The effect of chain flexibility and chain mobility on radiation crosslinking of polymers

Radiation crosslinking of polymers mainly depends on the structure of polymer chain. The flexibility and mobility of chain directly influence the possibility of the reactive radicals recombination. Flexible chain is easier to crosslink than rigid-chain polymer. The latter must be crosslinked at high temperature, as most polymers can only crosslink above their melting point. Structural effect also influences the mechanism of radiation crosslinking of polymers. We find from the results in literature and in our laboratory that, the flexibility chain polymer mainly crosslinked with H type, but the rigid chain polymer mainly crosslinked with Y type. (C) 2001 Published by Elsevier Science Ltd.

Radiation effects on the immiscible polymer blend of nylon1010 and high-impact strength polystyrene (II): mechanical properties and morphology

The paper studies the morphology and mechanical properties of immiscible binary blends of the nylon 1010 and HIPS through the radiation crosslinking method. In this blend, the HIPS particles were the dispersed phases in the nylon 1010 matrix. With increasing of dose, the elastic modulus increased, However, the tensile strength. elongation at bleak and the energy of fracture increased to a maximum at a dose of 0.34 MGy, then reduced with the increasing of dose. SEM photographs show that the hole sizes are not changed obviously at low dose and at high dose, remnants that cannot be dissolved in formic acid and THF can be observed in the holes and on the surface. TEM photographs showed that radiation destroys the rubber phases in the polymer blend. (C) 2001 Elsevier Science Ltd. All rights reserved.

Effect of electron radiation on crystal structure transition of trans-1, 4-polybutadiene

trans-1,4-Polybutadiene (PTBD) was synthesized by rare earth catalyst system, The effect of electron radiation on phase transition from monoclinic phase to hexagonal phase was observed by TEM, Electron diffraction patterns of monoclinic phase, hexagonal phase and two coexistent phases were recorded, The mechanism of phase transition was also discussed in this paper.

Advanced research work on radiation cross-linking of polymers in CIAC

Recent research carried out at the Chinese Institute of Applied Chemistry has contributed significantly to the understanding of the radiation chemistry of polymers. High energy radiation has been successfully used to cross-link fluoropolymers and polyimides. Here chain flexibility has been shown to play an important role, and T-type structures were found to exist in the cross-linked fluoropolymers. A modified Charlesby-Pinner equation, based upon the importance of chain flexibility, was developed to account for the sol-radiation dose relationship in systems of this type. An XPS method has been developed to measure the cross-linking yields in aromatic polymers and fluoropolymers, based upon the dose dependence of the aromatic shake-up peaks and the F/C ratios, respectively. Methods for radiation cross-linking degrading polymers in polymer blends have also been developed, as have methods for improving the radiation resistance of polymers through radiation cross-linking.

Influence of interface on radiation effects of crystalline polymer - radiation effects on polyamide-1010 containing BMI

Aimed at saving the radiation dose required to crosslinking the polyamid-1010, BMI/PA1010 systems containing different amounts of difunctional crosslinking agent N,N'-bis-maleimide-4,4'-biphenyl methane (BMI) were prepared and the structure changes at the crystallographic and supermolecular levels before and after irradiation were studied by using WAXD, SAXS, and DSC techniques. It was found that by incorporation of BMI the microcrystal size L-100 is lowered due to the formation of hydrogen bond between the carbonyl oxygen of BMI and the amide hydrogen of PA1010 in the hydrogen bonded plane, and the overall crystallinity W-c is also decreased. The presence of BMI causes the crystal lamella thickness d(c) to decrease and greatly thickens the transition zone d(tr) between the crystalline and amorphous regions. As for the irradiated specimen, the maximum increments in the L-100 and W-c against dose curves decrease with BMI content, and the interception point D-i, at which the L-100 and W-c curves intercept their respective horizontal line of L-100/L-100(0) and W-c/W-c(0)=1, shift to lower dose with an increase in BMI concentration. In addition. the mechanism of the radiation chemical reactions in the three different phases under the action of BMI are discussed with special focus on the interface region. (C) 1999 Published by Elsevier Science Ltd. All rights reserved.

Thermal, mechanical and ionic conductive behaviour of gamma-radiation induced PEO/PVDF(SIN)-LiClO4 polymer electrolyte system

An effort has been made to modify the mechanical behaviour of our previously reported gel-type gamma-radiation crosslinked polyethylene oxide (PEO)-LiClO4 polymer electrolyte. A highly polar and gamma-radiation crosslinkable crystalline polymer, polyvinylidene fluoride (PVDF), was selected to blend with PEO and then subjected to gamma-irradiation in order to make an simultaneous interpenetrating network (SIN), which was used as a polymer host to impart stiffness to the plasticized system. Experimental results have shown that the presence of PVDF in the system, through gamma-radiation induced SIN formation, could not only give a rather high mechanical modulus of 10(7) Pa at ambient temperature, but also maintain the room temperature ionic conductivity at a high level (greater than 10(-4) S/cm). DSC, DMA and conductivity measurement techniques were used to examine the effects of blending, gamma-irradiation and plasticization on the variations of glass transition and melting endotherm, on the appearance of high elastic plateau and on the temperature dependence of ionic conductivity: In addition, it was found that, in contrast with the unplasticized system, the ionic conductivity mechanism of this gel-type electrolyte seems to conform to the Arrhenius model, suggesting that, as a result of the high degree of plasticization, the polymer chains act mainly as the skeleton of the networks or polymer cages to immobilize the liquid electrolyte solution, whereas the ionic species migrate as if they were in a liquid medium. (C) 1997 Elsevier Science Ltd.

Radiation-induced crystallization of polyamide-1010 containing heterogeneous nuclei

Radiation-induced crystallization of polyamide-1010 (PA1010) or nylon-1010 containing heterogeneous nuclei (neodymium oxide, Nd2O3) is discussed in this paper by Wide Angle X-ray Diffraction (WAXD) and Differential Scanning Calorimetry (DSC). The results show that at low dosage the crystallinities of the irradiated specimens increase, while crystallite size (L(hkl)) decreases, indicating that some new crystallites are produced in the course of irradiation. The new centers were brought about in the fold surface of the lamellae. Copyright (C) 1997 Elsevier Science Ltd

gamma-Radiation damage to nylon 1010 containing neodymium oxide

A comparison of radiation damage to nylon 1010 (denoted nylon-a) and nylon 1010 containing neodymium oxide (Nd2O3) (denoted nylon-b) was made by DSC, WAXD, ESR and the determination of gel fractions. The results show that radiation damage to nylon-b is delayed, and radiation damage to nylon-a is more severe than that to nylon-b, due to the protection of the fold surface of the lamellae. Furthermore, the fact that the damage begins with the fold surface of the lamellae is confirmed. (C) 1996 Elsevier Science Limited

Exploration of post radiation effects on polyamide-1010

Irradiated polyamide-1010 (PA1010) with and without heat treatment after gamma-ray irradiation was compared by wide angle x-ray diffraction (WAXD), differential scanning calorimeter (DSC) and the determination of gel fractions. The results indicate that post radiation effects due to post radiation crosslinking and scissions affect physical properties. Post radiation effects restrain the formation and perfection of the planes (010), and make the crystals imperfect. Post radiation effects change the crystalline structures of polyamide-1010.

Influence of the fold surface of the lamellae on radiation effects - Research on irradiated polyamide-1010 containing heterogeneous nuclei

Irradiated polyamide-1010 (PA1010) and PA1010 containing 0.5% (wt) heterogeneous nuclei were studied by ESR, WAXD, DSC and the determination of gel fractions. The fold surface of the lamellae plays an important role in the effects of radiation on crystalline PA1010. The results show that the direct radiation effects on both samples vary, while after being heated to 220 degrees C, the final radiation effects are identical, regardless of the difference in the amount of the fold surface of the lamellae. The post-radiation effects result predominantly from the fold surface.

Chemiluminescence studies of radiation induced oxidation of various polyethylenes

The chemiluminescence (CL) emission from three kinds of polyethylene, HDPE, LLDPE and LDPE, which had been exposed to 80 kGy dose from Co-60 in both air and nitrogen, has been examined. CL measurement was done under both nitrogen and oxygen atmosphere. The results show that the CL emission from irradiated samples does not result from irradiation itself, but from the oxidation reactions occurring during and after irradiation. Addition of 1 phr of an antioxidant, Irganox 1010, can effectively inhibit the radiation induced oxidation in LLDPE and LDPE. In the case of HDPE, however, it was found that pure HDPE has the best resistance to radiation-induced oxidation of the polymers examined in this work. However, incorporation of Irganox 1010 was found to have not only a stabilizing effect against radiation induced oxidation, but also to promote the oxidation in some cases.

WAXD and SAXS study on gamma-radiation damage to polyamide-1010 crystal structure

In the present work we attempt to settle the controversy on the district wherein the radiation induced reaction preferentially occurs through examining the structural changes of the irradiated polyamide-1010 specimens on both the crystallographic and the supermolecular level by using WAXD and SAXS techniques. Experimental results indicated that the chain crosslinking and scission of the irradiated specimens occur mainly in the amorphous region and on the crystal surface (or interphase), and extend into the inner portion of the crystal with increasing radiation dose.

THE INFLUENCE OF GAMMA-RADIATION ON POLYAMIDE-1010 AGGREGATE STRUCTURES

The influence of gamma-radiation on polyamide 1010 aggregate structures and crystal damage were examined by using wide angle X-ray diffraction (WAXD) and small angle X-ray scattering (SAXS) techniques. The results revealed that some structural parameters of the aggregated state, the density differences and the degree of crystallinity W-c,W-x, essentially decreased with increasing radiation dose, but the specific surface O-s increased. Crosslinking and scission of irradiated polyamide 1010 samples occurred mainly in amorphous and interphase regions, and crystal damage and amorphization induced by gamma-radiation spread from the interphase and extended into the crystal phase with increasing radiation dose. This result also indicated that the (010) reflection with the hydrogen bond was more susceptible to the action of radiation.

GAMMA-RADIATION INDUCED CROSS-LINKED PEO-LICLO4 SOLID-ELECTROLYTE SYSTEM

Aimed at raising the room temperature ionic conductivity of PEO-based solid polymer electrolyte and considered that the ionic conduction preferentially occurs in the amorphous phase, we lightly crosslinked the high MW PEO through gamma-irradiation and further suppressed the residual crystallinity by plasticizing with propylene carbonate. By incorporating LiClO4 salt to the above described polymer host, the ambient (25 degrees C) ionic conductivity of the electrolyte system could reach as high as 6.8 X 10(-4) S/cm. As the electrolyte was a crosslinked system, it was mechanically self-supportable. Based on the preliminary results of the electrochemical performance of the secondary lithium battery, assembled by using this kind of solid electrolyte and polyaniline as positive electrode, it is realized that the electrolyte thus prepared is of high expectancy.

GAMMA-RADIATION DAMAGE TO POLYAMIDE-1010 CRYSTAL-STRUCTURE

Radiation effects on polyamide-1010 specimens having various states of aggregation were studied using wide angle X-ray diffraction, electron spin resonance, calorific and sol measurement techniques. Experimental results indicated that chain crosslinking