Cure kinetics and mechanical properties of the blend system of epoxy/diaminodiphenyl sulfone and amine terminated polyetherimide-carboxyl terminated poly(butadiene-co-acrylonitrile) block copolymer

The cure kinetics of blends of epoxy resin (4,4’-tetraglycidyl diaminodiphenyl methane; TGDDM)/curing agent (diaminodiphenyl sulfone; DDS) with ATPEI (amine terminated poly-etherimide) -CTBN (carboxyl terminated poly (butadiene-co-acrylonitrile)) block copolymer (AB type) were studied using differential scanning calorimetry under isothermal conditions to determine the reaction kinetic parameters such as activation energy and reaction constants. Final cure conversion decreased with increasing amount of AB in the blends. A diffusion controlled reaction was observed as the cure conversion increased, and the curing reaction was successfully analyzed by incorporating the diffusion control term in the rate equation for the epoxy/DDS/AB blends. The fracture toughness was improved to about 350% compared to that of the unmodified resin at 30% of AB block copolymer. This is attributed to the formation of co-continuous morphology between the epoxy phase and AB block copolymer phase. By increasing the amount of AB, the modulus of the cured blends decreased, which was due to the presence of CTBN rubbery phases.     

Evidence of a redox equilibrium assisted chain propagation mode for aniline polymerization: in situ spectral investigation in dodecylbenzene sufonic acid based system

Detailed in situ absorption spectral investigation of chemical oxidative polymerization of aniline in dodecylbenzene sufonic acid (DBSA) based system revealed that the chain propagation is assisted by redox equilibrium intermediate (REI) rather than a fully oxidized pernigraniline. The continuous reduction (addition of aniline) and oxidation (by oxidant) of REI, propagate the chain. The polymerization process consists of three prominent stages called induction period (IP), chain propagation and termination. The initial stage of polymerization is realized as IP, the time taken to establish REI. The presence of fully developed polaron band indicates REI has delocalized structure. Invariant spectral features together with tremendous increase in absorbance at propagation phase indicate REI undergoes reductive addition of aniline and oxidation by APS (ammonium persulfate) while maintaining equilibrium structure. The greatly increased absorbance with time at this stage is due to well-known autoacceleration phenomenon observed for aniline polymerization. The increase in redox potential of REI with increase in chain length accelerates the reaction and accounts for autoacceleration. The termination of polymerization would be reduction or oxidation depending on the availability of aniline or oxidant respectively. In a system where the oxidant is the limiting agent, reduction continues until it reaches emeraldine salt that is incapable of further reduction. On the other hand an excess of oxidant, results in the formation of pernigraniline by continuous oxidation.     

KINETICS AND MECHANISM OF THE REACTION BETWEEN OZONE AND O-CRESOL IN AQUEOUS SOLUTIONS

The stopped-flow spectrophotomctric method was applied to study the kinetics of the ozonation of o-cresol in aqueous solutions of pH values varying from 2 to 9 at 10 to 40°C. The fast reaction between o-cresol and ozone is second order overall with first order in each reactant. The ozonation rale increases with the temperature and pH value of the solution. In neutral solutions, the overall rate constant increases from 422,000 M^-1S^-1 at 10°C to 1,549,000 M^-1 S^-1 at 40°C. The activation energy is about 30 KJ/mol in the neutral solutions; it increases slightly with the acidity of the solution.

A mechanism based on the initial attack of ozone moleculesat the ortho and para positions of o-cresol is proposed for the ozonation reaction. According to this mechanism, three moles of ozone are required to react with each mole of o-cresol resulting in the rupture of the aromatic ring and production of various acids. The oxidation products were identified by these and other investigators. The proposed mechanism yields a second order kinetics for the overall reaction, as confirmed by the kinetic experiments.     

Modeling the Direct Synthesis of Dimethyl Ether using Artificial Neural Networks

Artificial neural networks (ANNs) are designed and implemented to model the direct synthesis of dimethyl ether (DME) from syngas over a commercial catalyst system. The predictive power of the ANNs is assessed by comparison with the predictions of a lumped model parameterized to fit the same data used for ANN training. The ANN training converges much faster than the parameter estimation of the lumped model, and the predictions show a higher degree of accuracy under all conditions. Furthermore, the simulations show that the ANN predictions are also accurate even at some conditions beyond the validity range.     

缓蚀剂阳极脱附现象的研究：V.缓蚀剂脱附与金属阳极过程

根据缓蚀剂阳极脱附与金属阳极溶解相互作用的分析，建立了描述缓蚀剂系中金属阳极过程动力学规律的物理模型。依据该模型讨论了缓蚀覆盖度随电位与浓度的变化。脱附电位与半盖电位，电位扰动与浓度扰动的电流响应及稳态阳极极化曲线。     

氯盐溶液中铅置换银的动力学

应用旋转圆盘技术研究了饱和氯化钠溶液中铅置换银的动力学。置换速率明显受到温度、搅拌速率、初始银浓度及溶液ｐＨ值的影响。溶液ｐＨ值由中性降至弱酸性时，有利于置换反应的进行。适当条件下，每平方米铅板上银的沉积量在１．５ｈ内可达到０．２６ｋｇ以上。体系的置换反应机理符合扩散控制机理。动力学数据服从一级反应速率的规律。     

压应力对Cr-Mo钢连续冷却贝氏体相变的影响

采用Gleeble-1500热模拟试验机测量了Cr-Mo钢在1-90℃／s的冷却速度下奥氏体连续冷却过程中的温度．膨胀曲线，用origin软件进行数据处理，获得了实验钢的CCT曲线；同时测量了施加轴向载荷为0、40MPa、80MPa和120MPa的压应力时奥氏体连续冷却过程中的温度．膨胀曲线，冷却速度分别为50℃／s、70℃／s和90℃／s。利用杠杆定律，根据不同温度下的膨胀量计算得到贝氏体相变动力学曲线，研究了压应力对贝氏体相变动力学和贝氏体相变温度的影响。结果表明，在以冷却速度为50℃／s和70℃／s连续冷却时，压应力抑制前期阶段的贝氏体相变，促进后期阶段的贝氏体相变；在以冷却速度为90℃／s连续冷却时，压应力对整个贝氏体相变过程都有促进作用，特别是应力较大时；压应力使贝氏体相变开始温度Bs升高，贝氏体相变终了温度Bf降低。     

Modelling Industrial Wastewater Ozonation In Bubble Contactors. 1. Rate Coefficient Determination

A study of the ozonation of distillery and tomato wastewaters was carried out in a small bubble contactor in order to obtain kinetic data for scaling-up. Thus, several parameters, such as chemical oxygen demand (COD), 254 nm absorbance (A₂₅₄) and organic carbon content (OC), were followed during ozonation at different experimental conditions.

For distillery wastewaters all parameters investigated have the highest decreases during the first minutes of ozonation, A₂₅₄ showing the highest disappearance rates. Thus, during the first fifteen minutes of ozonation an important decrease of the 254 nm absorbance (? 75%) was observed. At further reaction times values of all parameters studied decrease slowly, eventually reaching a plateau value. During approximately the first two hours of reaction, dissolved ozone was never found, which suggested that fast or moderate gas-liquid reactions took place in the wastewaters.