Completely biodegradable composites of poly(propylene carbonate) and short,lignocellulose fiber Hildegardia populifolia

The composites of biodegradable poly(propylene carbonate) (PPC) reinforced with short Hildegardia populifolia natural fiber were prepared by melt mixing followed by compression molding. The mechanical properties, thermal properties, and morphologies of the composites were studied via static and dynamic mechanical measurements, thermogravimetric analysis, and scanning electron microscopy (SEM) techniques, respectively. Static tensile tests showed that the stiffness and tensile strength of the composites increased with an increasing fiber content. However, the elongation at break and the energy to break decreased dramatically with the addition of short fiber. The relationship between the experimental results and the compatibility or interaction between the PPC matrix and fiber was correlated. SEM observations indicated good interfacial contact between the short fiber and PPC matrix. Thermogravimetric analysis revealed that the introduction of short Hildegardia populifolia fiber led to a slightly improved thermooxidative stability of PPC. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 666–675, 2004     

Adhesive bonding of glassy polymer surfaces by an ultrathin layer of a semicrystalline polymer

To develop a greater understanding of interfacial interactions between a semicrystalline polymer and a glassy polymer, adhesion tests were performed on very thin layers of poly(ethylene oxide) (PEO) sandwiched between two layers of poly(tetramethyl bisphenol A polycarbonate) (TMPC). The tests were designed to provide intimate contact between the surfaces while they were heated above the melting point of the PEO and cooled back to room temperature. A contact mechanics approach, based on the Johnson, Kendall, and Roberts theory, was used to determine values of the energy release rate describing the energetic driving force for crack propagation within the interfacial region. The ability to measure crack propagation at large values of the energy release rate was limited by rupture of the silicone elastomer that was used to provide a sufficiently compliant matrix for the adhesion experiment. By cycling the tensile stress at relatively low loading levels, we were able to measure fatigue crack propagation at values of the energy release rate that did not result in failure of the elastomer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3809–3821, 2004     

Ionic conductivity of multiarm star polymer/LiClO4 electrolytes

A series of polymer electrolytes based on multiarm polymers and lithium salt complexes were characterized by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and impedance measurement. The relationships of conductivity with salt concentration, temperature, and arm numbers are discussed. It is suggested that the star polymer has a higher solvency and ion transfer ability on lithium salts than on linear polymers. The conductivity maximum appeared at a higher salt concentration ([EO]/[Li] = 4). Impedance measurement suggested that the optimum conductivity was 2 × 10^?4 s · cm^?1. The conductivity increased with temperature and the dependence of ionic conductivity on temperature fits the Arrhenius equation. Among the studied systems, the star polymer with a five arm number performs better than other structures. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4195–4198, 2004     

Thermal behavior of metallodendrimers possessing bis(terpyridinyl)Ru(II) connectivity and different surface functionality

A series of metallodendrimers, assembled by means of bis(terpyridinyl)Ru^(II) connectivity on poly(propylene imine) dendrimer scaffolds, with homogeneous or heterogeneous surfaces, were prepared. Differential scanning calorimetry and thermogravimetric analysis were used to determine their thermal behavior, glass‐transition temperatures, and the decomposition kinetics and temperatures; no synergy effects for these properties were observed for the heterogeneously surfaced constructs in contrast to the corresponding homogeneously coated materials, which exhibited different values depending on their surface functionalities. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1487–1495, 2004     

Physical properties of glycosaminoglycan hydrogels

The chemical composition of glycosaminoglycan (GAG) hydrogels was found to have a profound effect on the physical properties of gels. Hyaluronan (HA) and chondroitin sulfate (CS) were each modified with adipic dihydrazide (ADH) with carbodiimide chemistry. The resulting polymer was crosslinked with various concentrations of poly(ethylene glycol) dialdehyde (PEG‐diald) to produce a series of hydrogels. The physical properties of these GAG hydrogels varied in a concentration‐dependent fashion. Maximal crosslinking was observed at a theoretical crosslinking of 50% for the HA‐ADH‐PEG‐diald hydrogels and 75% for the CS‐ADH‐PEG‐diald hydrogels. Adding PEG‐diald beyond the optimum for crosslinking prolonged the in vitro enzymatic degradation time of the hydrogels. The swelling of the crosslinked GAG hydrogels was correlated with the amount of PEG‐diald used rather than with the crosslinking density. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4344–4356, 2004     

Permeability of N2, Ar,He, O2, and CO2 through as‐extruded amorphous and biaxially oriented polyester films: Dependence on chain mobility

For as‐extruded amorphous and biaxially orientated polyester films based on poly(ethylene terephthalate), poly(ethylene naphthalate), and copolymers containing poly(ethylene terephthalate) and poly(ethylene naphthalate) moieties, permeability, diffusion, and solubility coefficients are interpreted in terms of chain mobility. The influence of polymer morphology is determined by comparison of the data for as‐extruded amorphous sheets and materials produced with different biaxial draw ratios. The crystallinities of the samples were assessed using differential scanning calorimetry and density measurements. Changes in mobility at a molecular level were investigated using dielectric spectroscopy and dynamic mechanical thermal analysis. The study, in conjunction with our earlier work, leads to the conclusion that the key to understanding differences in gas transport is the difference in local chain motions rather than in free volume. This was illustrated by the permeability results for He, Ar, N₂, and O₂ in the range of polyesters. However, the permeability of CO₂ was found to require alternative explanations because of polymer–penetrant interactions. For biaxially oriented samples, the differences in diffusivity are not only due to differences in local chain motions, but also additional constraints resulting from the increased crystallinity and chain rigidity—which also act to hinder segmental mobility. The effectiveness of the reduction in permeability in the biaxially oriented films is consequently determined by the ability of the polymer chains to effectively align and form crystalline structures. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2916–2929, 2004     

Influence of solvents on the formation of ultrathin uniform poly(vinyl pyrrolidone) nanofibers with electrospinning

Although there have been many reports on the preparation and applications of various polymer nanofibers with the electrospinning technique, the understanding of synthetic parameters in electrospinning remains limited. In this article, we investigate experimentally the influence of solvents on the morphology of the poly(vinyl pyrrolidone) (PVP) micro/nanofibers prepared by electrospinning PVP solution in different solvents, including ethanol, dichloromethane (MC) and N,N‐dimethylformamide (DMF). Using 4 wt % PVP solutions, the PVP fibers prepared from MC and DMF solvents had a shape like a bead‐on‐a‐string. In contrast, smooth PVP nanofibers were obtained with ethanol as a solvent although the size distribution of the fibers was somewhat broadened. In an effort to prepare PVP nanofibers with small diameters and narrow size distributions, we developed a strategy of using mixed solvents. The experimental results showed that when the ratio of DMF to ethanol was 50:50 (w/w), regular cylindrical PVP nanofibers with a diameter of 20 nm were successfully prepared. The formation of these thinnest nanofibers could be attributed to the combined effects of ethanol and DMF solvents that optimize the solution viscosity and charge density of the polymer jet. In addition, an interesting helical‐shaped fiber was obtained from 20 wt % PVP solution in a 50:50 (w/w) mixed ethanol/DMF solvent. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3721–3726, 2004     

Viscosity,particle size distribution,and structural investigation of tetramethyloxysilane/2‐hydroxyethyl methacrylate sols during the sol–gel process with acid and base catalysts

The tetramethoxysilane (TMOS)/2‐hydroxylethyl methacrylate (HEMA) hybrid gels were synthesized with acid and base catalysts, via the in situ polymerization of HEMA, with and without the cosolvent methanol. With methanol in the TMOS/HEMA sol, the enhanced esterification and depolymerization reactions of the silanols resulted in a slower growth of silica particles. The silica particles that were synthesized with an acid catalyst were less than 40 nm. The thermal resistance of the poly(2‐hydroxyethyl methacrylate) (PHEMA) chains was enhanced by the addition of colloidal silica. The Fourier transform infrared characterizations and the exothermal peaks on the differential scanning calorimetry traces of these hybrid gels indicated chemical hybridization occurring as a result of condensation of the colloid silica and PHEMA at higher temperatures. Hence, the residual weight content of the hybrid gel after its synthesis with the base catalyst was even higher than the content of TMOS in the hybrid sol. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3476–3486, 2004     

Time-resolved chemiluminescence technique for the microdetermination of proteins based on their complexation with copper(II).

Based on the complexation between proteins and Cu(II) coupled with the time-resolved chemiluminescence (CL) technique, a highly sensitive and quantitative assay for measuring proteins in solution is described. The complexes of proteins with Cu(II) have a strongly catalytic effect on the luminol-H2O2 CL reaction. Because the CL emission produced by the complexes is much more long-lived than that by Cu(II), the CL signals originating from proteins can be easily identified and measured with a time-resolved technique. On this basis, bovine albumin fraction V (BAF V) can be quantitatively determined in the range of 0.01 - 5.0 microg/ml with a detection limit of 5.8 ng/ml. The results show that the proposed assay exhibits a small variation in the response values for the same amount of different proteins, as compared to the Lowry as well as Bradford assays. The CL assay has also been studied for the detection of immobilized proteins.     

Determination of polymeric aluminum in soil extracted with a modified anion-exchange resin as a solid-phase adsorbent by ICP-AES.

In the present work, a new method was established by applying solid-phase extraction (SPE) to preconcentrate and separate polymeric aluminum (Al) and using ICP-AES to determine the polymeric Al, the total monomeric Al, and the total Al in soil extracts, respectively. A modified resin was prepared with impregnated 8-hydroxyquinoline-5-sulfoxinate (HQS) on the anion-exchange resin. It has good recognition ability for Al fractions, compared to the commonly used cation ion-exchange resin, which has a better ability to adsorb cations and a weak ability to recognize detailed Al species. The optimum conditions for Al fractionation sorption, elution and separation and the interference of foreign ions were studied with the prepared resin by continuous column and batch procedures. Monomeric Al was bound to Pyrocathecol Violet (PCV) at pH 6.2, whereas the polymeric Al species did not react with PCV for at least 15 min. Because a stable complex of Al-PCV was not absorbed on the HQS modified resin, the polymeric Al could be preconcentrated on-line by the HQS-modified resin. The adsorbed polymeric Al was eluted with 3 mL of 3 mol L(-1) of HCl, and then detected by ICP-AES. The method has been applied to directly determine polymeric Al in soil extracts with high selectivity as well as a high preconcentration factor. It gives a limit of detection of 0.6 ng mL(-1) with a relative standard deviation of less than 5.7% (n = 5, 0.24 microg mL(-1) Al).