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).     

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     

Structure of a poly(2,5‐benzimidazole)/phosphoric acid complex

As‐cast films of poly(2,5‐benzimidazole) exhibit uniplanar orientation in which the planes of the aromatic rings lie parallel to the film surface. Upon doping with phosphoric acid, the original crystalline order is lost, but the doped film can be stretched to produce films with uniaxial orientation. After thermal annealing at 540 °C, nine Bragg reflections are resolved in the fiber diagram, and these are indexed by an orthorhombic unit cell with the dimensions a = 18.1 Å, b = 3.5 Å, and c = 11.4 Å, containing four monomer units of two chains. The absence of odd‐order 00l reflections points to a 2₁ chain conformation, which is probably planar so that the aromatic units can be stacked along the b axis. The water and phosphoric acid contents of the crystalline structure cannot be determined exactly because of the presence of extensive amorphous regions that probably have different solvation. The best agreement between the observed and calculated intensities is for an idealized structure containing two phosphoric acids and two water molecules per unit cell. However, the phosphoric acid is probably present mainly in the form of pyrophosphoric acid and its higher oligomers. In addition, the X‐ray data are consistent with a more disordered structure containing chains with random (up and down) polarity and a lack of c‐axis registry. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2576–2585, 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     

Pressure and temperature dependence of the gas‐transport properties of dense poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] membranes

The gas‐transport properties of poly[2,6‐toluene‐2,2‐bis(3,4‐dicarboxylphenyl)hexafluoropropane diimide] (6FDA‐2,6‐DAT) have been investigated. The sorption behavior of dense 6FDA‐2,6‐DAT membranes is well described by the dual‐mode sorption model and has certain relationships with the critical temperatures of the penetrants. The solubility coefficient decreases with an increase in either the pressure or temperature. The temperature dependence of the diffusivity coefficient increases with an increase in the penetrant size, as the order of the activation energy for the diffusion jump is CH₄ > N₂ > O₂ > CO₂. Also, the average diffusion coefficient increases with increasing pressure for all the gases tested. As a combined contribution from sorption and diffusion, permeability decreases with increases in the pressure and the kinetic diameter of the penetrant molecules. Even up to 32.7 atm, no plasticization phenomenon can be observed on flat dense 6FDA‐2,6‐DAT membranes from their permeability–pressure curves. However, just as for other gases, the absolute value of the heat of sorption of CO₂ decreases with increasing pressure at a low‐pressure range, but the trend changes when the feed pressure is greater than 10 atm. This implies that CO₂‐induced plasticization may occur and reduce the positive enthalpy required to create a site into which a penetrant can be sorbed. Therefore, a better diagnosis of the inherent threshold pressure for the plasticization of a glassy polymer membrane may involve examining the absolute value of the heat of sorption as a function of pressure and identifying the turning point at which the gradient of the absolute value of the heat of sorption against pressure turns from a negative value to a positive one. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 354–364, 2004     

Structure and properties of the mesophase of syndiotactic polystyrene—III. Selective sorption of the mesophase of syndiotactic polystyrene

Syndiotactic polystyrene (sPS) has various crystalline forms such as α, β, γ, and δ forms, and a mesophase depending on the preparation method. In this study, we focused on the mesophase with the molecular cavity of sPS, which is obtained by step‐wise extraction of the guest molecules from the sPS δ form. To prepare the mesophase containing different shapes and sizes of the cavity, two kinds of the sPS δ form membrane cast from either toluene or chloroform solution were first prepared and then the guest molecules were removed by a step‐wise extraction method using acetone and methanol. We could succeed in the preparation of two kinds of mesophase with different shapes and sizes of the molecular cavity. Either toluene or chloroform vapor sorption to the sPS mesophase membranes was examined at 25 °C. Sorption analysis indicates that the mesophase with large molecular cavities can mainly sorb large molecules; on the other hand, the mesophase with small cavities can sorb only the small molecules, and is unable to sorb a large amount of large molecule because the cavity was too small to sorb the large molecules. Therefore, the sPS mesophase membrane has sorption selectivity based on the size of the molecular cavity. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 238–245, 2004     

Multiphysical modeling and meshless simulation of electric‐sensitive hydrogels

According to a multiphase mixture theory, we have mathematically developed a multiphysical model with chemoelectromechanical coupling considerations, termed the multieffect‐coupling electric‐stimulus (MECe) model, to simulate the responsive behavior of electric‐sensitive hydrogels immersed in a bath solution under an externally applied electric field. For solutions of the MECe model consisting of coupled nonlinear partial differential governing equations, a meshless Hermite–Cloud method with a hierarchical iteration technique has been used for a one‐dimensional steady‐state analysis of a hydrogel strip. The computed results are compared with the experimental data, and there is very good agreement. Simulations within the domains of both hydrogels and surrounding solutions also present distributions of the ionic concentrations and electric potential as well as the hydrogel displacement. The effects of various physical parameters on the response behavior of electric‐stimulus responsive hydrogels are discussed in detail. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1514–1531, 2004     

Ultrahigh‐molecular‐weight‐polyethylene‐fiber surface treatment by electron‐beam‐irradiation‐induced graft polymerization and its effect on adhesion in a styrene–butadiene rubber matrix

Aiming to develop a high‐performance fiber‐reinforced rubber from styrene–butadiene rubber (SBR), we applied a special technique using electron‐beam (EB)‐irradiation‐induced graft polymerization to ultrahigh‐molecular‐weight‐polyethylene (UHMWPE) fibers. The molecular interaction between the grafted UHMWPE fibers and an SBR matrix was studied through the evaluation of the adhesive behavior of the fibers in the SBR matrix. Although UHMWPE was chemically inert, two monomers, styrene and N‐vinyl formamide (NVF), were examined for graft polymerization onto the UHMWPE fiber surface. Styrene was not effective, but NVF was graft‐polymerized onto the UHMWPE fibers with this special method. A methanol/water mixture and dioxane were used as solvents for NVF, and the effects of the solvents on the grafting percentage of NVF were also examined. The methanol/water mixture was more effective. A grafting percentage of 16.4% was the highest obtained. This improved the adhesive force threefold with respect to that of untreated UHMWPE fibers. These results demonstrated that EB irradiation enabled graft polymerization to occur even on the inert surface of UHMWPE fibers. However, the mechanical properties of the fibers could be compromised according to the dose of EB irradiation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2595–2603, 2004