) denote the CH stretching and CH deformation normal modes, respectively. Each group has its own characteristic frequency zone. The bands of B, D, and E, which are second-order combinations or overtones, are weaker by 1/10-1/50 than those of A and C, which are first-order combinations or overtones. The near-infrared spectra of the CH2 sequence show "window zones" of very weak or no absorptions. This suggests that we can perceive the characteristic near-infrared bands of a functional group through the window zones, and we give an example to demonstrate this. The first-order combination bands of type A only of CH2X2 are reasonably assigned to a pair of the normal modes of v(CH) and delta(CH). From this we predict that the first-order combination bands should give structural information on the CH2 chain, similar to the infrared fundamental bands.     

CVD金刚石薄膜(111)与(100)取向生长的热力学分析

用非平衡热力学耦合模型计算了CVD金刚石薄膜生长过程中C2H2与CH3浓度之比[C2H2]/[CH3]随衬底温度和CH4浓度的变化关系,从理论上探讨了金刚石薄膜（111）面和（100）面取向生长与淀积条件的关系。在衬底温度和CH4浓度由低到高的变化过程中,[C2H2]/[CH3]逐渐升高,导致金刚石薄膜的形貌从（111）晶面转为（100）晶面。添加氧后C2H2与CH3浓度都将下降,但C2H2下降得更多,因而添加氧也使[C2H2]/[CH3]下降,从而有利于生长（111）晶面的金刚石薄膜。     

Kinetics of the degradation of sulfur mustard on ambient and moist concrete

The rate of degradation of the chemical warfare agent sulfur mustard, bis(2-chloroethyl) sulfide, was measured on ambient and moist concrete using (13)C Solid State Magic Angle Spinning Nuclear Magnetic Resonance (SSMAS NMR). Three samples of concrete made by the same formulation, but differing in age and alkalinity were used. The sulfur mustard eventually degraded to thiodiglycol and 1,4-oxathiane via the intermediate sulfonium ions CH-TG, H-TG, H-2TG and O(CH(2)CH(2))(2)S(+)CH(2)CH(2)OH on all of the concrete samples, and in addition formed 8-31% vinyl moieties on the newer, more alkaline concrete samples. This is the first observation of the formation of O(CH(2)CH(2))(2)S(+)CH(2)CH(2)OH on a solid substrate. The addition of 2-chloroethanol to concrete on which mustard had fully degraded to thiodiglycol and 1,4-oxathiane resulted in the formation of O(CH(2)CH(2))(2)S(+)CH(2)CH(2)OH, thus demonstrating the reversibility of sulfur mustard degradation pathways. The sulfur mustard degradation half-lives on ambient concrete at 22 degrees C ranged from 3.5 to 54 weeks. When the substrates were moistened, the degradation half-lives at 22 degrees C ranged from 75 to 350h. The degradation of sulfur mustard occurred more quickly at elevated temperatures and with added water. The non-volatile toxic sulfonium ions persisted for months to years on concrete at 22 degrees C and weeks to months on concrete at 35 degrees C, before decomposing to the relatively non-toxic compounds thiodiglycol and 1,4-oxathiane.     

Near-infrared combination and overtone bands of CH in CHX3, CHX(2)-CHX2, and CHX(2)-CX(2)-CHX2

In the present report we studied spectral characteristics of the near-infrared combination and overtone bands of CH vibrations of a CH sequence. The near-infrared bands of the CH in CHX3 (X, halogen), which were interpreted in terms of the CH stretching and CH deformation fundamentals without any ambiguity, typically showed how the frequency and intensity of a combination or an overtone depend on the vibrational excited state. In the CH-C-CH of CHX2CX2CHX2, the vibrations of one CH are isolated from those of the other CH, and the combination and overtone bands were similarly interpreted as those of the CH, although each of the combination bands was split into two because of non-degeneracy of the CH deformation. In the CH-CH of CHX2CHX2, the CH deformations only have coupled modes. The first combination showed four narrowly separate bands, which were reasonably interpreted on the basis of the CH stretching and the coupled CH deformation modes. We demonstrated that the first combination of coupled modes as well as the combination of up to, at least, the third order of isolated modes have the nature of the characteristic bands.     

The catalytic incineration of (CH3)2S and its mixture with CH(3)SH over a Pt/Al(2)O(3) catalyst

Catalytic incineration is one of the cost-effective technologies to solve the troublesome volatile organic compounds (VOCs). However, some sulfur containing VOCs, such as dimethyl sulfide, may deactivate the Pt catalyst that is commonly used in the catalytic incineration process. This paper provides information on the poisoning effect of (CH3)2S. The catalytic incineration of (CH3)2S, typically emitted from the petrochemical industry, over a Pt/Al(2)O(3) fixed bed catalytic reactor was studied. The effects of operating parameters including inlet temperature, space velocity, (CH3)2S concentration, O2 concentration and catalyst size were characterized. Catalytic incineration on a mixture of (CH3)2S with CH(3)SH was also tested. The results show that the conversions of (CH3)2S increase as the inlet temperature increases and the space velocity decreases. The higher the (CH3)2S concentration is, the lower its conversion is. The O2 concentration has a positive effect on the conversion of (CH3)2S. (CH3)2S has a poisoning effect on the Pt/Al(2)O(3) catalyst, especially at lower temperatures. The conversion of (CH3)2S is significantly suppressed by the existence of CH(3)SH.     

High-precision direct measurements of (13)CH(4)/(12)CH(4) and (12)CH(3)D/(12)CH(4) ratios in atmospheric methane sources by means of a long-path tunable diode laser absorption spectrometer

Measurements of (13)CH(4)/(12)CH(4) and (12)CH(3)D/(12)CH(4) ratios in atmospheric methane (CH(4)) sources provide important information about the global CH(4) budget as well as about CH(4) production and consumption processes occurring within the various sources. As an alternative to the conventional mass spectrometer (MS) technique, which requires conversion of CH(4) to CO(2) and H(2), we have developed a tunable diode laser absorption spectrometer (TDLAS), which permits rapid direct measurements of the (13)CH(4)/(12)CH(4) and (12)CH(3)D/(12)CH(4) ratios. An intercomparison between TDLAS and MS techniques for samples from natural wetlands, landfills, and natural gas sources resulted in a mean deviation of Δδ(13)C = 0.44‰ and ΔδD = 5.1‰. In the present system the minimum mixing ratios required are 50 parts in 10(6) by volume (ppmv) CH(4) (sample size 2 μmol CH(4)) for direct δ(13)C measurements and 2000 ppmv (sample size 80 μmol CH(4)) for direct δD measurements. These mixing-ratio limits are adequate for most CH(4) source characterization studies without requiring sample preconcentration.     

Catalytic oxidation of dichloromethane and toluene over platinum alumite catalyst

Catalytic oxidation technology is one of the most promising technologies for the reduction of volatile organic compound (VOC) emissions. It is very necessary to study the catalytic oxidation of mixture of VOCs and volatile organic compounds (CVOCs), because VOCs are always emitted accompanying with CVOCs. Hence, the catalytic oxidation reaction of toluene and CH2Cl2 is explored on a platinum alumite catalyst in this work. The results show that the addition of toluene has no effect on the decomposition of CH2Cl2, although it can suppress CH3Cl formation because the steam generated from the catalytic combustion of toluene suppresses the formation of CH3Cl from CH2Cl2. High concentrations of CH2Cl2 have a negative effect on the catalytic combustion of toluene.     

基于热饱和溶液法CH3NH3PbI3单晶的制备及表征

采用热饱和溶液法,通过调控前驱体溶液1,4-丁内酯中PbI2和CH3NH3I的配比,进而对前驱液100℃进行加热,简单易操作地得到单晶CH3NH3PbI3。计算了不同调控条件下单晶CH3NH3PbI3的产率;利用SEM和XRD对其形貌和结晶度进行表征;通过吸收和荧光光谱对单晶的光谱性能进行表征。结果表明,单晶CH3NH3PbI3的最佳摩尔配比为n(PbI2)∶n(CH3NH3I)=2.3∶1,PbI2最佳浓度为1.229 mmol/mL。     

磷酸镍基类分子筛材料的吸附性质研究

主要研究了磷酸镍基类分子筛材料VSB-1和CoVSB-1对H₂和H₂NCH₂CH₂NH₂的吸附性质. VSB-1和CoVSB-1对H₂的吸附是一种超临界物理吸附. VSB-1和CoVSB-1H₂NCH₂CH₂NH₂的吸附量比对H₂O分子、C₂H₅OH分子以及其他有机胺蒸汽分子的吸附量大, 分别是19.7wt％和24.3wt％, 通过XRD、FT-IR和UV-Vis等光谱表征证实了VSB-1和CoVSB-1 H₂NCH₂CH₂NH₂的化学吸附机理, 即H₂NCH₂CH₂NH₂与VSB-1和CoVSB-1骨架结构中的过渡金属Ni和Co离子活性位的螯合作用.     

Growth and structure of TiCxNy coatings chemically vapour deposited on graphite substrates

TiCxNy coatings were grown on graphite substrates in a computer-controlled, hot-wall chemical vapour deposition (CVD) reactor, using gas mixtures of TiCl4–CH4–N2–H2 at a total pressure of 10.7 kPa (80 torr) and at a temperature of 1400 K. Growth rate, composition, morphology and crystallographic texture of the TiCxNy coatings were investigated as a function of the CH4/CH4+N2 ratio in the range 0–1 at a constant CH4+N2 flow rate of 370 standard cubic centimeters per minute (sccm). The C/C+N ratio and growth rate of the TiCxNy coatings increased with increasing CH4/CH4+N2 ratio in the gas phase. The compositions of the coatings with C/C+N ratios in the range 0–1 were found to be between the thermodynamic and the kinetic predictions. Morphology and preferred orientation of the coatings were observed to be strongly affected by the CH4/CH4+N2 ratio in the gas phase.