低温等离子体对塑料表面处理——低温等离子体对高密度聚乙烯表面处理的ESR研究

本文研究了不同处理条件(处理功率、处理时间和处理压力)下等离子体气体(Ar、N₂、O₂和空气等)对高密度聚乙烯表面处理产生的自由基的ESR谱。我们观察到等离子体处理产生的自由基是相当稳定的,它的ESR信号强度随处理功率和处理时间增加而增加。但处理压力对它影响不大。我们证明了紫外线对高密度聚乙烯表面产生自由基作用随处理条件而变化。并初步解释了谱的超精细相互作用。     

Electron beam induced modification of poly(ethylene terephthalate) films

Electron beam processing of poly(ethylene terephthalate) (PET) films is found to promote significant changes in the melting heat, intrinsic viscosity and polymer film-liquid (water, isooctane and toluene) boundary surface tension. These properties are featured with several maximums depending on the absorbed dose and correlating with the modification of PET surface functionality. Studies using adsorption of acid-base indicators and IR-spectroscopy revealed that the increase of PET surface hydrophilicity is determined by the oxidation of methylene and methyne groups. Electron beam treatment of PET films on the surface of N-vinylpyrrolidone aqueous solution provided graft copolymerization with this comonomer at optimum process parameters (energy 700 keV, current 1 mA, absorbed dose 50 kGy).     

Vibrational EELS and DFT study of propionic acid and pyruvic acid on Ni(1 0 0): Effects of keto group substitution on room-temperature adsorption and thermal chemistry

The room-temperature adsorption and thermally induced processes of propionic acid and pyruvic acid on Ni(1 0 0) have been investigated by electron energy loss spectroscopy (EELS). Computational vibrational analysis of the optimized bidentate structures for acid-Ni model complexes (involving the organic acid and a Ni atom) has been performed by using the two-layer ONIOM method with the Density Functional Theory and used to interpret the vibrational EELS data. Dehydrogenation of the hydroxyl group is found to result in bonding of the carboxylate group in the propionate and pyruvate adspecies to either a single Ni surface atom in a bidentate configuration or two neighbouring Ni atoms in a bridge configuration. Given the similarities in the total energies and related vibrational frequencies obtained by the calculations in the case of pyruvate adspecies, it is difficult to differentiate the alternate adsorption structure, in which the keto O and hydroxyl O atoms are bonded to a Ni atom in a five-member chelate ring configuration. Furthermore, temperature-dependent EELS studies show that both the propionate and pyruvate adspecies could decompose upon annealing to above 400 K and further dissociate to CO adspecies above 550 K and to C and/or O above 600 K.     

EPR investigations of oxidation effects in (V1−xMox)2−δO3

Electron paramagnetic resonance (EPR) investigations has been carried out on the new family of molybdenum doped vanadium sesquioxides (V_1−xMo_x)_2−δO₃. The oxidation effects were monitored from the rate of paramagnetic V⁴⁺ created when the sample is exposed to the air. The effects of the oxidation time, sample temperature, and annealing at 1000 °C under a diluted hydrogen atmosphere on the EPR signal features are analyzed. The V⁴⁺ concentration in the oxidized samples is determined and the relaxation effects driven by the conduction electrons are pointed out from the thermal behaviour of the EPR line features. EPR spectra of all the oxidized samples also reveal a small ferromagnetic contribution strongly correlated with the V⁴⁺ content.     

低阻抗二极管产生的强流电子束能谱分布的数值模拟

 给出了低阻抗二极管产生的电子束能谱分布及外加磁场对二极管阻抗影响的数值模拟研究结果。结果表明，即使在外加电压恒定的条件下，二极管产生的电子束也具有一定的能谱分布，这说明用二极管电压、电流波形计算脉冲电子束能谱分布是不正确的。另外,外加磁场对低阻抗二极管的阻抗特性具有较大影响，其阻抗随外加磁场的增大而减小。分析认为这是由于外加磁场强度的变化改变了二极管中束电子的运动轨迹。当没有外加磁场或外加磁场较小时，低阻抗二极管产生的电子束发生自箍缩，此时二极管电流是自箍缩饱和顺位流；当外加磁场足够强时，电子束的自箍缩被抑制，二极管电流是没有箍缩时的空间电荷限制电流。束电流小于自箍缩临界电流的二极管其阻抗将不随外加磁场的变化而变化。     

A Generalized Unpaired Electron Spin Density Equation and Organic Hyperconjugation Mechanism

A large class of stereochemcial and related interactions in organic chemistry are repulsive and others are attractive, but the relative orientation of two methyl groups and the amount of energy required to twist one relative to the other (the hindered rotation energy barriers), or the alignment of such a group with respect to a conjugated ring to which it is attached (widely attributed to a mechanism called “hyperconjugation”) are estimated to be small in compared with the total energy of the molecule. We used theories of both isotropic and anisotropic proton hyperfine interactions in the π‐electron systems developed in the early sixties. They are approximated by the magnetic dipole nteractions between each proton and an electron spin magnetization that is distributed in 2s and 2p Slater atomic orbitals center on carbon atoms. We have extended these theories to the non‐planar olefinic cation radicals, which are very important in biochemistry as well as in petroleum catalysis. A three dimensional electron spin density equation has been developed in this paper to handle some Jahn‐Teller vibronic molecules. The new electron spin density equation related the observed proton hyperfine splittings to the non‐planar structures of the open‐chain alkene cation radicals generated by radiolysis and various chemical oxidation methods. The spin densities and the conformational calculations based on valence bond theory and symmetry principles are compared with some more elaborated molecular orbital calculations in the literature. The localized valence bond approaches are better in accord with our experimental results. The anomalous line‐width effect of the four methyl groups observed in the 2,3‐dimethyl‐2‐butene cation radicals also confirmed the positive sign of the electron‐proton hyperfine constant of hyper‐conjugation mechanism. A methyl substituent attached to a conjugated molecule often behaves as if it formed part of the region of conjugation; the charge appears to flow from the methyl group into the π electron system and it may also give rise to an appreciable dipole moment. Methylation also gives rise to an appreciable dipole moment, and the resultant red shift of electronic absorption bands is of some importance in the design of dye molecules.     

Nondispersive two-electron wave packets in driven helium

We provide a detailed quantum treatment of the spectral characteristics and of the dynamics of nondispersive two-electron wave packets along the periodically driven, collinear frozen planet configuration of helium. These highly correlated, long-lived wave packets arise as a quantum manifestation of regular islands in a mixed classical phase space, which are induced by nonlinear resonances between the external driving and the unperturbed dynamics of the frozen-planet configuration. Particular emphasis is given to the dependence of the ionization rates of the wave packet states on the driving field parameters and on the quantum mechanical phase space resolution, preceded by a comparison of 1D and 3D life times of the unperturbed frozen planet. Furthermore, we study the effect of a superimposed static electric field component, which, on the grounds of classical considerations, is expected to stabilize the real 3D dynamics against large (and possibly ionizing) deviations from collinearity. Received 7 November 2002 / Received in final form 2 December 2002 Published online 28 January 2003     

HL—1装置中心热区电子热传导初步分析

在电流及温度分布满足“不变性”原理的基础上,本文分析了等离子体中心热区的能量平衡,求出了电子热传导系数,根据实验数据拟合出HL-1装置电子热传导系数的定标关系为X_e=6.8(n_(eq1))~(-1.2)。此关系与其他托卡马克装置的结果类似。     

Current R & D activities at TRCRE in polymer processing by EB

The current status of the R & D activities is presented on electron beam processing of polymers being carried out at TRCRE. Topics included are sterilization of medical products, graft polymers for selective separation or absorbents and curing of liquid prepolymer-monomer systems.