Theoretical analysis of the Rose-Fowler-Vaisberg model

Results of numerical calculations based on the Rose-Fowler-Vaisberg model of radiation-induced conductivity in a case polymer upon long (10⁴ s) irradiation at doses of 5 × 10⁵–10⁷ Gy are reported. Two irradiation modes were considered: (1) preliminary irradiation and irradiation repeated at variable times after the end of the first irradiation and (2) probing the virgin and irradiated polymer with a standard pulse of ionizing radiation. It was shown that the properties of radiation-induced conductivity, such as its overshoot kinetics, a considerable difference between current transients for the initial and the repeated irradiation, extremely long annealing times of dose effects, and the absence of a steady state, are naturally explained in terms of this model (with allowance for the generation of radiation-induced traps as regards the last property). The Rose-Fowler-Vaisberg theory should be considered at present a well-approved semiempirical model of radiation-induced conductivity in polymers.     

Effect of dose on radiation-induced conductivity in polymers

Numerical simulation of radiation-induced conductivity in polymers upon long-term irradiation on the basis of the generalized Rose-Fowler-Vaisberg model, which allows for both dipolar carrier transport and generation of radiation traps during irradiation, was performed. The unusual properties of radiation-induced conductivity, such as the appearance of a maximum on current transients, the absence of a steady state, and a substantial difference between these curves for the first and subsequent irradiation, are rationalized in terms of the formation of free radicals, the major feature of radiolysis in the chemical aspect. This interpretation does not require the involvement of degradation or crosslinking processes, unlike other interpretations that appear in the literature. With the use of low-density polyethylene as an example, it was shown that radiation-induced conductivity both upon pulse and continuous irradiation can satisfactorily be described with the unified set of parameters of the generalized Rose-Fowler-Vaisberg model.     

Dose effects in radiation-induced conductivity of polypyromellitimide

Dose effects in radiation-induced conductivity of polypyromellitimide were numerically simulated in terms of the Rose-Fowler-Vaisberg model with allowance for bipolar carrier transport and the generation of radiation traps during irradiation. The reasons for the lack of a noticeable dose effect in this polymer upon pulse irradiation in light of its presence in the case of continuous irradiation are discussed.     

The role of stable free radicals in the radiation-induced conductivity of low-density polyethylene

The radiation-induced conductivity (RIC) of low-density polyethylene (LDPE) under continuous irradiation with fast electrons (50 keV) was experimentally studied. The dose dependence of the concentration of stable paramagnetic centers was determined. The kinetics of RIC in LDPE was calculated on the basis of the Rose-Fowler-Vaisberg (RFV) model taking into account the buildup of radiation-induced traps. Good correlation between the experimental results and calculated data was found.     

Dose dependence of the radiothermoluminescence intensity of polyethylene crystalline regions

The dose dependence for the intensity of all radiothermoluminescence peaks of polyethylene crystalline regions has been studied in the dose (D) range of 1.3?C30 kGy. The initial portion of the dose dependence curve at doses below 5 kGy has the same pattern for all the peaks; the first derivative is dI/dD > 0 at D = 0 and only decreases with the dose. This type of the dependence suggests that charge traps present in the polymer (in intracrystalline regions) at low doses have existed before irradiation. These traps can be regular segments of polymer chains in the crystalline regions. As the dose increases, radiation-induced traps appear and the dose dependence curves for peak intensities become dissimilar. Some of them show a decrease in intensity with the dose, others reach a limiting value and further do not vary in intensity, and the third ones display a permanent intensity rise.     

Electron transport of holes in molecularly doped polycarbonate and its radiation-induced conductivity

The salient features of charge transport in a typical molecularly doped polymer (polycarbonate + 30 wt % DEH hydrazone) were studied by time-of-flight and nonsteady-state radiation-induced conductivity measurements. It was shows that the mobility of holes (major carriers) is due to dispersive transport in the temperature range 296–353 K covering the glass transition temperature at an observation time of up to a few seconds. The appearance of a plateau on the current transient, presumably manifesting the establishing of quasiequilibrium (Gaussian) transport, is the artifact of the time-of-flight technique when the charge carrier generation takes place at the sample surface. All of the obtained results can be satisfactorily rationalized in terms of the Rose-Fowler-Weisberg model with a uniform set of parameters of the model. Such an approach is compatible with the basic concepts of the radiation chemistry of condensed phase (the Onsager theory and the Langevin recombination mechanism), structural features of a disordered medium (transport zone, structural traps), and rotational diffusion of small molecules or their molecular groups in vitrified polymers.     

Optical and electrical analysis of blue polymethyl methacrylate for high-dose dosimetry

The response to gamma radiation of polymethyl methacrylate (“blue PMMA”) containing a blue dye was investigated, with the aim of providing a high-dose dosimeter based on either spectrophotometry or electrical-conductivity measurements. It is found that the 3-mm thick pieces of blue PMMA can be used for dosimetry in a range of absorbed doses from about 5-50 kGy, for which the changes in optical transmission density (absorbance) at different wavelengths in the visible region (402, 596, 612, and 643 nm) are linear functions of dose. Results also show that irradiation of thin 0.1 mm films of blue PMMA produces two components of radiation-induced conductivity: a transient component which can be used to determine the absorbed dose rate and a steady-state component which registers the total absorbed dose in the range 20–80 kGy as based on a suitable calibration. The effects of post-irradiation storage time, day light, and storage temperature on the radiation-induced visible spectrum were investigated. The storage-temperature effect on post-irradiation conductivity measurement was also evaluated.     

Theoretical Analysis of the Mechanism of Slow Reversible Degradation of the Transport Properties of Photoconducting Polymers

The dose effect in photoconducting polymers is analyzed, concerning the buildup of minority charge carriers that act as recombination sites, which leads to a noticeable decrease in the effective mobility of majority carriers and degradation of the transport properties of polymer layers. This charge degradation mechanism is universal and completely reversible and can be rationalized in terms of the Rose–Fowler–Vaisberg model. The disorder parameter plays a determining role in the manifestation of the dose effect; when it decreases (<0.4), both the magnitude of the dose effect and the time required for its annealing strongly increase.     

Radiation-induced conductivity in polymers during long-term irradiation

Radiation-induced conductivity (RIC) in polystyrene, poly(ethylene terephthalate), polyvinylcarbazole, and low-density polyethylene during long-term (to 3.6 × 10³ s) irradiation with 50-keV electrons (dose rate of 6–830 Gy/s) was experimentally and theoretically studied. It was shown that the nonmonotonic RIC kinetics in the polymers is a direct consequence of the generation and the subsequent transport of charge carriers in them in the presence of traps distributed over a broad energy range almost according to the exponential law. This phenomenon has no relation to degradation and crosslinking processes that occur in irradiated polymers. The nonmonotonic RIC kinetics in polymers is a universal phenomenon, and it is described satisfactorily in terms of the Rose-Fowler-Vaisberg model.     

Electron emission during deformation of polymers

Electron emission was detected during deformation of both carbochain and heterochain polymers in vacuum. It was found that the features of emission are similar to those observed in molecular scissions under drawing of unoriented and oriented polymers. This fact indicates that there is a relationship between the fracture process and electron emission under deformation of polymers. This relationship is also obvious from the experiments with interruption of loading when electron emission during the repeated loading does not begin immediately at the moment of load application, but can be recorded only at the degree of deformation which is higher than that reached during the first loading. The interconnection between deformational electron emission and molecular scissions allowed visualization of the fracture process in the subsurface layers of polymers using an electron-optical convertor which gives a mechanoemission image of a stretched sample. It is supposed that the deformation-induced electron emission of polymers is caused by ionization of stressed macromolecules resulting from tunnel transitions of electrons into deep traps. During deformation, the traps are destroyed and a part of electrons escapes in vacuum.     

Mechanism of radiothermoluminescence of crystalline tetracosane

Radiothermoluminescence (RTL) of tetracosane irradiated in liquid nitrogen with γ-rays is due to trapped charges. At doses below 2 kGy, all processes leading to RTL are localized in tetracosane intracrystalline areas in traps with a depth of 0.1–2.0 eV that were present in tetracosane before irradiation. With increasing the dose, radiation-induced traps with a depth of 3 eV or higher appear in addition. At the same time, part of the charges reach the surface and become available for interaction with an electron acceptor. The presence of shallow traps (less than 0.15 eV) leads to a decrease in the RTL intensity over the entire temperature range from 100 to 300 K during storage of irradiated samples in liquid nitrogen.     

Radiation-Induced Injection Conductivity of Polymers

Steady-state currents flowing through planar polymer layers under irradiation with 15–50 keV electrons were studied experimentally and theoretically. The ultimate range of electrons was somewhat below the layer thickness. The Monte Carlo method was used to determine the basic transport characteristics of fast electrons in polymers (maximum range, depth distribution of absorbed dose and forward current). It was shown that significant steady-state currents (1 to 10% of the electron beam current) were observed only if the thickness of blocking (unirradiated) layer did not exceed 5 m. The magnitude of these currents was almost unaffected by the polymer type (polymers with minimum radiation-induced conductivity and polymers with electron or hole conductivity were examined). It was found that conventional theories of conductivity of dielectrics failed to explain the observed experimental data. Additional arguments in favor of the hypothesis of streamer mechanism of injection currents through an unirradiated polymer layer were obtained. It is emphasized that the radiation-induced heating of polymer samples can play an important role in the phenomenon under study, acting as an undesirable technical factor, that strongly distorts obtainable experimental data.     

HALS和抗氧剂对PE辐射致色的影响

聚乙烯;稳定剂;HALS和抗氧剂对PE辐射致色的影响     

Study of radiation-induced polymerization of vinyl monomers adsorbed on inorganic substances. V. Effects of p-benzoquinone and dose rate on methyl methacrylate–silica gel system

In order to elucidate the mechanism of radiation-induced polymerization of methyl methacrylate adsorbed on silica gel, the effects of p-benzoquinone addition and dose rate were studied in detail. Most of the polymerization is inhibited by p-benzoquinone at levels above 10^-2 mole/l. The GPC spectra of both graft polymers and homopolymers show two peaks. The high molecular weight material appears to have been formed by polymerization by a radical mechanism, because these peaks decrease as p-benzoquinone concentration increases; on the other hand, their low molecular weight polymers seem to be products of an ionic polymerization mechanism because those peaks are almost not affected by p-benzoquinone. The four GPC peaks differ in dose rate dependences of their polymerization rate. The dose-rate exponents of polymerization rate were obtained for the four GPC peaks. The behavior of the low molecular weight peaks of graft polymers and homopolymers were quite different, suggesting that the polymers differ considerably in formation mechanism.     

A Monte Carlo simulation of radiation-induced conductivity of disordered solids

The Monte Carlo method was used to perform a theoretical study of the kinetics of radiation-induced conductivity under pulsed irradiation of a disordered solid with traps having different energy distributions. The kinetics of radiation-induced conductivity in a weak electric field was satisfactorily described by the Rose-Fowler-Vaisberg model. In a strong field, radiation-induced conductivity became a nonlinear field strength function because of distortions of the energy spectrum of trap centers.     

Waveguide spectroscopic characterization of 3D anisotropies in conventionally photooriented and annealed films of liquid crystalline and amorphous azobenzene polymers

Films of azobenzene-containing polymers were photooriented in the glassy state in such a way that the azobenzene side groups were oriented preferably perpendicular to the electric field vector. In the case of liquid crystalline polymers ,the photoinduced anisotropies generated in the glassy state were modified by thermotropic self-organization due to annealing above T(g). The conventional photoorientation process results in an oblate order. The changes in photoinduced anisotropies brought about by annealing in the liquid crystalline phase were investigated quantitatively for the first time by us for different polymer compositions and experimental conditions. Different biaxial and homeotropic orders result for liquid crystalline polymers, depending on the experimental conditions. Different polymer structures are compared and the influence of the interfaces is investigated. Orientational gradients can be induced by irradiation or annealing and are for the first time determined by the WKB (Wentzel-Kramers-Brillouin) method.     

Study on the concentration effects in size exclusion chromatography VII. A quantitative verification for the model theory of concentration and molecular mass dependences of hydrodynamic volumes for polydisperse polymers

A model theory of concentration effects for polydisperse polymers was proposed in 1988. It is successful in relating the concentration of the injected solution to the effective hydrodynamic volumes of peak, the retention volumes of peak and the polydispersity index (Dc = (Vhcw)/(Vhcn) of hydro-dynamic volume distribution for polydisperse polymers at a given concentration. The dependence of the concentration of injected polymer solution on the effective hydrodynamic volumes, the retention volumes of peak and the polydispersity index of hydrodynamic volume distribution for narrow disperse and polydisperse polystyrene, poly(dodecyl methacrylate), poly(tridecyl methacrylate) and poly(methyl methacrylate) in tetrahydrofuran solvent were studied. The proposed theory was verified by these experimental data. Results show that the proposed theory can predict the concentration effects in GPC for polydisperse polymers quantitatively and can provide a theoretical foundation for the two methods of calibrating the universal calibration curves with polydisperse polymers and of determining the second virial coefficients (A2) of polymers. It is found that the determined values of A2 for narrow disperse and polydisperse polymers by the proposed method are in agreement with those obtained by the LALLS method, and the two universal calibration curves with narrow disperse and polydisperse polymers are in excellent agreement.     

高透明抗冲聚苯乙烯树脂的辐射合成与性能表征

以过氧化苯甲酰为引发剂,采用苯乙烯、甲基丙烯酸甲酯为共聚单体,先经本体自由基预聚合,再经γ辐照聚合法合成甲基丙烯酸甲酯 苯乙烯共聚物(MS)树脂.系统研究了吸收剂量和剂量率对MS树脂的分子量及其分布的影响,同时研究了树脂的化学结构、热性能、透过率和力学性能.结果表明,辐射合成的MS树脂是一种无规共聚物,具有很好的光学性能,较好的韧性和强度.     

Physicomechanical properties of grafted polymers obtained by radiation-induced polymerization by radical and ionic mechanisms

The radiation-induced grafting of acrylonitrile, 4-vinylpyridine, and styrene was carried out by both radical and ionic mechanisms. Grafted polymers with equal percentages of graft were obtained by the radical and ionic propagation of the grafted chains. The molecular weight of homopolymers has been determined. The thermomechanical properties of the graft polymers were investigated. The yield temperatures for the graft polymers obtained by ionic propagation of the grafted chains is higher than that of graft polymers obtained by a radical mechanism. This is attributed to the higher molecular weight of the grafted chains obtained by the radiation-induced grafting by the ionic mechanism. The radiation-induced grafting of polyacrylonitrile increases significantly the thermal stability of polyethylene. The differential thermal analysis shows no marked differences in properties of the polymers.