Effect of hydrophobic hexafluoroisopropylidene group on the water sorption behaviors of rigid poly(p‐phenylene pyromellitimide) polyimide thin films

We prepared poly(p‐phenylene pyromellitimide) (PMDA–PDA), poly(p‐phenylene 4,4′‐hexafluoroisopropylidene diphthalimide), and their copolyimides with various compositions to explore the relationship between the water sorption and structure. The water sorption behaviors were gravimetrically investigated as a function of composition and temperature and interpreted with a Fickian diffusion model in films. Overall, the water sorption behaviors were strongly dependent on the changes in morphological structure, which originated from the variations in composition. When the content of the bulky hexafluoroisopropylidene group (6FDA) was increased, the water uptake decreased from 5.80 to 3.18 wt %, whereas the diffusion coefficient increased from 3.6 × 10^?10 to 11.3 × 10^?10 cm²/s. The relatively high water uptake in the PMDA–PDA polyimide film was successfully healed by the incorporation of 6FDA, which may have resulted from the increases in the intermolecular packing order and hydrophobicity. The degree of orientation and crystallinity, which are in‐plane characteristics, were directly correlated to the diffusion coefficient and activation energy in the polyimide film. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3442–3446, 2003     

Selective O-Alkylation Reaction of Hydroquinone with Methanol over Cs Ion-Exchanged Zeolites

O-alkylation reaction of hydroquinone with excess methanol was performed by using alkali metal ion-exchanged zeolite catalysts in a slurry type reactor to substitute the solid zeolite catalysts for the homogeneous liquid phase catalysts. This was also done to produce selectively mono-alkylated 4-methoxyphenol, a valuable intermediate for the perfume, flavor, food and photo industries. The effects of the basicity of various zeolites and reaction conditions such as temperature, reaction time and the amount of catalyst on the catalytic activity and selectivity were tested to maximize the yield of 4-methoxyphenol. Thus far, 84% selectivity at 95% conversion of hydroquinone was obtained at the optimum reaction conditions (240 ‡C, reaction with 0.6 g catalyst for 16 h), which was thought to result from the strong basic property and shape selectivity of the Cs ion-exchanged NaX zeolite.     

Hydrodynamic characteristics of a FCC regenerator

The hydrodynamic and gas mixing characteristics have been determined in a FCC regenerator (0.48 m I.D.x3.4 m high) with FCC particles. Solids holdup in the dense bed decreases with increasing gas velocity, but it increases in the freeboard region. The bubble/void fraction increases with an increase along the bed height at a given gas velocity and increases with increasing gas velocity at a constant bed height. Backmixed tracer gas at the wall region is higher than that at the center region of the bed. The gas backmixing coefficient decreases with increasing gas velocity.     

Stormer-numerov approximation for numerical solutions of ordinary and partial differential equations

Stormer-Numerov approximations of high accuracy were developed for solutions of non-linear boundary value problems and nonlinear elliptic partial differential equations. The approximations can be easily adopted also for parabolic partial differential equations in one and more space dimensions and feature fourth-order accuracy. For boundary value problems only three nodes are necessary to obtain the desired fourth order accuracy. The finite difference formula for parabolic partial differential equations can be readily generalized to a nonequidistant mesh so that automatic regridding in space may be used. The Stomer-Numerov approximations are important for solution of problems where storage limitations and computer time expenditure preclude standard second order methods. Because of the fourth order approximations a low number of mesh points can be used for a majority of chemical engineering problems. The application of Stormer-Numerov approximations is illustrated on a number of examples.     

模数对无机富锌涂料和涂层性能的影响

硅酸钾富锌涂料是目前广泛使用的钢铁防腐蚀涂料。作为涂料粘结剂的高模数硅酸钾溶液对涂料和涂层的性能有重要影响。本研究考察了硅酸钾粘结剂的模数变化对涂料及涂层性能产生的影响。实验结果表明：粘结剂模数的提高可以提高固化后涂层的耐水性能，当粘结剂模数在5.0左右时，所得富锌涂层具有最佳的耐磨性能，但当粘结剂模数超过5.5时会造成涂料施工性能和贮存稳定性下降，涂层柔韧性降低，从而降低涂层的耐磨性能。     

Kinetics of cellobiose decomposition under subcritical and supercritical water in continuous flow system

The effects of reaction temperature, pressure and residence time were investigated with a flow apparatus. Cellobiose decomposition kinetics and products in suband supercritical water were examined at temperatures from 320 to 420 °C at pressures from 25 to 40 MPa, and at residence times within 3 sec. Cellobiose was found to decompose via hydrolysis and pyrolysis. The yield of desired hydrolysis product, glucose, was the maximum value of 36.8% at 320 °C, 35 MPa, but the amount of 5-(hydroxymethyl)furfural (HMF), fermentation inhibitor increased too because residence time increased in the subcritical region owing to decrease of reaction rate. Meanwhile, though the yield of glucose is low in the supercritical region, the yield of HMF decreased compared with the subcritical region; and at the minimum yield of HMF (380 °C, 25 MPa), the yield of glucose was 21.4%. The decomposition of cellobiose followed first-order kinetics and the activation energy for the decomposition of cellobiose was 51.05 kJ/mol at 40MPa.     

Electrochemical cell current requirements for toxic organic waste destruction in Ce(IV)-mediated electrochemical oxidation process

The electrochemical cell for cerium oxidation and reactor for organic destruction are the most important operation units for the successful working mediated electrochemical oxidation (MEO) process. In this study, electrochemical cells with DSA electrodes of two types, single stack and double stack connected in series, were used. The performances towards the electrochemical generation of Ce(IV) in nitric acid media at 80 °C were studied. The current-voltage curves and cerium electrolysis kinetics showed the dependence on number of cell stacks needed to be connected in series for the destruction of a given quantity of organic pollutant. The presence of an optimum region for Ce(III) oxidation with a contribution of oxygen evolution, especially at low Ce(III) concentration (high conversion ratios), was found. The cells were applied for the Ce(IV) regeneration during the organic destruction. The cell and reactor processes were fitted in a simple model proposed and used to calculate the current needed in terms of Ce(III) oxidation rate and the number of cell stacks required for maintaining Ce(IV)/Ce(III) ratio at the same level during the organic destruction. This consideration was based on the kinetic model previously developed by us for the organic destruction in the MEO process.     

含氟有机化合物氟化反应研究进展

介绍了含氟有机化合物的优点,一些常用的含氟有机化合物的分类和适用性,并介绍了主要的合成方法,按照合成物质的种类分为含氟非成环烷烃类、含氟环烷烃类及其衍生物和各自不同的应用.叙述了引入F原子或引入含氟端基的方法:电化学反应法、聚合反应法和其它反应法.     

Preparation and characterization of eugenol‐grafted chitosan hydrogels and their antioxidant activities

The hydrogels composed of chitosan and eugenol were prepared to enhance and sustain antioxidant activities. The vinyl groups of eugenol monomer were directly grafted on the amino groups of chitosan, using ceric ammonium nitrate. The graft of eugenol onto chitosan was confirmed by using Fourier‐transform infrared and proton nuclear magnetic resonance spectroscopies. Results from the swelling behavior, thermal stability, and wide‐angle X‐ray diffraction revealed that the equilibrium water content decreased with increase of graft yields, because of the hydrophobicity of eugenol, although the introduction of eugenol as a side chain disturbed the ordered arrangement of chitosan's crystalline structure. The eugenol‐grafted chitosan hydrogels showed lower pH sensitivity in comparison with chitosan alone, because the amino groups, which were pH sensitive, of chitosan were grafted with eugenol. The scavenging activity of the tested hydrogels increased with graft yield of eugenol, because phenolic groups in the eugenol could play a major role as potent free‐radical terminators, in the results of improved antioxidant activity in eugenol‐grafted chitosan hydrogel in comparison with chitosan alone. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99:3500–3506, 2006     

Catalytic characteristics of various rubber-reinforcing carbon blacks in decomposition of methane for hydrogen production

Carbon black has recently been reported to act as an effective catalyst for methane decomposition and to exhibit stable catalytic behavior despite carbon deposition, and thus it can be used for CO₂-free production of hydrogen from natural gas. In this work, various carbon blacks with different primary particle size were investigated with respect to methane decomposition under atmospheric pressure from 1123 to 1223 K. Catalytic characteristics, such as activity, activation energy and reaction order, were investigated and compared. It was observed that with decreasing primary particle size (or increasing specific surface area), the specific activity increased and the activation energy decreased. The reaction orders for various pelletized, rubber-reinforcing carbon blacks were 0.6–0.7, about the same regardless of the primary particle size, while they were near 1 for fluffy carbon blacks. Fluffy carbon black showed higher activity and activation energy than the pelletized carbon black of the same primary particle size. Changes of the surface morphology during carbon deposition were observed by TEM. Variations of the number of active sites were discussed in regard of the primary particle size, carbon deposition and binder. The presence of different types of active sites was also suggested.