Modification of leather properties by grafting. I. Effect of monomer chain on the physico‐mechanical properties of grafted leather

Although leather has a number of desirable properties such as thermal stability and fire retardancey, in addition to high toughness, it has a few drawbacks such as weight, high water absorption, poor soil and rot resistance, and nonuniformity. If these defects are overcome, leather's usefulness would be further enhanced and its competitive position with respect to synthetics would increase. This study reports the physical and mechanical properties of buffalo leather after chemical graft copolymerization with ethyl acrylate, butyl acrylate, and 2‐ethyl hexyl acrylate using benzoyl peroxide as an initiator. The optimum conditions for grafting (e.g., monomer and initiator concentrations, temperature and time of grafting, and solvent leather ratio) were extensively investigated. The study achieved outstanding properties for buffalo leather in reduction of water uptake after grafting, especially on using 2‐ethyl hexyl acrylate and butyl acrylate monomers. FT‐IR and solid ¹³C‐NMR for leather before and after grafting confirmed the grafting process.© 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1478–1483, 2003     

Influence of continuous stabilization on the physical properties and microstructure of PAN-based carbon fibers

A continuous stabilization and carbonization process was used to prepare polyacrylonitrile (PAN)-based carbon fibers. The stepwise stabilization of PAN fibers was tried at various temperatures. The effect of stepwise stabilization on the physical properties and microstructure of the final carbon fibers is reported in this article. The fixed temperature in stepwise stabilization is kept below the fusion temperature of PAN precursors to avoid overstabilization of the fibers. The optimum stepwise stabilization process not only increases the amount of ladder polymer in stabilized fiber but also improves the physical and mechanical properties of the resultant carbon fibers. The formation of closed pores from open pores in carbon fiber occurs at 1100°C, but the formation of closed pores occurs at 200°C lower for carbon fiber developed from overstabilized fiber. The effect of continuous stepwise stabilization on the properties of resulting stabilized fibers and the variation in physical properties, element composition, and microstructure of carbon fibers during the carbonization process are also reported in this article.     

Modeling the large‐strain constitutive behavior of polycarbonate under isothermal and anisothermal conditions

The tensile behavior of polycarbonate was studied at large strains below the glass‐transition temperature. Experiments were carried out at a series of constant temperatures and also under conditions of falling temperatures. The specimens necked with a natural draw ratio of approximately 2, and the study was mainly focused on the necked material. Isothermal experiments revealed an elastic mechanism that initiated beyond the natural draw ratio. A model consisting of an Eyring process and two Gaussian elastic mechanisms was found to be applicable to both the isothermal and anisothermal stress‐relaxation and stress–strain results. The same model also produced reasonable estimates of the stresses generated during the necking process. In addition, a simple relationship between the isothermal and anisothermal stress relaxation was demonstrated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2105–2116, 2005     

Preparation,characterization, and some physical properties of polypropylene/poly(methyl acrylate)‐grafted glass wool composites

Polypropylene/poly(methyl acrylate)‐grafted glass wool (PMA‐g‐GW) mixes were prepared. The polymerization process was carried out using potassium persulfate (PPS) and PPS/acetone sodium bisulfite (ASBS) as a redox‐pair initiation system at 60 and 70°C. The effect of using PPS or PPS/ASBS on the grafting percent and conversion percent reveals that the conversion percent values on using PPS as an initiator are higher than those of PPS/ASBS, while in the case of grafting, the inverse is true, that is, using PPS as an initiator gives grafting percent values lower than those that can be obtained using PPS/ASBS. The dielectric properties, thermal diffusivity, specific heat capacity, and thermal conductivity of PP loaded with modified glass wool as a function of different types and concentrations of initiators—used in the grafting polymerization process, namely, PPS and the redox initiating system—were also studied. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 723–732, 2003     

Monodisperse polymer/metal composite particles by electroless chemical deposition: Effect of surface functionality of polymer particles

Micron‐sized polymer particles were coated with layers of nickel compounds by plating electrolessly in the presence of aqueous solutions of nickel chloride, sodium hypophosphite, sodium citrate, and ammonium chloride at elevated temperature. The uniform functional polymer particle could be obtained by seeded polymerization. To investigate the effect of surface functionality on the conditions for nickel deposition, the polymer particle was functionalized with the thiol group. From morphological observation, it was found that the mode of nickel deposition was greatly dependent on the surface functionality of the polymer particle. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 420–424, 2003     

Evaluation of Polyester Resin as a New Compatibilizer for SBR/PVC Blends

A polyester (PE) based on the glycolyzed products of PET was prepared and added in different concentrations to a series of SBR/PVC blends. The addition of the polyester showed that all properties of SBR/PVC blends were improved by incorporation of PE. Highest mechanical strength values were obtained at a polyester concentration of 7.5 phr. Thermal analysis as well as dynamic mechanical properties of SBR/PVC blends after the addition of 7.5 and 10 phr polyester indicated one single glass transition temperature. The dielectric losses (?") were analyzed in the frequency domains in the two terms of Fröhlich related to the Maxwell Wagner effect and the orientation of the aggregates caused by the movement of the main chain. The permittivity (?') values were found to increase by increasing the polyester content. This increase was followed by a decrease in the ?" up to a 7.5 phr polyester content after which no pronounced change was noticed.     

Thermal and crystallization characteristics of poly(ethylene terephthalate) with poly(oxybenzoate‐p‐trimethylene terephthalate) copolymer

Poly(ethylene terephthalate) (PET) was blended with two different poly(oxybenzoate‐p‐trimethylene terephthalate) copolymers, designated T28 and T64, with the level of copolymer varying from 1 to 15 wt %. All samples were prepared by solution blending in a 60/40 (by weight) phenol/tetrachloroethane solvent at 50°C. The crystallization behavior of the samples was studied by DSC. The results indicate that both T28 and T64 accelerated the crystallization rate of PET in a manner similar to that of a nucleating agent. The acceleration of PET crystallization rate was most pronounced in the PET/T64 blends with a maximum level at 5 wt % of T64. The melting temperatures for the blends are comparable to that of pure PET. The observed changes in crystallization behavior are explained by the effect of the physical state of the copolyester during PET crystallization as well as the amount of copolymer in the blends. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1599–1606, 2002     

High catalytic activity of PdOx/MnO2 for CO oxidation and importance of oxidation state of Mn

PdO_x/MnO₂ has been examined as a catalyst for CO oxidation using a conventional flow reactor at reaction temperatures between 50 and 150°C. In the reaction conditions of GHSV (gashourlyspacevelocity) of 1.22 × 10⁵/h and CO concentration of 2000 ppm, PdO_x/MnO₂ showed higher catalytic activity compared with PdO_x/Mn₂O₃, which had been previously reported as an effective catalyst due to the cooperative action of Pd and Mn₂O₃ for this reaction. The reason for higher activity of PdO_x/MnO₂ than PdO_x/Mn₂O₃ has been investigated using TPR (temperatureprogrammed reduction) and XPS studies. TPR showed that PdO_x/MnO₂ could be reduced by CO at much lower temperature than PdO_x/Mn₂O₃. During the experiment of reduction and oxidation, XPS showed that the valence of Mn in the PdO_x/MnO₂ was between 4+ and 3+, which is higher than that of Mn in the PdO_x/Mn₂O₃ catalyst of which the valence has been reported to be between 3+ and 2+. It is known that in this catalyst system the support supplies oxygen onto Pd, where the oxidation occurs with adsorbed CO, and the ability of the support to provide oxygen improves the performance of the catalyst. Therefore, it was concluded that the readiness of MnO₂ to be reduced with maintaining a higher oxidation state showed higher CO oxidation activity than Mn₂O₃ as support for PdO_x.     

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