利用分子轨道法计算黑索金的生成热和分子结构

 利用分子轨道方法MNDO、AM1、PM3等计算了高能炸药RDX（C₃H₆N₆O₆）及其中间产物C₃H₆N₅O₄ 、C₃H₆N₄O₂ 、(H₂C)(N—CH₂)(N—CH₂)NN、CH₂＝N—NO₂的分子结构与热力学性质。用PM3方法给出了可与实验直接比较的生成热。     

液态烷的高温密度物态方程理论研究

采用热力学统计理论研究了液态甲烷在高温高压下分子分解反应特点及该体系的物态方程。着重讨论了体系中ＣＨ４－Ｈ２分子间有效势在对体系化学反应平衡及物态方程的影响，并根据实验Ｈｕｇｏｎｉｏｔ点（ＰＨ，Ｖ）优化确定出其ｅｘｐ－６势函数中的参数值。该势函数的排斥部分值比理想的混合条件下Ｌｏｒｅｎｔｚ－Ｂｅｒｔｈｅｌｏｔ规则给出的势函数值低约５０％，预示着主压下ＣＨ４和Ｈ２之间存在着某种亲合性，用该势函数计算     

感应读出式自猝灭流光计数器

本文介绍了自猝灭流光计数器的新技术——具有阻性阴极的感应读出式自猝灭流光计数器的特点及初步实验结果. 用不同比例的Ar/C₄H₁₀、Ar/CH₄或Ar/CO₂作为基本工作气体, 研究了阳极丝直径、电子学死时间等对计数率坪曲线的影响; 研究了几种不同的猝灭剂(H₂C(OCH₃)₂、C₂H₅OH、C₆H₆、C₇H₁₂)含量与坪曲线的关系; 也测量了该计数器的探测效率和死时间.     

漂移室退化效应的观测

利用5MeV的电子束照射漂移室, 在Ar/CO₂, Ar/CH₄及Ar/iC₄H₁₀等不同气体混合物条件下研究了漂移室的暗电流, 输出脉冲幅度, 能量分辨及计数率坪曲线随单位长度阳极丝上所收集到的总电荷数的变化.     

环氧丙烷点火的光谱研究

 利用多种光谱技术，提出了一种确定燃料冲击点火延迟时间的新方法。用这种方法所获得的实验值比国内外常用光电二极管（峰值波长约在800 nm）方法的所测值更接近实际值。环氧丙烷受冲击后，反应中间产物出现的时间是不同的，辐射强度也不同。在冲击波作用下，基团出现的顺序便可确定，它们依次为O、CH₂O、C₂、CH、CH₃O、CO₂、H₂O等，而O原子总是首先出现。     

CH4-O2-N2预混气体爆炸二维数值模拟

 利用CFD软件,基于ISAT算法和简化的甲烷氧化基元反应模型,建立了CH₄-O₂-N₂预混气体的二维湍流爆炸模型。数值计算结果表明,该模型较好地模拟了CH₄-O₂-N₂预混气体在高温气团作用下的点火、燃烧和爆炸过程。计算中,考察了高温点火气团的初始温度和混合气体初始组分对CH₄-O₂-N₂预混气体燃烧和爆炸过程的影响。结果表明：高温气团的初始温度对CH₄-O₂-N₂预混气体的点火延迟时间和燃烧初始阶段有重要影响,但对CJ爆燃没有影响;惰性气体N₂的加入,降低了混合气体的反应活性,导致点火延迟时间增大,燃烧反应速度、爆炸超压和重要自由基浓度都随之减小。相同条件下爆炸超压峰值的计算结果与实验测量结果符合较好。     

高温高压下硝基甲烷快速反应的光谱研究

 利用多台单色仪、光电系统及高速数据采集系统，成功地研究了硝基甲烷和氧混合物点火后快速反应的光谱。实验观察到CH₃O、CH、CH₂O、OH、CHO、CO、CO₂、H₂O、NO、NO₂等中间产物及最终产物的辐射。时间分辨的光谱测量发现：在爆炸激波管中，硝基甲烷快速反应的机理明显不同于硝基甲烷热分解和冲击引爆时的结果。     

液态水、苯和壬基乳化剂混合物冲击压缩特性的实验研究

 利用二级轻气炮在3.75~57.87 GPa 压力范围内,对体积比为10∶10∶1的液态水-苯-壬基酚聚氧乙烯醚混合体系进行了动高压加载实验,获得了10个Hugoniot数据。拟合结果表明,该混合体系的D-u关系可近似用直线方程D=1.407+1.503u_p描述,拟合精度约为0.102。混合体系H₂O-C₆H₆-C₃₅H₆₄O₁₁的冲击压缩实验结果基本符合体积相加原理,而在给定的实验压力区间内,冲击绝热曲线发生多次拐折的事实意味着该系统可能在6 GPa、10 GPa和30 GPa压力点附近发生了多次结构性相变。另外,还讨论了Lawrence-Berthlot混合规则中修正因子对高密度条件下指数-6型相互作用势排斥部分的影响。     

用甲醇-氢混合气源在不锈钢上生长金刚石薄膜的研究

 利用甲醇-氢（CH₃OH-H₂）混合气体为气源，30 nm厚的无定形硅为过渡层，借助于微波等离子体化学气相沉积（MWCVD）成功地将金刚石薄膜生长在不锈钢上，其最低生长温度可至420 ℃，并且甲醇-氢混合气体比传统的甲烷-氢（Ch₄-H₂）更具优势，测试表明这种金刚石薄膜有希望作为耐磨层在工业上应用。     

硬脂酸晶体压力效应的FT-IR光谱研究

 本文在0~4 GPa范围内研究了预压力对硬脂酸晶体的相关场劈裂和固态-熔融态相变过程的影响。通过γCH₂面内摇摆振动模和γ'CH₂相关场模的强度和频率变化,发现预压力对晶体内的相关场合分子链取向有明显的影响。预压力对硬脂酸的熔点虽然没有影响,但对γ'CH₂模有“硬化”作用。并且由此出发,对硬脂酸的预熔过程作了讨论。     

水高温高密度状态方程理论研究

 采用MCR方法计算由exp-6势描述的水分子作用体系的pVT状态方程。与MD数值模拟结果比较后发现，由于水分子间强烈的吸引作用有利于分子有序化过程的发生，在较高温度（2 000~4 000 K）条件下，水分子作用体系仍呈现出固态特征。该物相区内体系的热力学性质不能用MCR理论描述但MCR理论准确预言了水分子作用体系高温液相区pVT状态方程。     

Mass spectroscopy and ablation characteristics of nylon 6.6 in the ultraviolet

We report on the mass spectroscopic and the laser ablative characteristics of nylon 6.6 [-NH-(CH₂)₆-NH-CO-(-CH₂)₄-CO-] at 193 and 248 nm, using the ArF and KrF excimer lasers. The characteristic parameters of the laser ablative process, such as etch rate at different fluences, the threshold fluence, and the absorption coefficient for both wavelengths were determined. Even at low laser energy, there was a complete breaking of the polymeric chain bonds. The following photofragments were observed at 248 nm: H, H₂, C, CH, CH₂, N, NH, O, OH, H₂O, C₂H, C₂H₂, CN, C₂H₃, HCN, N₂, CO, C₂H₄, COH, C₂H₅, N₂H, NO, C₂H₆, H₂CO, N₂H₂, C₂, CH₂NH, O₂, C₃H₃, C₃H₄, C₃H₅, C₃H₆, CNO, HCNO, and H₂CNO. At 193 nm no photofragments were observed for m/e larger than 30 amu. The photofragments with two carbon atoms have a relatively higher probability to be dissociated from the parent monomer, than heavier photofragments with four carbon atoms. The mass spectroscopic studies and the absorption spectrum of nylon 6.6 in the ultraviolet, suggest photochemical bond-breaking at 248 and 193 nm. The monomer dissociates into fragments with the predominant mass at 28 amu for both laser wavelengths. Therefore the amide group is mainly involved in the photodissociation process of nylon 6.6 in the ultraviolet. The experimental results suggest that the photochemical dissociation of the polymeric chain is the dominant mechanism of the laser ablation of nylon 6.6 at 193 and 248 nm.     

Acetaldehyde oxidation at elevated pressure

A detailed chemical kinetic model for oxidation of CH₃CHO at intermediate to high temperature and elevated pressure has been developed and evaluated by comparing predictions to novel high-pressure flow reactor experiments as well as shock tube ignition delay measurements and jet-stirred reactor data from literature. The flow reactor experiments were conducted with a slightly lean CH₃CHO/O₂ mixture highly diluted in N₂ at 600–900 K and pressures of 25 and 100 bar. At the highest pressure, the oxidation of CH₃CHO was in the NTC regime, controlled to a large extent by the thermal stability and reactions of peroxide species such as HO₂, CH₃OO, and CH₃C(O)OO. Model predictions were generally in good agreement with the experimental data, even though the predicted temperature for onset of reaction was overpredicted at 100 bar. This discrepancy was attributed mainly to uncertainties in the CH₃C(O)OO reaction subset. Predictions of ignition delays in shock tubes and species profiles in JSR experiments were also satisfactory. At temperatures above the NTC regime, acetaldehyde ignition and oxidation is affected mainly by the competition between dissociation of CH₃CHO and reaction with the radical pool, and by reactions in the methane subset.     

Oxidation of H2/CO2 mixtures and effect of hydrogen initial concentration on the combustion of CH4 and CH4/CO2 mixtures: Experiments and modeling

An experimental investigation of the oxidation of hydrogen diluted by nitrogen in presence of CO₂ was performed in a fused silica jet-stirred reactor (JSR) over the temperature range 800-1050 K, from fuel-lean to fuel-rich conditions and at atmospheric pressure. The mean residence time was kept constant in the experiments: 120 ms at 1 atm and 250 ms at 10 atm. The effect of variable initial concentrations of hydrogen on the combustion of methane and methane/carbon dioxide mixtures diluted by nitrogen was also experimentally studied. Concentration profiles for O₂, H₂, H₂O, CO, CO₂, CH₂O, CH₄, C₂H₆, C₂H₄, and C₂H₂ were measured by sonic probe sampling followed by chemical analyses (FT-IR, gas chromatography). A detailed chemical kinetic modeling of the present experiments and of the literature data (flame speed and ignition delays) was performed using a recently proposed kinetic scheme showing good agreement between the data and this modeling, and providing further validation of the kinetic model (128 species and 924 reversible reactions). Sensitivity and reaction paths analyses were used to delineate the important reactions influencing the kinetic of oxidation of the fuels in absence and in presence of additives (CO₂ and H₂). The kinetic reaction scheme proposed helps understanding the inhibiting effect of CO₂ on the oxidation of hydrogen and methane and should be useful for gas turbine modeling.     

On the reaction mechanism of CO2 reforming of methane over a bed of coal char

CO₂ reforming of methane was studied over a bed of coal char in a fixed bed reactor at temperatures between 1073 and 1223 K and atmospheric pressure with a feed composition of CH₄/CO₂/N₂ in the ratio of 1:1:8. Experimental results showed that the char was an effective catalyst for the production of syngas with a maximum H₂/CO ratio of one. It was also found that high H₂/CO ratios were favoured by low pressures and moderate to high temperatures. These results are supported by thermodynamic calculations. A mechanism of seven overall reactions was studied and three catalytic reactions of CH₄ decomposition, char gasification and the Boudouard reaction was identified as being of major importance. The first reaction produces carbon and H₂, the second consumes carbon, and the third (the Boudouard reaction) converts CO₂ to CO while consuming carbon. Equilibrium calculations and experimental results showed that any water present reacts to form H₂ and carbon oxides in the range of temperatures and pressures studied. Carbon deposition over the char bed is the major cause of deactivation. The rate of carbon formation depends on the kinetic balance between the surface reaction of the adsorbed hydrocarbons with oxygen containing species and the further dissociation of the hydrocarbon.     

PRELIMINARY TEST FOR AGEING EFFECT OF DRIFT CHAMBERS

The degradation of some performances of the drift chambers irradiated with 5 MeV electron beam has been tested. The gas mixtures filled were Ar/CO₂, Ar/CH₄ and C₄H₁₀ in proportion.
The dark current, the pulse height, the energy resolution and the counting rate plateau have been measured during the irradiation.     

等容条件下H2O-CO2-CH4混合流体的高温拉曼光谱就位分析

 以合成包裹体作为腔体，用显微激光拉曼探针就位分析了H₂O-CO₂-CH₄混合流体的高温特性。研究结果表明，在高温下，CH₄和CO₂相互之间对各自拉曼光谱的影响不大，水分子对它们的拉曼峰有比较大的影响。在等容条件下，流体均一前，随着温度的升高，水分子的氢键几乎呈线性减少，均一为气相的流体，水分子伸缩振动拉曼峰的变化与一般气体变化相似；随着温度升高，体系压力的增加，最大峰频率呈很微小的降低趋势。均一为液相的流体中的水分子，在均一温度时，氢键变化发生了转折，均一后流体中水分子的氢键受温度的影响比均一前明显要小，在测量的最高温度520 ℃，水分子存在着一定的氢键作用。一直到拉曼光谱测量的最高温度580 ℃还未均一的流体，液相中水分子存在比较强的氢键作用。     

A DRIFT CHAMBER WITH UNIFORM ELECTRIC FIELD AND MEASUREMENTS OF THE ELECTRON DRIFT VELOCITY

The measurements of the electron drift velocity as a function of the electric field have been made in a small drift chamber with uniform electric field for Ar/CH₄, Ar/i-C₄H₁₀, Ar/CO₂ and SQS gas mixtures. The values of the electric field range from obout 0.3 to 2.5kV/cm. The results of the measurements are discussed.     

灯丝温度对原位吸收光谱和金刚石薄膜生长的影响

 报道了原位红外吸收光谱在气相合成金刚石薄膜生长过程中的应用，研究了灯丝温度对原位红外吸收光谱和金刚石薄膜生长的影响。较高的灯丝温度使甲烷分解更充分，从而产生更多诸如C₂H₂等可能对金刚石薄膜生长有利的基团，导致金刚石薄膜质量和生长速率的提高。     

Spectral Study of Effects of Aluminium Nanoparticles on Fast Reaction of Nitromethane

Fast reactions between nitromethane and aluminium nanoparticles are studied using transient spectral methods. In comparison with species produced by pure nitromethane, the emergence time for species produced by nitromethane after addition of 1 g of aluminium nanoparticles decreases by 46-58% and the emission intensity increases by 13-100%. The results demonstrate that aluminium nanoparticles have positive effect on accelerating the decomposition rate of nitromethane and that the explosion efficiency of nitromethane is greatly improved. Fast reactions carried out between nitromethane and aluminium nanoparticles in different environments （CO2, H2O and O2） reveal that O2 and an appropriate amount of H2O improve the explosion efficieney of nitrornethane, whereas CO2 has the weakest effect on improving this parameter. The investigations provide insights into the process occurring in actual systems involving propellants and fuel-air explosives.