Kinetics study of Ti[O(CH2)4OCHCH2]4 initiated ring‐opening polymerization of ε‐caprolactone by differential scanning calorimetry

Chemical shrinkage was used for the in situ measurement of the progressing chemical stabilization reactions and the influence of ozone during the stabilization of polyacrylonitrile. A method for evaluating the activation energy through the sensitivity temperature is presented. The calculated results show that the activation energies were 161.57 kJ/mol in air and 181.23 kJ/mol in ozone-enriched air. Therefore, the chemical reactions were postponed during stabilization in ozone-enriched air. Ozone seemed to act in three ways: first, ozone promoted the formation of the serious skin–core structure. Second, ozone accelerated the chemical reactions and shortened the stabilization time at lower heating rates. Third, ozone postponed the chemical reactions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Novel approach in investigation of the poly(acrylic acid) hydrogel swelling kinetics in water

The swelling kinetics curves of structurally defined poly(acrylic acid) hydrogel in bidistilled water at temperatures: 25, 30, 35, 40, and 45°C were determined. The possibility of kinetically explaining the isothermal swelling process by applying the following models: reaction controlled by diffusion, first order chemical reaction kinetics, and second order chemical reaction kinetics, was investigated. It was found that kinetically explaining the swelling process using these methods was limited to only certain parts of the process. The swelling process in bidistilled water was described in full range assuming that the hydrogel's swelling rate was a kinetically controlled reaction by the rate of the movement of reactive interface of hydrogel. Based on that model, the kinetic parameters, activation energy (E_a) and preexponential factor (A), of the swelling process were determined to be E_a = 35 kJ/mol and lnA = 8.6. A possible mechanism of the investigated swelling process was discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Kinetic study of the decompositions involved in the thermal degradation of commercial azodicarbonamide

The transitions and reactions involved in the thermal treatment of several commercial azodicarbonamides (ADC) in an inert atmosphere have been studied by dynamic thermogravimetry analysis (TGA), mass spectrometry and Fourier transform infrared (FTIR) spectroscopy. A pseudo‐mechanistic model, involving several competitive and non‐competitive reactions, has been suggested and applied to the correlation of the weight loss data. The model applied is capable of accurately representing the different processes involved, and can be of great interest in the understanding and quantification of such phenomena, including the simulation of the instantaneous amount of gases evolved in a foaming process. In addition, a brief discussion on the methodology related to the mathematical modeling of TGA data is presented, taking into account the complex thermal behaviour of the ADC. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

生烃化学动力学在川东北普光气田的应用

普光气田是四川盆地近期发现的规模最大、埋藏最深、资源丰度最高的气田。通过认识普光气田各个烃源岩层的贡献量、生烃关键期与构造演化的关系、油气成藏具体模式等，建立生烃化学动力学模型、标定参数，结合地区烃源岩参数和地史、热史资料，定量描述该地区的生烃过程及油裂解成气过程。认为：普光地区的主力烃源岩为下志留统泥岩；主要干酪根生油期为早二叠世末到早三叠世末期（距今286Ma至240Ma）；主要干酪根生气期为中三叠世（距今240Ma至230Ma）；主要气源是原油后期热裂解气，原油裂解成气的时间比较晚，主要油裂解成气期为早白垩世（距今144Ma至97．5Ma），从而决定了普光气田的成藏模式为“多期成藏，油气转化，晚期定位”。图2表3参33     

Characterization of Thai limestone for desulphurization in a fluidized bed combustor

The objective of this study is to determine the chemical kinetics of desulphurization of Thai limestone in an atmospheric fluidized bed combustor (AFBC). The experiments, which employed the batch technique using the limestone samples from six major sources in Thailand, were performed in a laboratory‐scale AFBC. The results obtained were analysed and correlated in the form of apparent reaction rate and deactivation rate constants as a function of operating conditions of the furnace and their properties, respectively. The formulae derived from these correlations were kept as general as possible in order that they could be used as input parameters for the selected mathematical model of desulphurization in an AFBC that is suitable for practical use. The predicted results were in good agreement with the experimental data reported in the literature. Copyright © 2003 John Wiley & Sons, Ltd.     

Computational study of transport processes in a single-screw extruder for non-newtonian chemically reactive materials

A numerical study of the transport phenomena arising in a single-screw extruder channel is carried out. A non-Newtonian fluid is considered, using a power law model for the variable viscosity. Chemical reaction kinetics are also included. Finite difference computations are carried out to solve the governing set of partial differential equations for the velocity, temperature and species concentration fields, over a wide range of governing parameters for the case of a tapered screw channel. The numerical treatment for this combined heat and mass transfer problem is outlined. A marching procedure in the down-channel direction is adopted and the validity of the scheme for practical problems discussed. For large viscous dissipation, the material heats up considerably due to the prevailing shear field, affecting the viscosity significantly, and results in large changes in the pressure development at the end of the channel. The rate of reaction controls the mass diffusion rate which in turn affects viscosity and the flow significantly. The dimensionless throughput,q _v , is one of the most important parameters in the numerical solution. The dimensionless pressure variation is very sensitive toq _v , and orders of magnitude changes are possible for small variations inq _v . Schemes for dealing with other important effects such as back flow, heat transfer by conduction in the barrel, and the effect of the die are also outlined. A list of symbols is given at the end of the paper This is publication No. F-10544-4-91 of the New Jersey Agricultural Experiment Station supported by State Funds and the Center for Advanced Food Technology (CAFT). The Center for Advanced Food Technology is a New Jersey Commission on Science and Technology Center. This work was also supported in part by the US Army Research Office.     

TPC方法研究催化剂热分解动力学

设计了ＴＰＣ方法研究催化剂前驱体的热分解；对ＴＰＣ方法求取催化剂的热分解动力学方程进行了理论推导；采用ＴＰＣ方法试验求得了Ｎｉ－Ｚｎ／Ｃ催化剂的热分解动力学参数。试验表明，ＴＰＣ方法能直观、灵敏、方便地反映催化剂活性组份前驱体的本征热分解。     

超高强度钢CF裂纹扩展的超载效应 Ⅰ．定量模型及预测

将Ｗｉｌｌｅｎｂｏｒｇ的超载残余应力场模型与裂尖形变动力学、裂尖表面析氢反应电化学动力学以及裂尖材料内部氢的扩散动力学和热力学相结合，建立了氢脆腐蚀疲劳裂纹扩展（ＣＦＣＧ）超载效应的定量描述模型，给出了超载对裂尖表面析氢电化学反应及裂尖氢扩展影响的一系列判据和表达式．用上述模型进行的预测表明，对于超高强度钢，当两次超载周次之间裂纹扩展长度ａｄ远小于超载塑性区尺寸ｒｐＯＬ与恒载塑性区尺寸ｒｐＣＬＡ之差，即ａｄ＜＜ｒｐＯＬ－ｒｐＣＬＡ时，ＣＦＣＧ会发生比空气疲劳还强烈的超载迟滞效应．而当ａｄ＞ｒｐＯＬ－ｒｐＣＬＡ时，可能会发生超载加速效应．这种预测在后文中由试验的宏观规律与断口特征得到充分验证．     

Modelling of addition polymerization processes — Free radical,ionic, group transfer,and ziegler–natta kinetics

A brief review of addition polymerization processes is presented with a summary of the key characteristics classified by kinetic mechanism (free-radical, anionic, cationic, group transfer, or Ziegler–Natta), phase behavior, and reactor type. A practical approach to modelling in the industrial R & D environment is discussed in terms of a CAD package for polymerization processes.