Epoxidation of high trans‐1,4‐polyisoprene and its properties

A new organic‐solvent‐free water‐phase suspension method was used to synthesize partially epoxidized high trans‐1,4‐polyisoprene (TPI) to improve its properties, including oil resistance and wet‐skid resistance. The epoxidation was conducted in an aqueous peracetic acid solution and on the TPI granules prepared by a bulk precipitation method with supported titanium catalyst. The effects of the synthesis conditions, including reaction temperature, reaction time, and pH value, on the epoxy content were investigated. Epoxidized trans‐1,4‐polyisoprene (ETPI) with epoxy contents between 10 and 80% were obtained within 4 h. Both the amorphous and crystalline regions of TPI were epoxidized. The crystallization properties decreased with increasing epoxy content. ETPIs possessed lower mechanical properties than TPI but could be enhanced by vulcanization. The oil resistance and wet‐skid resistance were significantly improved after epoxidation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of poly(N‐vinyl‐2‐pyrrolidone) grafted sodium alginate hydrogel beads for the controlled release of indomethacin

Graft copolymers of sodium alginate (NaAlg) with N‐vinyl‐2‐pyrrolidone were prepared using azobisisobutyronitrile as initiator. The graft copolymers (NaAlg‐g‐PVP) were characterized with Fourier transform infrared spectroscopy, elemental analysis, and differential scanning calorimetry. Polymeric hydrogel beads of NaAlg and NaAlg‐g‐PVP were prepared by crosslinking method using glutaraldehyde (GA) as a crosslinker in the hydrochloric acid catalyst (HCl) and these beads were used to deliver anti‐inflammatory drug, indomethacin (IM). Chemical stability of the IM after encapsulation into beads was confirmed by FTIR. Preparation conditions of the NaAlg‐g‐PVP beads were optimized by considering the percentage entrapment efficiency, particle size, swelling capacity and their release data. In vitro release studies were performed in simulated gastric fluid (pH 1.2) for the initial 2 h, followed by simulated intestinal fluid (pH 7.4) for 4 h. Effects of GA concentration, exposure time to GA, drug/polymer (d/p) ratio, and concentration of HCl on the release of IM were discussed. It was observed that IM release from the beads decreased with increasing GA concentration and exposure time. IM release also decreases with increasing d/p ratio and HCl concentration. The highest IM release was obtained to be 77% for beads crosslinked with 0.027M GA. Swelling experiments were also performed to compute molecular mass between crosslinks of the beads. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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     

Preparation and Characterization of Carboxymethyl Chitosan and β-Cyclodextrin Microspheres by Spray Drying

Three kinds of carboxymethyl chitosan/β-cyclodextrin microspheres loaded with theophylline were prepared by spray drying intended for pulmonary delivery. Mucociliotoxicity, permeation rate, and drug release characteristics of the product were investigated. The microspheres obtained by spray drying were found to be spherical with smooth or wrinkled surfaces. The mean particle size was between 3.39 and 6.06 µm. The microspheres demonstrated high product yield (43.7-50.2%), high drug loading (13.7-38.1%), and high encapsulation efficiency (86.9-92.8%). FT-IR indicated that there were interactions of theophylline with carboxymethyl chitosan matrix. Further studies on mucociliotoxicity and permeation confirmed that microspheres had better adaptability and high permeation rate. In vitro drug release from the microspheres was not related to the drug/polymer ratios.     

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.     

罗坡坝水电站泄水建筑物设计及试验研究

罗坡坝水电站拱坝设置有三个溢流表孔,中间孔高程低于两侧的孔,三个泄水孔设有差动式挑坎。通过模型试验表明,不发生危及岸坡稳定的泄流雾化问题,此外,适当控制泄流水舌射程可以减少坝下冲坑深度,消能效果良好。     

Fire performance of wood (Pinus radiata) treated with fire retardants and a wood preservative

In this work, we co‐formulated an oil‐borne copper naphthenate/permethrin wood preservative system with synthetic polymer‐based fire‐retardant additives prior to the impregnation of Pinus radiata sapwood. We evaluated what effect, if any, the preservative had upon the fire performance properties of the fire retardants and whether the fire retardants impacted on the fungicidal and termiticidal efficacy of the preservative. The fire retardants included halogenated and phosphorus‐based systems. A mass loss calorimeter, in conjunction with a thermopile, was used to measure the time to ignition and the peak heat release rate (PHRR) from which the fire performance index (FPI) was determined. The preservative properties were evaluated using termite and soil‐block decay bioassays. In summary, we found that the rate of fire growth was reduced when the fire retardants were used in combination with the wood preservative. We also found that the PHRR was a better determinant of fire performance than the FPI. The performance of the wood preservative was enhanced against fungal decay and termite attack when used in combination with the fire retardants. The fire retardants also demonstrated some wood preservative properties of their own. Copyright © 2008 John Wiley & Sons, Ltd.