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     

Determination of the degree of cure under dynamic and isothermal curing conditions with electrical impedance spectroscopy

This article presents a new methodology for the quantitative determination of the progress of the curing reaction of a thermosetting resin, using the results of electrical impedance spectroscopy. The method is an extension of the use of the imaginary impedance maximum as a reaction progress indicator and is based on the demonstration of a close correlation between the reaction rate, as measured by conventional differential scanning calorimetry, and the rate of change of the value of the imaginary impedance spectrum maximum. Tests on a commercial aerospace epoxy resin under both isothermal and dynamic heating conditions with calorimetry and impedance spectroscopy have demonstrated the validity of the method and set the accuracy limits involved. This technique can be used as a real-time online control tool for thermoset composite manufacturing. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 146–154, 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     

Brominated poly(isobutylene‐co‐para‐methylstyrene) (BIMS)‐clay nanocomposites: Synthesis and characterization

In this work, preparation and properties of different nanoclays modified by organic amines (octadecyl amine, a primary amine, and hexadecyltrimethylammonium bromide, a tertiary amine) and brominated polyisobutylene‐co‐paramethylstyrene (BIMS)‐clay nanocomposites are reported. The clays and the rubber nanocomposites have been characterized with the help of Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and X‐ray diffraction (XRD). The X‐ray diffraction peaks observed in the range of 3 °–10 ° for the modified clays disappear in the rubber nanocomposites. TEM photographs show predominantly exfoliation of the clays in the range of 12 ± 4 nm in the BIMS. In the FTIR spectra of the nanocomposites, there are common peaks of virgin rubber as well as those of the clays. Excellent improvement in mechanical properties like tensile strength, elongation at break, and modulus is observed on incorporation of the nanoclays in the BIMS. Structure‐property correlation in the above nanocomposites is attempted. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4489–4502, 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     

Bio‐based nanocomposites from functionalized plant oils and layered silicate

Some discovery work was done on the synthesis of clay nanocomposites based on renewable plant oils. Functionalized triglycerides, such as acrylated epoxidized soybean oil, maleinized acrylated epoxidized soybean oil, and soybean oil pentaerythritol maleates, combined with styrene were used as the polymer matrix. The miscibility of these monomers and clay organomodifier was assessed by solubility parameters. The formation of nanocomposites was confirmed by both X‐ray data and transmission electron microscopy. The morphology showed a mix of intercalated and partially exfoliated sheets. The flexural modulus increased 30% at only 4 vol % clay content, but there was no significant effect on flexural strength, glass‐transition temperature, and thermal stability. Property enhancement was related to the degree of exfoliation that depends on both the polarity and flexibility of the monomers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1441–1450, 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     

Extractive spectrophotometric determination of Cobalt(II) in synthetic and pharmaceutical samples using Cyanex 923.

Cyanex 923 has been proposed as a sensitive analytical reagent for the direct extractive spectrophotometric determination of cobalt(II). Cobalt(II) forms a blue-colored complex with Cyanex 923 in the organic phase. The maximum absorbance of the complex is measured at 635 nm. Beer's law was obeyed in the range 58.9 - 589.0 microg of cobalt. The molar absorptivitiy and Sandell's sensitivity of the complex was calculated to be 6.79 x 10920 l mol(-1) cm(-1) and 0.088 microg cm(-2), respectively. The nature of the extracted species was found to be Co(SCN)2 x 2S. An excellent linearity with a correlation coefficient value of 0.999 was obtained for the Co(II)-Cyanex 923 complex. Stability and regeneration of the reagent (Cyanex 923) for reuse is the main advantage of the present method. The method was successfully applied to the determination of cobalt in synthetic mixtures and pharmaceutical samples was found to give values close to the actual ones. Standard alloy samples, such as high-speed tool BCS 484 and 485, have been tested for the determination of cobalt for the purpose of validating the present method. The results of the proposed method are comparable with atomic absorption spectrometry and were found to be in good agreement.