Novel Process Applications Using PHI-TEC II Adiabatic Calorimeter

This paper presents several applications of the PHI-TEC II that are not commonly associated with adiabatic calorimeters but which have proved to be extremely valuable. These include simulation of a deep oil well for enhanced oil recovery, isothermal calorimetry of a semibatch reaction, catalyst research using flow through reactors (both plug flow and CSTR) with controlled feeds of high pressure liquid and gas.This revised version was published online in November 2005 with corrections to the Cover Date.     

Effect of Solvent Composition on DSC Exothermic Peak of Human Serum Albumin Suspended in Pyridine-n-Hexane Mixtures

Human serum albumin (HSA) immersed in pyridine-n-hexane mixtures was analyzed using differential scanning calorimetry (DSC). State of the solid HSA in organic solvent mixtures is the non-equilibrium state which is seen as the exothermic peak on the DSC curves. The enthalpy change corresponding to this exothermic peak approaches zero when going from pure pyridine to pure n-hexane. Dependence of the enthalpy change on the pyridine concentration is suggestive that the non-equilibrium state of the immersed HSA results from the HSA-pyridine interactions 'frozen' at the lower temperature. Most likely the temperature-initiated exothermic peak observed on the DSC curves reflects the swelling of HSA by pyridine. This revised version was published online in August 2006 with corrections to the Cover Date.     

Al-TiO2-B2O3反应体系中B2O3/TiO2摩尔比对热扩散反应合成铝基复合材料磨损性能的影响

利用Al-TiO2-B2O3体系热扩散反应合成(XD)法制备了铝基复合材料;采用销-盘摩擦磨损试验机考察了所制备的铝基复合材料在干摩擦条件下同GCr15钢配副时的磨损性能;采用扫描电子显微镜和光学金相显微镜观察分析了复合材料微观组织结构及其磨损表面和剖面形貌,探讨了其磨损机理.结果表明:所制备的铝基复合材料的磨损性能随Al-TiO2-B2O3反应体系中B2O3/TiO2摩尔比的增加而提高;复合材料的磨损质量损失随着滑动速度的增加而增加,当滑动速度为0.9 m/s左右时最大,随后开始减小;磨损质量损失与滑动距离基本呈线性关系.当B2O3/TiO2摩尔比为0.0时,增强相由Al2O3和Al3Ti组成,相应的复合材料的抗磨性能较差,其磨损主要表现为Al3Ti的犁沟切削、亚表层剥落、塑性基体流失导致Al2O3颗粒裸露脱落以及Al3Ti棒断裂导致的磨粒磨损;加入B2O3后,棒状Al3Ti的数量减少,有利于基体晶粒细化,提高复合材料强度和塑性,故抗磨性能提高.当B2O3/TiO2摩尔比为1.0时,复合材料中的Al3Ti基本消失,抗磨性能显著改善,主要磨损机制为粘着磨损和轻微磨粒磨损.     

Al-TiO2系XD合成Al3Ti的形貌及其影响因素分析

本文主要研究了Al-TiO2系XD合成铝基复合材料的反应产物Al3Ti的形貌及其演变的影响因素.研究表明Al-TiO2系反应产物由Al2O3和Al3Ti组成,Al2O3为细小颗粒,与铝液不润湿,偏聚于基体颗粒的界面;Al3Ti呈棒状,优先生长方向为<110>;随着增强相体积分数的增加,反应温度提高,活性Ti原子的扩散能力增强,扩散路程变短,有利于Al3Ti择优生长,但Al2O3颗粒的浓度增加,使Ti原子的扩散阻力和Al3Ti的生长阻力同步增大,Al3Ti的择优生长倾向反而减弱,其形貌由棒状向块状演变;在纯铝液中Al3Ti的生长形貌为细长棒状,而在真空中则为薄片状;随着保温时间的延长,其轴向尺寸明显增大,径向尺寸增加不明显.     

Multi-Objective Optimization of Braun-Type Exothermic Reactor for Ammonia Synthesis

The exothermic reactor for ammonia synthesis is a primary device determining the performance of the energy storage system. The Braun-type ammonia synthesis reactor is used as the exothermic reactor to improve the heat release rate. Due to the entirely different usage scenarios and design objectives, its parameters need to be redesigned and optimized. Based on finite-time thermodynamics, a one-dimensional model is established to analyze the effects of inlet gas molar flow rate, hydrogen–nitrogen ratio, reactor length and inlet temperature on the total entropy generation rate and the total exothermic rate of the reactor. It’s found that the total exothermic rate mainly depends on the inlet molar flow rate. Furthermore, considering the minimum total entropy generation rate and maximum total exothermic rate, the NSGA-II algorithm is applied to optimize seven reactor parameters including the inlet molar flow rate, lengths and temperatures of the three reactors. Lastly, the optimized reactor is obtained from the Pareto front using three fuzzy decision methods and deviation index. Compared with the reference reactor, the total exothermic rate of the optimized reactor is improved by 12.6% while the total entropy generation rate is reduced by 3.4%. The results in this paper can provide some guidance for the optimal design and application of exothermic reactors in practical engineering.     

A numerical method of computing the kinetic parameters

A numerical method of computing the kinetic parameters (the activation energy (E), the preexponential constant (A) and the reaction order (n)) of exothermic decomposition of energetic materials via the exothermic rate equation is presented. The values ofE, A, andn are reported for the exothermic decomposition of six typical energetic materials, 1,6-diazido-2,5-dinitrazahexane (I), 1,5-diazido-3-nitrazapentane (II), 2,2,4,7,9,9-hexanitro-5-methyl-4,7-dinitrazadecane (III), 2,2,2-trinitroethyl-4,4,4-trinitrobutyrate (IV), 1,4-dinitro-2,3-dioxo-1,4-dinitrazacyclohexane (V) and 1,3,5-trianitro-1,3,5-triazafurazano[3,4-f]cycloheptane (VI).

     

理想气体热力学过程吸放热情况的图像判断法

如何简便地判断一个热力学过程的吸放热情况,对于了解此热力学过程是至关重要的．传统的方法是借助热力学第一定律,通过计算该热力学过程中的热学三量（功、热量和内能）来确定．文章通过分析简单热力学过程中的热容,得出：从绝热线上一点出发的微过程,过程曲线在绝热线下方,为放热过程;反之,为吸热过程．进一步,文章指出对于一些复杂的热力学过程,除使用传统的比较功大小的方法外,还可以利用热力学过程的末态相对等温线的位置而简单得出其吸放热情况。     

论理想气体p-V图中负斜率直线过程

本文通过对理想气体p-V图中负斜率直线过程温度及吸、放热变化的综合讨论，使我们对该过程有一个全面、清晰的认识，以开拓我们对热学过程讨论的方法及思路．     

Synthesis and characterization of copolyperoxides of indene with styrene, α‐methylstyrene,and α‐phenylstyrene

The oxidative copolymerization of indene with styrene, α‐methylstyrene, and α‐phenylstyrene is investigated. Copolyperoxides of different compositions have been synthesized by the free‐radical‐initiated oxidative copolymerization of indene with vinyl monomers. The compositions of the copolyperoxides obtained from the ¹H and ¹³C NMR spectra have been used to determine the reactivity ratios of the monomers. The reactivity ratios indicate that indene forms an ideal copolyperoxide with styrene and α‐methylstyrene and alternating copolyperoxides with α‐phenylstyrene. Thermal degradation studies via differential scanning calorimetry and electron‐impact mass spectroscopy support the alternating peroxide units in the copolyperoxide chain. The activation energy for thermal degradation suggests that the degradation is dependent on the dissociation of the peroxide (? O? O? ) bonds in the backbone of the copolyperoxide chain. Their flexibility has been examined in terms of the glass‐transition temperature. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 2004–2017, 2002     

Surface Laser Sintering of exothermic powder compositions

This work reports the temperature behavior associated with formation of new metal-polymer, intermetallic, and ceramic materials by Selective Laser Sintering. Here, experimental data produced from temperature measurements for inert as well as reaction powder compositions and the combustion wave front is reported. Analysis using an analog-digital-analog computer converter allowed some control of laser movement and hence some control of the exothermal reaction — in so doing it provided near optimum conditions for forming layered 3D articles.