RADIATION STABILITY OF PTFE WITH DIFFERENT CRYSTALLINITY

In this work, the effects of radiation on polytetrafluoroethylene (PTFE) samples with different crystallinity were studied. Using Suwa's equation for calculating the number-average molecular weight of PTFE, the radiation-induced reduction in molecular weight was followed and the G values for scission of PTFE were also obtained on the basis of the changes in molecular weight. The G(scission) for as-polymerized PTFE was 2.15 +/- 0.01, whereas for sintered sample, which has a relative low crystallinity, G(scission) = 6.0 +/- 0.14.

MISCIBILITY AND PHASE-BEHAVIOR IN BLENDS OF POLY(HYDROXYETHER OF BISPHENOL-A) WITH POLY(ETHYLENE OXIDE-CO-PROPYLENE OXIDE)

The miscibility of poly(hydroxyether of bisphenol A) (phenoxy) with a series of poly(ethylene oxide-co-propylene oxide) (EPO) has been studied. It was found that the critical copolymer composition for achieving miscibility with phenoxy around 60-degrees-C is about 22 mol % ethylene oxide (EO). Some blends undergo phase separation at elevated temperatures, but there is no maximum in the miscibility window. The mean-field approach has been used to describe this homopolymer/copolymer system. From the miscibility maps and the melting-point depression of the crystallizable component in the blends, the binary interaction energy densities, B(ij), have been calculated for all three pairs. The miscibility of phenoxy with EPO is considered to be caused mainly by the intermolecular hydrogen-bonding interactions between the hydroxyl groups of phenoxy and the ether oxygens of the EO units in the copolymers, while the intramolecular repulsion between EO and propylene oxide units in the copolymers contributes relatively little to the miscibility.

GAS PERMEABILITIES OF POLY(TRIMETHYLSILYLPROPYNE) MEMBRANES SURFACE MODIFIED WITH CF4 PLASMA

Surface fluorination of poly (trimethylsilylpropyne) (PTMSP) membranes by CF4 plasma was studied. The surface fluorination of the membranes was carried out in an atmosphere of CF4 in a capacitively coupled discharge apparatus with external electrodes. Dramatic increase in selectivity (P(O2)/P(N2)) was observed. The effect of fluorination conditions such as duration of treatment and discharge power on the permeabilities of the membranes was studied. X-ray photoelectron spectrometric data of modified PTMSP membranes showed a drastic alternation in the surface layer. The P(O2) and P(O2)/P(N2) of the membranes were observed to be dependent on the F/C atomic ratio. At F/C > 1, the P(O2/P(N2) value of the membranes could be more than four.

CRYSTALLIZATION OF RARE-EARTH OXIDE-FILLED POLYPROPYLENE

A study has been made of the crystallization behavior of polypropylene (PP) filled with rare earth oxides under isothermal conditions. These rare earth oxides include lanthanum oxide (La2O3), yttrium oxide (Y2O3), and a mixture of rare earth oxides containing 70% Y2O3 (Y2O3-0.70). A differential scanning calorimeter was used to monitor the energetics of the crystallization process from the melt. During isothermal crystallization, dependence of the relative degree of crystallinity on time was described by the Avrami equation. It has been shown that the addition of any of the three rare earth oxides causes a considerable increase in the overall crystallization rate of PP but does not influence the mechanism of nucleation and growth of the PP crystals. The analysis of kinetic data according to nucleation theories shows that the increase in crystallization rate of PP in the composites is due to the decrease in surface energy of the extremity surfaces. The relative contents of the beta-form in the composites are somewhat higher than that in the plain PP. However, the contents of the beta-form in the plain PP and the composites are all very low relative to those of the alpha-form and the influence of the formation of the beta-form on the crystallization kinetics can be neglected.

THE EFFECT OF RADIATION-INDUCED CROSS-LINKING ON THE RELAXATION OF TAUT TIE MOLECULES DURING ANNEALING OF DRAWN LDPE

Shrinkage, retractive stress, and infrared dichroism of the drawn low-density polyethylene (LDPE) as-drawn and irradiated by Co-60-ray have been measured under different annealing conditions. The shrinkage and the disorientation of the irradiated sample was undergone more rapidly than that of unirradiated one as the temperature was continuously increased, surpassing a certain value, and a higher degree of shrinkage and disorientation was achieved finally for the irradiated sample when the samples were annealed with free ends. For the samples heated isothermally with fixed ends, the retractive stress went through a maximum and then attenuated to a limited value, and the degree of such a stress attenuation for the unirradiated sample was much more than that for the irradiated sample. These results show that the taut tie molecules (TTMs) in drawn PE can relax by the pulling of chain segments out of crystal blocks that they anchored in at elevated temperatures higher than the a transition and also by the displacing of microfibrils if the samples were annealed with free ends. The cross-links produced by irradiation prohibit the former process. It was further observed that the dependence of the average extinction coefficient of the band at 2016 cm-1 on that of the band at 1894 cm-1 is related to irradiation and annealing conditions, which has also been explained by the relaxation of TTMs and the function of irradiation-induced cross-linking on the relaxation.

XPS STUDIES ON RADIATION-INDUCED STRUCTURAL-CHANGES IN THE COPOLYMER OF TETRAFLUOROETHYLENE AND ETHYLENE

In this work, the radiation-induced structural changes in the copolymer of tetrafluoroethylene and ethylene (F-40) were studied by X-ray photoelectron spectroscopy (XPS). During irradiation, some CF2 groups in the polymer were found to have been converted into carbon structures that bonded indirectly with fluorine atoms.

BLENDS OF POLY[3,3-BIS(CHLOROMETHYL)OXETANE] WITH POLY(VINYL ACETATE) .1. THERMAL AND MECHANICAL-PROPERTIES

Blends of poly[3,3-bis(chloromethyl)oxetane] (Penton) with poly(vinyl acetate) were prepared. Compatibility, morphology, thermal behavior, and mechanical properties of blends with various compositions were studied using differential scanning calorimetry (DSC), dynamic mechanical measurements (DMA), tensile tests, and scanning electron microscopy (SEM). DMA study showed that the blends have two glass transition temperatures (T(g)). The T(g) of the PVAc rich phase shifts significantly to lower temperatures with increasing Penton content, suggesting that a considerable amount of Penton dissolves in the PVAc rich phase, but that the Penton rich phase contains little PVAc. The Penton/PVAc blends are partially compatible. DSC results suggest that PVAc can act as a beta-nucleator for Penton in the blend. Marked negative deviations from simple additivity were observed for the tensile strength at break over the entire composition range. The Young's modulus curve appeared to be S-shaped, implying that the blends are heterogeneous and have a two-phase structure. This was confirmed by SEM observations.

PLASMA POLYMERIZATION OF OCTAFLUOROCYCLOBUTANE AND HYDROPHOBIC MICROPOROUS COMPOSITE MEMBRANES FOR MEMBRANE DISTILLATION

In this paper, hydrophilic microporous cellulose nitrate membranes have been surface-modified by plasma polymerization of octafluorocyclobutane (OFCB). The microporous composite membranes with a hydrophilic layer sandwiched between two hydrophobic layers have been obtained. The obtained composite membranes have been used in a membrane distillation (MD) process and have exhibited good performance. The effects of polymerization conditions, such as glow-discharge power and deposition time, on the structures and MD performances of the obtained composite membranes have been investigated by SEM, X-ray microscopical analysis, and XPS. The polymerization conditions should be as mild as possible in order to prepare the hydrophobic composite membrane with good MD performance. The typical MD behaviors of the obtained hydrophobic composite membranes are in agreement with that of hydrophobic membranes directly prepared from hydrophobic polymeric materials, like PVDF, PTFE, or PP.

RELATIONSHIP BETWEEN CRYSTALLIZATION OF THE PDMS BLOCK AND MORPHOLOGY OF POLY(BUTADIENE-B-DIMETHYLSILOXANE)

Studies using transmission electron microscopy, differential scanning calorimetry, and X-ray diffraction showed correlations between the crystallization behavior of the polydimethylsiloxane (PDMS) block and the morphology of the block copolymer poly (butadiene-b-dimethylsiloxane) (PB-PDMS). When the PDMS component existed as spheres dispersed in a PB matrix, the crystallization rate of the PDMS block was lower than when the PDMS phase existed in rod or cylinder form.

XPS STUDY OF RADIATION CROSS-LINKED COPOLYMER OF TETRAFLUOROETHYLENE WITH HEXAFLUOROPROPYLENE

In this work the radiation-induced structural changes in F-46 were studied by XPS. In carbon-1s spectra of a highly crosslinked F-46 sheet, the slight increase observed in relative area under the peak due to CF3 was explained by the radiation-induced scission of polymer chains. The peak at 287.6 eV appearing in the spectra caused by ionizing radiation was attributed to carbon structures without primary fluorine substituents, in both branching and unsaturated structures, while that at 289.3 eV was assigned to = CF groups in mid-chain double bonds.

STRUCTURE AND PROPERTIES OF SEQUENTIALLY POLYMERIZED PROPYLENE-B-[ETHYLENE-CO-PROPYLENE]-B-PROPYLENE COPOLYMERS

The structure and properties of presumed block copolymers of polypropylene (PP) with ethylene-propylene random copolymers (EPR), i.e., PP-EPR and PP-EPR-PP, have been investigated by viscometry, transmission electron microscopy, dynamic mechanical analysis, differential scanning calorimetry, gel permeation chromatography, wide-angle x-ray diffraction, and other techniques testing various mechanical properties. PP-EPR and PP-EPR-PP were synthesized using delta-TiCl3-Et2AlCl as a catalyst system. The results indicate that the intrinsic viscosity of these polymers increases with each block-building step, whereas the intrinsic viscosity of those prepared by chain transfer reaction (strong chain-transfer reagent hydrogen was introduced between block-building steps during polymerization) hardly changes with the reaction time. Compared with PP / EPR blends, PP-EPR-PP block copolymers have lower PP and polyethylene crystallinity, and lower melting and crystallization temperatures of crystalline EPR. Two relaxation peaks of PP and EPR appear in the dynamic spectra of blends. They merge into a very broad relaxation peak with block sequence products of the same composition, indicating good compatibility between PP and EPR in the presence of block copolymers. Varying the PP and EPR content affects the crystallinity, density, and morphological structure of the products, which in turn affects the tensile strength and elongation at break. Because of their superior mechanical properties, sequential polymerization products containing PP-EPR and PP-EPR-PP block copolymers may have potential as compatibilizing agents for isotactic polypropylene and polyethylene blends or as potential heat-resistant thermoplastic elastomers.