Isothermal crystallization behavior of hybrid biocomposite consisting of regenerated cellulose fiber,clay, and poly(lactic acid)

Quantitative analysis of isothermal crystallization kinetics of PLA/clay nanocomposite and PLA/clay/regenerated cellulose fiber (RCF) hybrid composite has been conducted. The crystallization rate constant (k) according to Avrami equation was higher in PLA/clay nanocomposite than in PLA/clay/RCF hybrid composite at the same crystallization temperature. The equilibrium melting temperature obtained by Hoffman–Weeks equation was almost same in both composites, whereas stability parameter was greater in hybrid composite than in nanocomposite. Activation energy of hybrid composite for crystallization was larger than that of nanocomposite. The value of nucleation parameter (K_g) and surface free energy (s_e) of hybrid composite were larger than nanocomposite, indicating that hybrid composite has a less folding regularity than nanocomposite. © 2008 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 adsorption behavior of a cellulose‐based,mixed‐mode adsorbent with a benzylamine ligand for expanded bed applications

A novel mixed‐mode expanded bed adsorbent with anion‐exchange properties was explored with benzylamine as the functional ligand. The cellulose composite matrix, densified with stainless steel powder, was prepared with the method of water‐in‐oil suspension thermal regeneration. High activation levels of the cellulose matrix were obtained with allyl bromide because of the relative inertness of the allyl group under the conditions of the activation reaction. After the formation of the bromohydrin with N‐bromosuccinimide and coupling with benzylamine, the activated matrix was derived to function as a mixed‐mode adsorbent containing both hydrophobic and ionic groups. The protein adsorption capacity was investigated with bovine serum albumin as a model protein. The results indicated that the prepared adsorbent could bind bovine serum albumin with a high adsorption capacity, and it showed salt tolerance. Effective desorption was achieved by a pH adjustment across the isoelectric point of the protein. The interactions between the cell and adsorbent were studied, and the bioadhesion was shielded by the adjustment of the salt concentration above 0.1M. Stable fluidization in the expanded bed was obtained even in a 2% (dry weight) yeast suspension. The direct capture of target proteins from a biomass‐containing feedstock without extra dilution steps could be expected with the mixed‐mode adsorbent prepared in this work, and this would be especially appropriate for expanded bed adsorption applications. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Use of postconsumer polyethylene in blends with polyamide 6: Effects of the extrusion method and the compatibilizer

Blends of polyamide and high‐density polyethylene show adequate properties for a large range of applications: they are used for the production of filaments, containers, and molding resins. The effect of the addition of 2 wt % of a compatibilizer, maleic anhydride grafted polyethylene, to the blend was studied and compared to the use of postconsumer polyethylene. The samples were extruded with single‐ and twin‐screw extruders with 25, 50, or 75 wt % f polyethylene, and the test specimens, molded by injection, were characterized by stress–strain tests, thermal properties, and morphologies. Processing the blends with postconsumer polyethylene in both extruders improved the mechanical properties in comparison to the blends processed with high‐density polyethylene and the compatibilizer. The morphologies of these blends showed that there was a decrease in the domain size of the disperse phase with the use of the compatibilizer or postconsumer polyethylene. The results indicate that for this blend, postconsumer polyethylene substituted, with advantages, for the necessity of a compatibilizer and the use of the high‐density polyethylene. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008.     

The effect of ionic interaction on the miscibility and crystallization behaviors of poly(ethylene glycol)/poly(L‐lactic acid) blends

The effect of end groups (2NH₂) of poly(ethylene glycol) (PEG) on the miscibility and crystallization behaviors of binary crystalline blends of PEG/poly(L ‐lactic acid) (PLLA) were investigated. The results of conductivity meter and dielectric analyzer (DEA) implied the existence of ions, which could be explained by the amine groups of PEG gaining the protons from the carboxylic acid groups of PLLA. The miscibility of PEG(2NH₂)/PLLA blends was the best because of the ionic interaction as compared with PEG(2OH, 1OH‐1CH₃, and 2CH₃)/PLLA blends. Since the ionic interaction formed only at the chain ends of PEG(2NH₂) and PLLA, unlike hydrogen bonds forming at various sites along the chains in the other PEG/PLLA blend systems, the folding of PLLA blended with PEG(2NH₂) was affected in a different manner. Thus the fold surface free energy played an important role on the crystallization rate of PLLA for the PEG(2NH₂)/PLLA blend system. PLLA had the least fold surface free energy and the fast crystallization rate in the PEG(2NH₂)/PLLA blend system, among all the PEG/PLLA systems studied. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Sheet molding compound characterization using spiral flow

Sheet molding compound (SMC) is a fiber‐reinforced polymeric composite. It is often used in automotive, marine, and industrial applications over other materials because of its high strength to density ratio, resistance to corrosion, and low cost. There is a demand in the SMC industry to be able to characterize SMC processability. This is particularly true for heavy truck body panels, one of the fastest growing applications of SMC. Because of their large size and high strength requirement, the molding forces have a major influence in the molding cycle. Also because of the long flow paths involved, the ability of the paste to carry glass needs to be properly characterized when developing new SMC materials. In this article, we demonstrate the benefits of using spiral flow as a processability tester. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Polysaccharide‐based artificial extracellular matrix: Preparation and characterization of three‐dimensional,macroporous chitosan,and heparin composite scaffold

Scaffold‐guided tissue engineering based on synthetic and natural occurring polymers has gained many interests in recent year. In this study, the development of a chitosan‐heparin artificial extracellular matrix (AECM) is reported. Three‐dimensional, macroporous composite AECMs composed of heparin (Hep) and chitosan (Chito) were prepared by an interpolyelectrolyte complex/lyophilization method. The Chito‐Hep composite AECMs were, respectively, crosslinked with glutaraldehyde, as well as cocrosslinked with N,N‐(3‐dimethylaminopropyl)‐N′‐ethyl carbodiimide (EDC/NHS) and N‐hydroxysuccinimide (NHS). The crosslinking reactions were examined by FT‐IR analysis. In physiological buffer solution (PBS), the EDC/NHS‐crosslinked Chito‐Hep composite AECM showed a relative lower water retention ratio than its glutaraldehyde‐crosslinked counterparts. The EDC/NHS‐crosslinked Chito‐Hep composite AECMs showed excellent biocompatibility, according to the results of the in vitro cytotoxic test. This result suggested that the EDC/NHS‐crosslinked Chito‐Hep composite AECMs might be a potential biomaterial for scaffold‐guided tissue engineering applications. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Dynamic photorheological analysis of photopolymerizable urethane dimethacrylate resins with varying diluent content and light fluence

The in situ measurement of dynamic changes in viscosity induced by illumination has been performed on a range of photosensitive urethane dimethacrylates (UDMA) evaluating the response at three different illuminations intensities (1, 2, and 5 W cm^?2) and at three different diluent concentrations (15, 30, and 50%), using 1,6‐hexanediol dimethacrylate (HDDMA). The initial viscosity value ranged between 1 and 10 Pa s for the mixtures with final viscosities approaching 1 × 10⁷ Pa s after illumination. The initial rise in viscosity was analyzed using an exponential model with an exponent ranging from 1.0 to 2.5 with time under exposure. Higher conversion rates were observed with both higher intensity and lower HDDMA content. The analytical approach taken here could aid in developing more sophisticated models that consider simultaneous flow and cure advancement in other thermosets. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects and properties of poly(arylene ether benzonitrile)s of various molecular weights blended with sulfonated poly(ether ether ketone)

Poly(arylene ether benzonitrile) (PAEBN) was synthesized with 2,6‐dichlorobenzonitrile and biphenol. PAEBNs with various molecular weights (MWs), 1,640,000 and 185,000 g/mol, were synthesized by control of the stoichiometry of the monomers and were blended with sulfonated poly(ether ether ketone) (SPEEK). The effects of MW on the water uptake, swelling, methanol permeability, and proton conductivity of the SPEEK/PAEBN blend membranes were investigated. The molecular mobility of the SPEEK/PAEBN blends was also examined in this study. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

EPR kinetics in irradiated syndiotactic polystyrene at elevated temperatures

Free radicals are formed upon irradiation of polymers. The annealing of γ-ray irradiated syndiotactic polystyrene (sPS) with doses 10, 23 and 36 kGy was studied with electron paramagnetic resonance (EPR) spectroscopy. The EPR spectra are possibly attributed to three types of radicals, (a) the benzyl radical Ra, (b) resonance structure of the phenyl radical Rb, and (c) carbon-superoxide-centered radical Rc with three-, four-, and single-line features, respectively. Radical Ra can be easily formed by the removal of the proton from the tertiary carbon; radical Rb is created from delocalization of the spin of the radical Ra onto the benzene ring; and radical Rc may be generated from the interaction of a carbon-centered radical with dioxygen from the air which forms a carbon-superoxide center. By comparing EPR spectra of the radicals with a DPPH standard, the spin numbers of the radicals can be calculated. The spin number of all radicals decreases exponentially with time in the temperature range of 60-90 °C regardless of dose of the irradiation. The annealing of Ra, Rb, and Rc follows first-order kinetics. The activation energies of the annihilation are determined to be 15.8-19.0, 16.0-19.5, and 23.2-26.6 kJ/mol for radicals Ra, Rb, and Rc, respectively. The kinetic study presented herein can serve as a criterion for γ-ray irradiation process in various applications, such as sterilization of polymer materials and devices.