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.     

高炉喷吹废塑料燃烧动力学研究

为了提供高炉喷吹废塑料新技术工业化应用的理论依据，通过对其动力学参数的求解，研究了高炉喷吹废塑料的燃烧动力学，得出了该燃烧反应是一级反应，且在温度为200℃、塑料配比为20％～25％时活化能最低、燃烧阻力小的结论。     

DSC study on simultaneous interpenetrating polymer network formation of epoxy resin and unsaturated polyester

A kinetic study on simultaneous interpenetrating polymer network formation of epoxy resin based on diglycidyl ether of Bisphenol A (DGEBA) and unsaturated polyester (UP) was performed by means of differential scanning calorimetry (DSC). Isothermal DSC characterizations of neat resins and their mixture (in a weight ratio of 50/50) were performed at different temperatures. Dynamic DSC characterization of the systems were performed at three different heating rates. A lower total heat of reaction developed during simultaneous polymerization in dynamic DSC tests was found, compared to the total heats developed during pure resins network formation. This phenomenon can be interpreted as an effect of network interlock that could not be compensated for completely by an increase in curing temperature. The kinetics of the reactions was described by empirical models. The DGEBA, in a 50/50 UP/DGEBA blend, indicated a higher rate constant than the pure DGEBA. The obtained results suggests that the hydroxyl end group of UP in the blend provided a favorably catalytic environment for the DGEBA cure. The results are in good agreement with the literature data. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 2689–2698, 2002     

Application of degradation kinetics to the rheology of poly(hydroxyalkanoates)

The time‐dependent rheological behavior of a series of 3‐hydroxybuytrate‐based semicrystalline copolymers is employed to determine the expected rheological curves that would be generated in the absence of any polymer degradation. Both dynamic frequency sweep and shear rate sweep experiments were analyzed. A model for the degradation kinetics, coupled with standard rheological relationships, was employed to extrapolate the measured sweeps to predicted curves at time zero, prior to degradation. The model is broadly applicable over a wide range of frequencies or shear rates, and generates a single degradation rate constant k for each polymer studied. A similar, although ad hoc, procedure was applied to the dynamic storage and loss moduli. The model provides a method for determining the rheological behavior of degrading polymers over a time interval, typically found in processing applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1794–1802, 2006     

Kinetics of phenol oxidation in a trickle bed reactor over active carbon catalyst

The wet air oxidation of phenol over a commercial active carbon catalyst was studied in a trickle bed reactor (TBR) in the temperature and oxygen partial pressure ranges of 120–160 °C and 0.1–0.2 MPa, respectively. The performance of the active carbon was compared in terms of phenol and COD destruction. The weight change of active carbon due to reaction was also measured. Finally, oxic phenol adsorption isotherms were assessed in batch conditions at 25, 125 and 160 °C. In order to use the conversion data obtained from the TBR for a kinetic study, special care was taken to check the kinetic control in the TBR experiments. Several kinetic models including power law or Langmuir–Hinshelwood expressions were considered to describe the catalytic oxidation of phenol over active carbon. The simple power law model with first order dependence on both phenol and oxygen concentration predicted satisfactorily the experimental data not only over the entire range of operating conditions studied, but also outside its validity range. Copyright © 2005 Society of Chemical Industry     

Acidic and basic hydrolysis of poly(N‐vinylformamide)

Poly(N‐vinylformamide) (PNVF) was synthesized and hydrolyzed to poly(vinylamine) (PVAm) in both HCl and NaOH solutions. The hydrolysis kinetics and the equilibrium hydrolysis were examined experimentally at different temperatures, polymer concentrations, and acid‐ or base‐to‐amide molar ratios. The hydrolysis kinetics strongly depended on temperature, polymer, and HCl or NaOH concentrations, but showed little dependence on PNVF molecular weight. The acid hydrolysis of PNVF exhibited limited conversions because of the electrostatic repulsion among the cationic amine groups generated during hydrolysis and proton hydrates. In the basic hydrolysis, complete amide conversions were observed when the NaOH/amide molar ratios were greater than unity. The effects of temperature and PNVF concentration on the equilibrium amide conversion appeared to be negligible in both acidic and basic hydrolysis. The equilibrium conversions of base hydrolysis were higher than those of acidic hydrolysis under the same reaction conditions. At NaOH/amide ratios of less than unity, the equilibrium hydrolysis experiments revealed that one base molecule could induce the hydrolysis of more than one amide group. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3412–3419, 2002     

Expressing the equivalence of non‐isothermal and isothermal heat sterilization processes

Currently, the sterility of heat‐processed food and pharmaceuticals is assessed in terms of an F₀ value, based on the equivalence of the heat treatment to an isothermal process at a reference temperature. This F₀ value, however, has a meaning if, and only if, the inactivation kinetics of the targeted spores (or cells) follow a first‐order relationship and the temperature dependence of the D value, the reciprocal of the rate constant, is log‐linear. There is growing evidence that these conditions are not satisfied by many spores, including those of Clostridium botulinum and vegetative cells. Consequently, a replacement for the F₀ value is proposed in the form of a momentary equivalent time at the reference temperature based on the actual survival pattern of the spores, which need not be log‐linear. This equivalent time can be calculated together with the theoretical survival ratio in real time, thus enabling an operator to monitor the lethality of ongoing industrial heat processes. The concept is demonstrated with published survival data of C. botulinum, for which the Weibullian and log‐logistic models served as primary and secondary models, respectively. The safety factor according to the proposed method is in the number of added minutes of processing, beyond the theoretical time needed to reduce the survival ratio of the targeted spores or cells to a level that would produce practical (or commercial) sterility. Copyright © 2006 Society of Chemical Industry     

Interfacial activity and rate of palladium(II) extraction with decyl pyridine monocarboxylates

Decyl isonicotiniate and decyl nicotiniate permit a rapid extraction of palladium(II) from its hydrochloride solutions. Decyl picoliniate is not a suitable extractant. 4-Octylphenylamine can act as a phase transfer catalyst when its concentration in the organic phase is at least 2·5 × 10^?4 M . It seems that the interfacial adsorption of pyridine carboxylates and of 4-octylphenylamine is not the decisive phenomenon in palladium(II) extraction. The negligible protonation of the pyridine-type extractants and the phase transfer catalysis explains well the quick extraction of palladium(II) with the commercial and highly hydrophobic extractant ACORGA CLX-50.