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     

Studies of photooxidative degradation of poly(vinyl chloride)/poly(ethylene oxide) blends

The photooxidative degradation of blends (in a full range of compositions) of amorphous poly(vinyl chloride) (PVC) with semicrystalline poly(ethylene oxide) (PEO) in the form of thin films is investigated using absorption spectroscopy (UV–visible and Fourier transform infrared) and atomic force microscopy (AFM). The amount of insoluble gel formed as a result of photocrosslinking is estimated gravimetrically. It is found that the PVC/PEO blendsí susceptibility to photooxidative degradation differs from that pure of the components and depends on the blend composition and morphology. Photoreactions such as degradation and oxidation are accelerated whereas dehydrochlorination is retarded in blends. The photocrosslinking efficiency in PVC/PEO blends is higher than in PVC; moreover, PEO is also involved in this process. AFM images showing the lamellar structure of semicrystalline PEO in the blend lead to the conclusion that the presence of PVC does not disturb the crystallization process of PEO. The changes induced by UV irradiation allow the observation of more of the distinct PEO crystallites. This is probably caused by recrystallization of short, more mobile chains in degraded PEO or by partial removal of the less stable amorphous phase from the film surface. These results confirm previous information on the miscibility of PVC with PEO. The mechanism of the interactions between the components and the blend photodegradation are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 585–602, 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     

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     

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     

Structure and properties of the mesophase of syndiotactic polystyrene. VIII. Solvent sorption behavior of syndiotactic polystyrene/p‐chlorotoluene mesophase membranes

A crystalline δ form of a syndiotactic polystyrene (sPS) membrane was prepared from a solution of sPS (1 wt %) and p‐chlorotoluene (p‐CT) by a solution‐casting method. The mesophase (δ empty form) of sPS was obtained by the extraction of the guest solvent from the δ form of sPS by a stepwise solvent‐extraction method. The sPS/p‐CT mesophase membrane [p‐CT (A‐M)] was used for the sorption of 1 mol % p‐CT for different times and for the sorption of different concentrations of p‐CT, chlorobenzene (CB), p‐xylene (p‐X), toluene, and chloroform for 48 h. The presence of solvents in the sPS membrane was confirmed by IR analysis. A thermal study revealed that the sorption amount of 1 mol % p‐CT increased with increasing immersion time, and the sorption amounts of different solvents increased with increasing solvent concentration. Differential scanning calorimetry results showed that the desorption peak temperature increased as the amount of the solvent increased in the clathrated sPS membrane. Wide‐angle X‐ray diffraction results showed that 2θ at 8.25° was slightly shifted toward 8°, and there was no change in the peak position at 10° for p‐CT (A‐M), which was immersed in different solvents (1 mol %); however, the intensity of 2θ at 10° was not similar for all the samples. Among the solvents used for the sorption studies at 1 mol %, p‐CT (A‐M) could sorb more p‐CT and CB than p‐X, toluene, and chloroform. The solvent sorption isotherm was the Langmuir sorption mechanism. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3439–3446, 2004     

Electrochemical reduction of 1-([(4-halophenyl)imino]methyl)-2-naphthols in aprotic media.

The electrochemical reduction of 1-([(4-halophenyl)imino]methyl)-2-naphthols on graphite electrodes was studied using cyclic voltammetry, chronoamperometry, constant-potential coulometry and preparative constant-potential electrolysis techniques. The data revealed that the reduction on graphite was irreversible and followed an EC mechanism. The diffusion coefficients and the number of electrons transferred were determined using the chronoamperometric Cottrell slope and the ultramicro disc Pt-electrode steady-state current. The number of electrons was also determined by bulk electrolysis. The compounds were subjected to constant-potential preparative electrolysis and the electrolysis products were purified and identified by spectroscopic methods. Based on these findings, a mechanism for the electro-reduction process is proposed.     

Influence of surfactant and lipid chain length on the solubilisation of phosphatidylcholine vesicles by micelles comprised of polyoxyethylene sorbitan monoesters

Photon correlation spectroscopy and freeze-fracture electron microscopy have been used to determine the ability of a range of micelle-forming, polyoxyethylene (20) sorbitan monoesters (Tweens) to solubilise vesicles prepared from phosphatidylcholines of different acyl chain lengths and degrees of saturation with a view to rationalising (in terms of their membrane toxicity) which of the micelle-forming surfactants to use as drug delivery vehicles. The phosphatidylcholines used were dimyristoyl-, dipalmitoyl-, distearoyl- and dioleoylphosphatidylcholine (DMPC, DPPC, DSPC and DOPC, respectively) while the nonionic polyoxyethylene sorbitan monoesters studied were polyoxyethylene (20) sorbitan monolaurate (Tween 20), a 9:1 weight ratio mixture of polyoxyethylene (20) sorbitan monopalmitate and monostearate (Tween 40), a 1:1 weight ratio mixture of polyoxyethylene (20) sorbitan monopalmitate and monostearate (Tween 60), and polyoxyethylene (20) sorbitan monooleate (Tween 80). The ability of the Tween micelles to solubilise phospholipid vesicles was found to depend both upon the length of the surfactant acyl chain and the length of the acyl chains of the phospholipid comprising the vesicle. Vesicles composed of long saturated diacyl chain phospholipids, namely DSPC and DPPC, were the most resistant to solubilisation, while those prepared from the shorter acyl chained DMPC were more readily solubilised. In terms of their solubilisation behaviour, vesicles made from phospholipids containing long, unsaturated acyl chains, namely DOPC behaved more akin to those vesicles prepared from DMPC. None of the Tween surfactants were effective at solubilising vesicles prepared from DPPC or DSPC. In contrast, there were clear differences in the ability of the various surfactants to solubilise vesicles prepared from DMPC and DOPC, in that micelles formed from Tween 20 were the most effective solubilising agent while those formed by Tween 60 were the least effective. As a consequence of these observations it was considered that Tween 60 was the surfactant least likely to cause membrane damage in vivo and, therefore, is the most suitable surfactant for use as a micellar drug delivery vehicle.     

Wide‐angle X‐ray diffraction and differential scanning calorimetry study of the crystallization of poly(ethylene naphthalate), poly(butylene naphthalate), and their copolymers

The crystallization behavior of a series of poly(ethylene‐co‐butylene naphthalate) (PEBN) random copolymers was studied. Wide‐angle X‐ray diffraction (WAXD) patterns showed that the crystallization of these copolymers could occur over the entire range of compositions. This resulted in the formation of poly(ethylene naphthalate) or poly(butylene naphthalate) crystals, depending on the composition of the copolymers. Sharp diffraction peaks were observed, except for 50/50 PEBN. Eutectic behavior was also observed. This showed isodimorphic cocrystallization of the PEBN copolymers. The variation of the enthalpy of fusion of the copolymers with the composition was estimated. The isothermal and nonisothermal crystallization kinetics were studied. The crystallization rates were found to decrease as the comonomer unit content increased. The tensile properties were also measured and were found to decrease as the butylene naphthalate content of the copolymers increased. For initially amorphous specimens, orientation was proved by WAXD patterns after drawing, but no crystalline reflections were observed. However, the fast crystallization of drawn specimens occurred when they were heated above the glass‐transition temperature. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 843–860, 2004     

Desorption behavior of a surfactant in a linear low‐density polyethylene blend at elevated temperatures

The desorption behavior of a surfactant in a linear low‐density polyethylene (LLDPE) blend at elevated temperatures of 50, 70, and 80 °C was studied with Fourier transform infrared spectroscopy. The composition of the LLDPE blend was 70:30 LLDPE/low‐density polyethylene. Three different specimens (II, III, and IV) were prepared with various compositions of a small molecular penetrant, sorbitan palmitate (SPAN‐40), and a migration controller, poly(ethylene acrylic acid) (EAA), in the LLDPE blend. The calculated diffusion coefficient (D) of SPAN‐40 in specimens II, III, and IV, between 50 and 80 °C, varied from 1.74 × 10^?11 to 6.79 × 10^?11 cm²/s, from 1.10 × 10^?11 to 5.75 × 10^?11 cm²/s, and from 0.58 × 10^?11 to 4.75 × 10^?11 cm²/s, respectively. In addition, the calculated activation energies (E_D) of specimens II, III, and IV, from the plotting of ln D versus 1/T between 50 and 80 °C, were 42.9, 52.7, and 65.6 kJ/mol, respectively. These values were different from those obtained between 25 and 50 °C and were believed to have been influenced by the interference of Tinuvin (a UV stabilizer) at elevated temperatures higher than 50 °C. Although the desorption rate of SPAN‐40 increased with the temperature and decreased with the EAA content, the observed spectral behavior did not depend on the temperature and time. For all specimens stored over 50 °C, the peak at 1739 cm^?1 decreased in a few days and subsequently increased with a peak shift toward 1730 cm^?1. This arose from the carbonyl stretching vibration of Tinuvin, possibly because of oxidation or degradation at elevated temperatures. In addition, the incorporation of EAA into the LLDPE blend suppressed the desorption rate of SPAN‐40 and retarded the appearance of the 1730 cm^?1 peak. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1114–1126, 2004