可发泡性酚醛树脂的合成研究

考查了可发泡性酚醛树脂的合成条件,如反应时间、温度和催化剂用量等对树脂活性、物理以及酚醛泡沫塑料容重和表观品质的影响,结果表明:催化剂用量越大,树脂粘度越大,泡沫固化时间越长;反应时间介于65～95min,泡沫塑料容重和表观品质较好;用加热板测定了合成的可发泡性树脂的固化速度,并求出固化反应活化能。     

Reaction kinetics of rye straw for thermnochemical conversion

Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were conducted on two common types of rye straws (Danko and Kustro) at a heating rate of 20°C/min in an oxidizing atmosphere (15% oxygen and 85% nitrogen, by volume) between ambient temperature and 700°C. The two step nature of the TGA curves and the dual peak characteristics of the DTA curves showed that rye straw had two distinct reaction zones. The initial degradation temperatures, the residual mass at 700°C, the thermal degradation rates in the first and second reaction zones and the kinetic parameters of each reaction zone (order of reaction, activation energy and pre-exponential factor) were determined. Higher thermal degradation rates were observed in the first reaction zone as compared to those in the second reaction zone.     

Electrochemical Behaviour of Al, Al—In and Al–Ga–In Alloys in Chloride Solutions Containing Zinc Ions

The electrochemical behaviour of Al, Al—In and Al–Ga–In alloys in 0.6 m NaCl solutions with and without Zn²⁺ was investigated. The study was performed by means of open circuit potential, potentiodynamic polarization, potentiostatic current-time and electrochemical impedance spectroscopy measurements as well as by SEM-EDAX examination. It was found that the Al—In alloy exhibits the highest negative open circuit potential in 0.6 m NaCl and the corrosion resistance of the tested electrodes decreases in the following order: Al > Al–Ga–In > Al—In. The greater activity of the Al—In alloy was interpreted on the basis of the autocatalytic attack by indium. The potentiostatic current–time measurements in Zn²⁺ containing electrolyte at potentials above the pitting potential revealed that Zn²⁺ has an insignificant influence on the Al electrode, while it enhances the corrosion of the Al–Ga–In alloy and improves the attack morphology of the Al—In alloy. Furthermore, the impedance spectra recorded under open circuit conditions showed a decrease in the polarization resistance of Al—In and Al–Ga–In alloys in presence of Zn²⁺ indicating the activating effect of Zn²⁺ ions.     

臭氧氧化法除地表水有机物试验研究

本文阐述臭氧化法除地表水有机物的重要意义，实验结果表明：臭氧氧化有机物的总氧化速率受活化控制，影响氧化率的最高显著因素是温度，其次是ｐＨ，接触时间等，臭氧很容易氧化腐植酸，在３０℃，ｐＨ９．０～１０．０，７ｍｉｎ内，ＣＯＤ去除率可达６０％以上，对邯郸热电厂生产处理也取得良好效果，３５℃，ｐＨ７．４～７．６，１０ｍｉｎ内，ＣＯＤ去除率可达６７％，可望将臭氧化水处理工艺应用于电厂水处理。     

Crystallization behavior of poly(N‐methyldodecano‐12‐lactam). IV. Nonisothermal crystallization

Nonisothermal crystallization of poly(N‐methyldodecano‐12‐lactam) (MPA) was investigated using DSC method at cooling rates of 2–40 K/min. With increasing cooling rate, crystallization exotherms decreased in magnitude and shifted toward lower temperatures. Subsequent heating runs (10 K/min) showed an exotherm just above T_g, which increased in magnitude with the rate of preceding cooling run, corresponding to the continuation of primary crystallization interrupted as the system crossed T_g on cooling. Kinetic evaluation by the Avrami method gave values of exponent n close to 2.0, suggesting two‐dimensional crystal growth combined with heterogeneous nucleation. The Tobin method, covering the intermediate range of relative crystallinities, provided n ? 2.20, suggesting possible partial involvement of homogeneous nucleation at later stages of nonisothermal crystallization. The crystallization rate parameter k^1/n showed a linear dependency on cooling rate for both methods, the Tobin values being slightly higher. The Ozawa approach failed to provide reasonable values of the kinetic exponent m of MPA. The Augis–Bennet method was used to determine the effective activation energy of the entire nonisothermal crystallization process of MPA. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 564–572, 2005     

Quick Activation of Optimized Zeolites with Microwave Heating and Utilization of Zeolites for Reusable Desiccant

Effectiveness of microwave heating in an activation treatment of zeolites was studied and utilization of zeolites for reusable desiccant was examined. X zeolite was chosen as a target material for its large adsorption capacity. Na-X zeolite easily caused a thermal runaway by microwave radiation of 500 W but Ca contained X zeolite merely reached ca. 573 K under the same conditions. Mixtures of Na-X and Ca-X with suitably mixed ratios did not cause the thermal runaway and their heating temperatures were controlled (>573 K) at will. Under the most suitable conditions, the mixture reached a dehydration degree of 92%. A degradation degree of adsorptive capacity of the mixture for water was examined after three treatments. The average degradation degree was 1.5% per treatment. The heating method is promising as a quick and easy technique to activate zeolite. By applying the method, the zeolites with suitable mixing ratios are usable as a reusable desiccant for home use.     

抗氧剂3114合成反应热力学和动力学的研究

研究了常温溶剂法合成抗氧剂3114反应热力学和动力学过程。控制温度在117±2℃,研究结果表明,反应是零级反应,反应速率常数k=1.91×10-3/min,反应的平衡常数K=138.4(mol/L)-6,反应活化能Ea=1366.2J/mol。     

Hydrogenolysis of alkanes and olefin polymerization on the silica-supported zirconium hydrides: A comparative DFT study

The model reactions of ethylene polymerization and hydrogenolysis of linear alkanes (propane, n-butane, and n-pentane) on the silica-supported zirconium hydrides (Si–O)₃Zr^IVH, (Si–O)₂Zr^IVH₂, and (Si–O)₂Zr^IIIH were studied using the DFT approach. Catalytic processes under study were shown to occur involving different surface hydrides. The ethylene polymerization was found to proceed at comparable rates on the zirconium monohydrides, (Si–O)₃ZrH, and dihydrides, (Si–O)₂ZrH₂. Cleavage of linear alkanes on the monohydrides (Si–O)₃ZrH is thermodynamically unfavorable; however, the dihydrides (Si–O)₂ZrH₂ can act as catalysts of the process under mild conditions. Hydrides of the trivalent zirconium, (Si–O)₂Zr^IIIH, can also contribute to the hydrogenolysis reaction. A feature of all the systems studied is low regioselectivity of the corresponding processes.     

The kinetics of B‐a and P‐a type copolybenzoxazine via the ring opening process

The structure of benzoxazines is similar to that of phenolic resin through thermal self‐curing of the heterocyclic ring opening reaction that neither requires catalyst nor releases any condensation byproduct. These polybenzoxazine resins have several outstanding properties such as high thermal stability and high glass transition temperature. To better understand the curing kinetics of this copolybenzoxazine thermosetting resin, dynamic and isothermal differential scanning calorimetry measurements were performed. Three models, the Kissinger method, the Flynn–Wall–Osawa method, and the Kamal method, were used to describe the curing process. Dynamic kinetic activation energies based on Kissinger and Flynn–Wall–Osawa methods are 72.11 and 84.06 KJ/mol, respectively. The Kamal method based on an autocatalytic model results in a total order of reaction between 2.66 and 3.03, depending on curing temperature. Its activation energy and Arrhenius preexponential are 50.3 KJ/mol and 7959, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 730–737, 2005     

Modeling of metadynamic recrystallization kinetics after hot deformation of low-alloy steel Q345B

Based on the steady-state strain measured by single-pass hot compression tests, the method by a double-pass hot compression testing was developed to measure the metadynamic-recrystallization kinetics. The metadynamic recrystallization behavior of low-alloy steel Q345B during hot compression deformation was investigated in the temperature range of 1 000–1 100 °C, the strain rate range of 0.01–0.10 s⁻¹ and the interpass time range of 0.5–50 s on a Gleeble-3500 thermo-simulation machine. The results show that metadynamic recrystallization during the interpass time can be observed. As the deformation temperature and strain rate increase, softening caused by metadynamic recrystallization is obvious. According to the data of thermo-simulation, the metadynamic recrystallization activation energy is obtained to be Q _md=100.674 kJ/mol and metadynamic recrystallization kinetics model is set up. Finally, the error analysis of metadynamic recrystallization kinetics model proves that the model has high accuracy (correlation coefficient R=0.988 6).