Amine‐cured epoxy/clay nanocomposites. II. The effect of the nanoclay aspect ratio

The thermophysical and mechanical properties of a nanocomposite material composed of amine‐cured diglycidyl ether of bisphenol A (DGEBA) reinforced with organomontmorillonite clay are reported. The storage modulus at 100 °C, which was above the glass‐transition temperature (T_g), increased approximately 350% with the addition of 10 wt % (6.0 vol %) of clay. Below the T_g, the storage modulus at 30 °C increased 50% relative to the value of unfilled epoxy. It was determined that the T_g linearly increased as a function of clay volume percent. The tensile modulus of epoxy at room temperature increased approximately 50% with the addition of 10 wt % of clay. The reinforcing effect of the organoclay nanoplatelets is discussed with respect to the Tandon–Weng and Halpin–Tsai models. A pseudoinclusion model is proposed to describe the behavior of randomly oriented, uniformly dispersed platelets in nanocomposite materials. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4391–4400, 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     

Distributions of major-to-ultratrace elements among the particulate and dissolved fractions in natural water as studied by ICP-AES and ICP-MS after sequential fractionation.

In order to elucidate the distributions of the elements among the particulate and dissolved fractions in pond water, major-to-ultratrace elements in different sizes of particles as well as in the filtrate passed through the 0.05 microm filter were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). The different sizes of particle samples (ca. 100-300 microg each) were collected on the membrane filters with pore sizes of 10, 3.0, 1.2, 0.4, 0.2 and 0.05 microm, respectively, by sequential fractionation. As a result, about 40 elements in different sizes of particles could be determined by ICP-AES and ICP-MS, after acid digestion using HNO3/HF/HClO4. Then, the fractional distribution factors of major-to-ultratrace elements among the particulate and dissolved fractions were estimated from the analytical results. The total contents of Al, Fe, Ti, REEs (rare earth elements), Bi, Pb and Ag in the particulate fractions (larger than 0.05 microm) were more than 80-90%, while those of Ca, Sr, Cs, W, Ba, Mn and Co in the dissolved fraction, which corresponded to the filtrate passed through the 0.05 microm membrane filter, were more than 80%. It was further found that the fractional distributions of Cu and Zn in the dissolved fraction were ca. 50%. In addition, the enrichment factors (EFs) of the elements in the particulate fractions with particle sizes of 3.0-10 microm and 0.05-0.2 microm were estimated to elucidate their geochemical characteristics in natural water.     

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.     

Plasticized microporous poly(vinylidene fluoride) separators for lithium‐ion batteries. II. Poly(vinylidene fluoride) dense membrane swelling behavior in a liquid electrolyte—characterization of the swelling kinetics

Some microporous poly(vinylidene fluoride) (PVdF) separators for lithium‐ion batteries, used in liquid organic electrolytes based on a mixture of carbonate solvents and lithium salt LiPF₆, were characterized by the study of the swelling phenomena on dense PVdF membranes. Various aspects of the kinetics of the carbonate solvents and the solvent mixture sorption in dense PVdF slabs were studied at different temperatures. Non‐Fickian behavior, characterized by S‐shaped sorption curves, was highlighted, and a salt effect, which resulted in two‐stage sorption, was studied. Diffusion coefficients and activation energies were calculated for the Fickian portions of the sorption curves, that is, at short times and low swelling ratios. A strong influence of the different interaction parameters was shown for the swelling kinetics. This study proved that the swelling of microporous PVdF membranes could be considered instantaneous. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 544–552, 2004     

Electrospinning of ultrafine cellulose acetate fibers: Studies of a new solvent system and deacetylation of ultrafine cellulose acetate fibers

Electrospinning of cellulose acetate (CA) in a new solvent system and the deacetylation of the resulting ultrafine CA fibers were investigated. Ultrafine CA fibers (∼2.3 μm) were successfully prepared via electrospinning of CA in a mixed solvent of acetone/water at water contents of 10–15 wt %, and more ultrafine CA fibers (0.46 μm) were produced under basic pH conditions. Ultrafine cellulose fibers were regenerated from the homogeneous deacetylation of ultrafine CA fibers in KOH/ethanol. It was very rapid and completed within 20 min. The crystal structure, thermal properties, and morphology of ultrafine CA fibers were changed according to the degree of deacetylation, finally to those of pure cellulose, but the nonwoven fibrous mat structure was maintained. The activation energy for the deacetylation of ultrafine CA fibers was 10.3 kcal/mol. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 5–11, 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     

Plasticized microporous poly(vinylidene fluoride) separators for lithium-ion batteries. III. Gel properties and irreversible modifications of poly(vinylidene fluoride) membranes under swelling in liquid electrolytes

Microporous poly(vinylidene fluoride) (PVdF) separators for lithium-ion batteries, used in liquid organic electrolytes, have been characterized with respect to the swelling phenomena on dense PVdF membranes (obtained through hot pressing). In the first and second parts of this study, we have described the swelling equilibria and swelling kinetics of dense PVdF. Here the thermal properties of PVdF gels and their irreversible modifications induced by swelling are characterized. Particular attention is paid to crystallinity modifications, polymer plasticization, and membrane degradation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2308–2317, 2004     

Effects of poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] on the charge distributions of low‐density polyethylene/polystyrene blends

The effect of the triblock copolymer poly[styrene‐b‐(ethylene‐co‐butylene)‐b‐styrene] (SEBS) on the formation of the space charge of immiscible low‐density polyethylene (LDPE)/polystyrene (PS) blends was investigated. Blends of 70/30 (wt %) LDPE/PS were prepared through melt blending in an internal mixer at a blend temperature of 220 °C. The amount of charge that accumulated in the 70% LDPE/30% PS blends decreased when the SEBS content increased up to 10 wt %. For compatibilized and uncompatibilized blends, no significant change in the degree of crystallinity of LDPE in the blends was observed, and so the effect of crystallization on the space charge distribution could be excluded. Morphological observations showed that the addition of SEBS resulted in a domain size reduction of the dispersed PS phase and better interfacial adhesion between the LDPE and PS phases. The location of SEBS at a domain interface enabled charges to migrate from one phase to the other via the domain interface and, therefore, resulted in a significant decrease in the amount of space charge for the LDPE/PS blends with SEBS. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2813–2820, 2004