Radiation effects on the thermal degradation of poly(vinyl chloride) and poly(vinyl alcohol)

Radiation effects on the formation of conjugated double bonds in the thermal degradation of poly(vinyl chloride) (PVC) and poly(vinyl alcohol) (PVA) were investigated. Thin films of PVC and PVA were either irradiated with γ-rays at ambient temperature (pre-irradiation) and then subjected to thermal treatment, or irradiated at elevated temperatures (in situ irradiation). An extensive enhancement of the thermal degradation was observed for the pre-irradiation of the PVC films, which was more effective than the effect of the in situ irradiation at the same absorption dose. For the PVA degradation, however, the effect of the in situ irradiation was larger than that of the pre-irradiation. The results were explained and related mechanisms were discussed based on radiation-induced chemical reactions and their individual contributions to the thermal degradation behaviors of the two polymers. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 3089–3095, 1998     

Physical properties of ion beam treated electrospun poly(vinyl alcohol) nanofibers

We show that the mechanical properties of nano-sized electrospun poly(vinyl alcohol) fibers can be modified using broad-energy ion beam implantation. The elastic moduli were determined using atomic force microscopy multi-point mechanical bending tests on individual fibers before and after treatment. With a dose of 8.0 × 10¹⁵ ions/cm² of nitrogen ion we observed 30% increases in fiber elastic modulus with a simultaneous fiber diameter reduction. Two additional doses of nitrogen ion as well as a 8.0 × 10¹⁵ ions/cm² of helium ion treatment showed that this stiffness improvement effect was dependent on ion dosage and ion species. The surface morphological features of the fiber mat were shown to be unaltered due to the ion beam treatment. Key chemical modifications via nitrogen ion treatment were the introduction of the functional groups amine and amide. These groups are important in promoting cell compatibility on polymer surfaces.     

Effect of poly(ethylene oxide) on the structure and properties of poly(vinyl alcohol)

To improve the drawability of poly(vinyl alcohol) (PVA) thermal products, poly(ethylene oxide) (PEO), a special resin with good flexibility, excellent lubricity, and compatibility with many resins, was applied, and the Fourier transform infrared spectroscopy, dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and wide‐angle X‐ray diffraction (WXRD) were adopted to study the hydrogen bonds, water states, thermal properties, crystal structure, and nonisothermal crystallization of modified PVA. It was found that PEO formed strong hydrogen bonds with water and PVA, thus weakened the intra‐ and inter‐hydrogen bonds of PVA, changed the aggregation states of PVA chains, and decreased its melting point and crystallinity. Moreover, the interactions among PVA, water, and PEO retarded the water evaporation and made more water remain in the system to plasticize PVA. The existence of PEO also slowed down the melt crystallization process of PVA, however, increased the nucleation points of system, thus made more and smaller spherulites formed. The weakened crystallization capability of PVA and the lubrication of PEO made PVA chains to have more mobility under the outside force and obtain high mechanical properties. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1946–1954, 2010     

Influence of electron beam irradiation on physicochemical properties of poly(trimethylene carbonate)

Electron beam (EB) irradiation of poly(trimethylene carbonate) (PTMC), an amorphous, biodegradable polymer used in the field of biomaterials, results in predominant cross-linking and finally in the formation of gel fraction, thus enabling modification of physicochemical properties of this material without significant changes in its chemical structure. PTMC films (M_w: 167-553 kg mol⁻¹) were irradiated with different doses using an electron accelerator. Irradiation with a standard sterilization dose of 25 kGy caused neither significant changes in the chemical composition of the polymer nor significant deterioration of its mechanical properties. Changes in viscosity-, number-, weight-, and z-average molecular weights of PTMC for doses lower than the gelation dose (D_g) as well as gel-sol analysis and swelling tests for doses above D_g indicate domination of cross-linking over degradation. EB irradiation can be considered as an effective tool for increasing the average molecular weight of PTMC and sterilization of PTMC-based biomaterials.     

Mechanical properties of blends of PAMAM dendrimers with poly(vinyl chloride) and poly(vinyl acetate)

Hybrid blends of poly(amidoamine) PAMAM dendrimers with two linear high polymers, poly(vinyl chloride), PVC, and poly(vinyl acetate), PVAc, are reported. The interaction between the blend components was studied using dynamic mechanical analysis, xenon nuclear magnetic resonance (NMR) spectroscopy, and tensile property measurements. The data suggest a much higher degree of interaction between components of PVAc-containing blends compared to those containing PVC. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 2111–2117, 1998     

On the distribution of dye molecules in stretched poly(vinyl alcohol)

The symmetry of the orientational distribution function of dye molecules in stretched PVA films is studied using polarized fluorescence. The different symmetries are monitored by a simple experimental technique in which angle-resolved fluorescence depolarization ratios are measured. A uniaxial distribution of rhodamine 6G molecules is obtained on stretching the film at temperatures above 60°C. In contrast a biaxial distribution of trypaflavine molecules is found for stretch temperatures in the 50–115°C range. It is suggested that the hydrogen bonding between the PVA chains, and between the dye molecules and the PVA chains, influences the symmetry of the distribution upon stretching.     

Effect of ozone on poly(vinyl chloride) degradation

The influence of ozone on the kinetics and mechanisms of poly(vinyl chloride) degradation has been studied. The rate constants for reaction of ozone with saturated and unsaturated units of macromolecules have been measured. The products of the reaction of ozone with double bonds are inactive and do not influence the subsequent thermal dehydrochlorination of the polymer. The products of reaction of ozone with saturated units greatly increase dehydrochlorination.     

弹性体偶联剂结构对PVC/PPC性能的影响

NBR－PPC弹性体偶联剂能促进PPC（聚丙撑碳酸酯）与PVC（聚氯乙烯）之间的相容性，改善共混物的力学性能，并在共混体系中产生轻度交联。偶联剂组成在NBR／PPC比例为70／30，NBR（丁腈橡胶）含腈量为34％，BPO过氧化苯甲酸用量为2．5份时，共混物的综合力学性能最佳，但偶联剂预先硫化时间不宜过长．     

Dynamic mechanical properties of plasticized poly(vinyl chloride)

The complex compliance in extension of gels of poly(vinyl chloride) (PVC) in di(2-ethylhexyl) phthalate (DOP) and in tricresyl phosphate (TCP) was measured over the frequency range from 0.6 to 0.006 cps and the temperature range from ?66 to 65°C: the weight fractions of DOP and TCP in the gels were 0.32, 0.40, 0.49, and 0.59. Measurements were carried out in an apparatus using forced low-frequency longitudinal osillations. Data for the gels could not be combined by the method of reduced variables, since there were gradual changes with decreasing temperature, attributable to an increase in crystallinity. Application of the reduction method of Ninomiya and Ferry for solutions of crystalline polymers was found to be successful. The apparent melting temperatures (T′_m) were obtained from the temperature dependence of the vertical shift factors. An apparent heat of fusion of ca. 120 cal/mole of monomer unit was found. This melting range was in agreement with that of secondary crystallinity in plasticized PVC reported in calorimetric studies by Juijn. With decreasing temperature, two phenomena occurred in the temperature range from T_g + ca. 80°C to T_g: the vitrification of a concentrated amorphous solution and the slight crystallization of the polymeric component. The larger the difference between T_g and T′_m the broader the primary dispersion zone on the frequency scale. This broadening effect was explained as due to the difference in dependence of T_g and T′_m on plasticizer concentration, without any need to consider any specific interaction between plasticizer and PVC.     

Modification of poly(vinyl chloride). XIII. Crosslinking of poly(vinyl chloride) with dithiols and properties of the crosslinked products

PVC was crosslinked by immersing PVC–dithiol blends in ethylenediamine at 30°C. Properties of the products depended on the chain length and chemical structure of the crosslinkage and on the molecular weight of the polymer chain between crosslinks M_c. Crosslinking by the agent of soft structure and long molecular chain resulted in high tensile strength at break and impact strength and low brittle temperature. The use of the crosslinking agent of short molecular chain gave high yield strength, Young's modulus, and heat distortion temperature. The relation of M_c and the chemical structure of the crosslinks to the properties of the crosslinked rigid polymer was discussed in regard to the crosslinking effect and plasticizing effect.     

Effects of electron beam irradiation on poly(butylene adipate)diol

Effects of electron beam (EB) irradiation on poly(butylene adipate)diol (PBAD) were studied by means of GPC, DSC, and X-ray diffractometry. Below 5 Mrad, chain scission predominantly occurs, while above 10 Mrad, crosslinking and chain scission take place in parallel. Structure of EB-irradiated PBAD is mainly characterized by the main reactions, degradation and crosslinking. Crystallinity of PBAD increased by EB irradiation. This phenomenon was explained by reorganization due to high molecular mobility of EB-irradiated PBAD. But, increment of crystallinity decreased with increasing dose because of formation of crosslinking, excessive degradation and thermal effect of EB. As the result, the crystallinity of EB-irradiated PBAD with a high dose becomes lower than that of original PBAD by thermal treatment.     

Retardation of discoloration of poly(vinyl chloride) and decolorization of discolored poly(vinyl chloride) with diimide

Retardation of discoloration of poly(vinyl chloride) with diimide was studied in dimethylformamide at 130°C. with the use of p-toluenesulfonylhydrazide (PSH) as a source of diimide. A process was proposed that involved prolonging the induction periods of discoloration by inhibiting the development of conjugated polyene structure. The optimum proportion of PSH was one fourth of the poly(vinyl chloride), the best results. Furthermore, poly(vinyl chloride) discolored by thermal degradation in o-dichlorobenzene or gamma-ray irradiation under vacuum was decolorized in solution at 130°C. by addition of PSH. The decolorized poly(vinyl chloride) thus obtained was thermally stable compared with that obtained by oxidative methods.     

Dynamic mechanical and dielectrical properties of poly(vinyl alcohol) and poly(vinyl alcohol)‐based nanocomposites

In this article we report on the investigation of the dynamics of poly(vinyl alcohol) (PVA) and PVA‐based composite films by means of dielectric spectroscopy and dynamic mechanical thermal analysis. Once the characterization of pure PVA was done, we studied the effect of a nanostructured magnetic filler (nanosized CoFe₂O₄ particles homogeneously dispersed within a sulfonated polystyrene matrix) on the dynamics of PVA. Our results suggest that the α‐relaxation process, corresponding to the glass transition of PVA, is affected by the filler. The glass‐transition temperature of PVA increases with filler content up to compositions of around 10 wt %, probably as a result of polymer–filler interactions that reduce the polymer chain mobility. For filler contents higher than 10 wt %, the glass‐transition temperature of PVA decreases as a result of the absorption of water that causes a plasticizing effect. The β‐ and γ‐relaxation processes of PVA are not affected by the filler as stated from both dynamic mechanical thermal analysis and dielectric spectroscopy. Nevertheless, both relaxation processes are greatly affected by the moisture content. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1968–1975, 2001     

Catalytic poly(vinyl alcohol) functionalized membranes obtained by gamma irradiation

Polymeric catalytic membranes bearing sulfonic acid functions have been prepared by mutual gamma irradiation at a ⁶⁰Co source, of poly(vinyl alcohol) (PVA) membranes and methanesulfonic acid. The effect of various synthesis conditions on membranes' physical–chemical properties and catalytic activity in the esterification reaction between acetic acid and isoamyl alcohol to obtain isoamyl acetate (banana flavor), was evaluated. The membranes were characterized by ATR-FTIR, TPP, AFM and SEM. Water contact angle determinations were also performed. The obtained results showed that within the range of conditions studied the increase in sulfonic acid groups' content is accompanied by an enhancement in the membranes catalytic activity, while the increase in absorbed dose leads to a decrease in catalytic activity.     

Some optical and mechanical properties of poly(vinyl chloride)

The optical and mechanical properties of poly(vinyl chloride) film were examined by observing both the stress and birefringence during stretching at constant rate, during relaxation at constant length and during a dynamic birefringence experiment. Experiments were also done by varying the temperature at constant length. The changes in birefringence are interpreted in terms of changes in negative distortional birefringence, changes in positive orientation birefringence, and possible reversible changes in birefringence with temperature arising from conformational changes in the polymer chain and changes in the contribution of birefringent crystals.     

Effect of thermal hysteresis on structural change of water restrained in poly(vinyl alcohol) pseudo-gel

The thermal properties of the poly(vinyl alcohol) pseudo-gel obtained by freezing have been investigated by differential scanning calorimetry in the temperature range 200–390 K. Determination of the enthalpies of melting and crystallization of the water contained within pseudo-gel allowed the classification of three different states of water viz. non-freezing, restrained and free water. It was also demonstrated by thermogravimetry that the water of pseudo-gel evaporated in three steps in the temperature range 340–420 K. The amount of non-freezing water was found to be constant, while those of restrained and free water were shown to depend on the thermal histories produced during the freezing. The size of ice crystals which formed in the gel was affected by the rate of freezing and it necessarily controlled the number of pseudo-crosslinks formed between poly(vinyl alcohol) molecules. A good relationship was observed between the amount of restrained water and the thermal stability of the gel.     

用DSC研究线形多嵌段聚氨酯与聚氯乙烯、氯化聚氯乙烯共混相容性

用示差扫描量热法（DSC）研究了线形多嵌段聚氨酯（PU）与聚氯乙烯（PVC）、氯化聚氯乙烯（CPVC）共混相容性，说明了PU／VC、PU／CPVC的相容是由于共混物中形成了新的氢键的缘故．聚酯型聚氨酯与PVC、CPVC的相容性要好子聚酸型聚氨酯，CPVC与PU的相容性又要好于PVC．聚氨酯中硬段的引入不利于PU／PVC、PU／CPVC的相容性．