Synthesis,Electrical, Electronic and Charge Transport Properties of Poly(aniline‐co‐p‐toluidine)

Copolymers of aniline with p‐toluidine were synthesized for different molar ratios of the respective monomers in acid medium. The electrical conductivity, charge transport and spectral characteristics upon incorporation of p‐toluidine units into the polyaniline backbone were investigated. The electrical conductivity of the copolymers showed frequency dependence which became more prominent with an increase in the number of p‐toluidine units in the polyaniline backbone. A direct relationship between the frequency dependence and electron localization was observed in the copolymers. Electronic spectra showed blue shifts in the π→π*and benzenoid→quinoid transitions revealing a decrease in the extent of conjugation in the copolymers. The protonated forms of the copolymers were soluble in DMSO giving polaron band around 400 nm. The decrease in electrical conductivity was attributed to the greater electron localizations as revealed from the broader ESR signals. Temperature dependence of electrical conductivity showed that charge transport was mainly through variable range hopping though a mixed conduction behavior was observed at higher temperature range.     

Polybenzimidazole-Ester-Imides

Thermostable heterocyclic polymers containing benzimidazole and imide rings, as well as flexible ester groups, have been synthesized by solution polycondensation of diaminobenzimidazoles with dianhydrides incorporating preformed ester linkages. The thermal stability and the electrical insulating properties of these products are discussed and compared with related heterocyclic polymers.     

Electrical Properties of a Highly Charged Cylindrical Particle in a Symmetric Electrolyte Solution

Based on the extended Langmuir's method, accurate analytic expressions for the electrical properties of cylindrical colloidal particle in a solution of symmetric electrolyte are derived from the nonlinear cylindrical Poisson-Boltzmann equation. Comparison is made with previous literature results. The present formulae have good agreement with literature values and are quite simple for practical use.     

Polymers-Copolymer as Flow Improvers for Fuel Oils and Their Electrical Conductivity

In order to find efficient cold flow improvers for fuel oil, polymethylmethacrylate (PMMA), polystyrene (PS), and a copolymer [styrene (S)–methylmethacrylate (MMA) were prepared. The structure of these polymers and the copolymer were characterized by infrared spectral analysis and their molecular weights were measured. These polymers-copolymer were used as additives for fuel oils in order to lower their pour point. Accordingly, they were evaluated as flow improvers for fuel oil. The results indicated that PMMA possesses less performance as pour point depressant. While the addition of PS and the copolymer (S–MMA) yield excellent pour point depressants for fuel oil. Upon studying the prepared additives and their properties, it was found that the electrical properties of the copolymer were changed due to the presence of polar ion in MMA effect on the electrical properties. The highest electrical conductivity was found when styrene:MMA molar ratio was 1:1.     

Electrical Properties of Cylindrical Reverse Micelle

In this article, accurate analytic expressions of the surface charge density/surface potential and adsorption excesses for cylindrical reverse micelle in a solution of symmetric electrolyte are derived from the nonlinear cylindrical Poisson–Boltzmann equation. These expressions are in good agreement with numerical values and Van Aken's results for cylindrical reverse micelle with high surface potentials and large κa.     

2,2,2-三硝基乙基-N-硝基甲胺的热安全性

为评价2,2,2-三硝基乙基-N-硝基甲胺(TNMA)的热安全性, 得到计算TNMA热安全性参数用的基本数据, 用经验式估算了TNMA的比热容(C_p)和热导率(λ). 用键能贡献于生成热Q_f的加和法, 估算了TNMA的标准生成焓Δ_cH_m^θ(TNMA, s, 298.15 K). 用热力学公式计算了TNMA的标准燃烧焓ΔU_m^θ(TNMA, s, 298.15 K)和标准燃烧能Δ_cH_m^θ(TNMA, s, 298.15 K). 用Kamlet-Jacobs 公式估算了爆速、爆压和爆热. 用经验式估算了分解热(Q_d). 通过差示扫描量热(DSC)曲线和高灵敏度布鲁顿玻璃薄膜压力计测得的逸出气体标准体积(V_H)-时间(t)曲线, 得到了TNMA放热分解反应的动力学参数. 用上述基本数据得到了评价TNMA的热安全性参数: 自加速分解温度(T_SADT), 热爆炸临界温度(T_be0和T_bp0), 绝热至爆时间(t_TIad), 撞击感度50%落高(H₅₀), 热点起爆临界温度(T_cr), 被300 K环境包围的半厚和半径为1 m的无限大平板、无限长圆柱和球形TNMA的热感度概率密度函数S(T), 相应于S(T)-T关系曲线最大值的峰温(T_S(T)max), 安全度(SD), 临界热爆炸环境温度(T_acr)和热爆炸概率(P_TE). 结果表明: (1) TNMA有较好的热安全性和对热抵抗能力, 与环三亚甲基三硝胺(RDX)相比, TNMA易从热分解过渡到热爆炸; (2) 不同形状大药量TNMA 热安全性降低的次序为: 球>无限长圆柱>无限大平板; (3)TNMA有高的燃烧能、高的爆轰化学能(爆热)和接近环四亚甲基四硝胺(HMX)的爆炸性能, 其对冲击敏感, 冲击感度与季戊四醇四硝酸酯(PETN)和特屈尔接近, 可用作混合炸药主组分.     

物理化学教学中安全工程教育的融合与内化实例*

如何强化安全工程教育是化学化工类专业高等教育的一个重要课题。通过对蒸汽锅炉爆炸、火灾爆燃事故以及锈蚀危害等3个实例的详细讲述,指出在物理化学的教学中,若适时融入相关的安全工程教育,可以使学生深刻理解安全事故发生及防范所依赖的物理化学原理,从而起到安全意识的内化作用。教学中现代教育技术的引入可以增强这一效果。     

真空中铝单丝电爆炸的实验研究

开展了铝单丝在负极性电流脉冲作用下电爆炸特性的研究.利用皮秒激光探针,搭建了阴影、纹影和干涉的光学诊断平台,得到了不镀膜铝丝典型的能量沉积过程,在电压崩溃时刻其沉积能量为2.4 eV/atom.为了增加金属丝内的沉积能量,开展了相同电参数及金属丝尺寸下的镀膜铝丝电爆炸实验,其沉积能量可达到5 eV/atom,实现了在电压崩溃之前铝丝完全气化(完全气化所需能量为4 eV/atom).阴影图像展示了高密度丝核区域的膨胀过程,不镀膜铝丝平均膨胀速度为2.2 km/s,而镀膜铝丝因为沉积能量大,其膨胀速度约为不镀膜铝丝的2.3倍,高密度区域膨胀速度为5 km/s.由于阴影不能反映低密度等离子体的膨胀,开展了平行双丝实验,通过测量自发光辐射,估算了低密度等离子体的膨胀速度.利用条纹相机拍摄了不镀膜铝丝电爆炸过程中自发光区域的图像.纹影图像清晰地展示了不镀膜铝丝在电爆炸过程中形成的核冕结构,而镀膜铝丝电爆炸过程中核冕结构得到了一定程度的抑制.从干涉图像计算了相移,在轴对称假设下对相移进行阿贝尔逆变换,重构了三维的铝原子数密度分布.     

The slowly reacting mode of combustion of gaseous mixtures in spherical vessels. Part 1: Transient analysis and explosion limits

Frank-Kamenetskii's analysis of thermal explosions is revisited, using also a single-reaction model with an Arrhenius rate having a large activation energy, to describe the transient combustion of initially cold gaseous mixtures enclosed in a spherical vessel with a constant wall temperature. The analysis shows two modes of combustion. There is a flameless slowly reacting mode for low wall temperatures or small vessel sizes, when the temperature rise resulting from the heat released by the reaction is kept small by the heat-conduction losses to the wall, so as not to change significantly the order of magnitude of the reaction rate. In the other mode, the slow reaction rates occur only in an initial ignition stage, which ends abruptly when very large reaction rates cause a temperature runaway, or thermal explosion, at a well-defined ignition time and location, thereby triggering a flame that propagates across the vessel to consume the reactant rapidly. Explosion limits are defined, in agreement with Frank-Kamenetskii's analysis, by the limiting conditions for existence of the slowly reacting mode of combustion. In this mode, a quasi-steady temperature distribution is established after a transient reaction stage with small reactant consumption. Most of the reactant is burnt, with nearly uniform mass fraction, in a subsequent long stage during which the temperature follows a quasi-steady balance between the rates of heat conduction to the wall and of chemical heat release. The changes in the explosion limits caused by the enhanced heat-transfer rates associated with buoyant motion are described in an accompanying paper.