Electron impact excitation rate coefficients of N II ion

This paper calculates the electron impact excitation rate coefficients from the ground term 2s(2)2p(2) P-3 to the excited terms of the 2s(2)2p(2), 2s2p(3), 2s(2)2p3s, 2s(2)2p3p, and 2s(2)2p3d configurations of N II. In the calculations, rnulticonfiguration Dirac-Fork wave functions have been applied to describe the target-ion states and relativistic distorted-wave calculation has been performed to generate fine-structure collision strengths. The collision strengths are then averaged over a Maxwellian distribution of electron velocities in order to generate the effective collision strengths. The calculated rate coefficients are compared with available experimental and theoretical data, and some good agreements are found for the outer shell electron excitations. But for the inner shell electron excitations there are still some differences between the present calculations and available experiments.

Graft chain propagation rate coefficients of acrylic acid in melt graft copolymerization with linear low density polyethylene

Graft chain propagation rate coefficients (k(p.g)) for grafting AA onto linear low density polyethylene (LLDPE) in the melt in ESR tubes have been measured via Fourier transform infrared (FTIR) spectroscopy and electron spin resonance (ESR) spectroscopy in the temperature range from 130 to 170 degrees C. To exclude the effect of homopolymerization on the grafting. the LLDPE was pre-irradiated in the air by electron beam to generate the peroxides and then treated with iodide solution to eliminating one kind of peroxides, hydroperoxide. The monomer conversion is determined by FTIR and the chain propagation free-radical concentration is deduced from the double integration of the well-resolved ESR spectra, consisting nine lines in the melt. The temperature dependence of k(p.g) is expressed:The magnitude of k(p.g) from FTIR and ESR analysis is in good agreement with the theoretical data deduced from ethylene-AA copolymerization, suggesting this method could reliably and directly provide the propagation rate coefficient. The comparison of k(p.g) with the data extrapolated from solution polymerization at modest temperature indicates that the extrapolated data might not be entirely fitting to discuss the kinetics behavior in the melt.

Electron collision cross sections and rate coefficients for the Na-like Cu ion

Collision cross sections are calculated using the R-matrix method for excitations between the three lowest LS states for Na-like Cu ion. The complex resonance structures are investigated. The collision rate coefficients have been calculated assuming a Maxwellian distribution of electron-impact energies. The results of the collision cross sections are in good agreement with those of the other theory.

Well-defined higher-molecular-weight polyacrylonitrile via RAFT technique in the presence of disulfide compounds as a source of chain transfer agent

Well-defined polyacrylonitrile with a higher number-average molecular weight (R.) up to 200,000 and a lower polydispersity index (PDI, 1.7-2.0) was firstly obtained via reversible addition-fragmentation chain transfer (RAFT) process. This was achieved by selecting a stable, easy way to prepare disulfide compound intermediates including bis(thiobenzoyl) disulfide (BTBDS) and bis(thiophenylacetoyl) disulfide (BTPADS) to react with azobis(isobutyronitrile) to directly synthesize RAFT agents in situ.

A Novel Strategy to Branched Polyacrylonitrile Via One-Pot RAFT Copolymerization of Acrylonitrile and an Asymmetrical Divinyl Monomer

Branched polyacrylonitriles were prepared via the one-pot radical copolymerization of acrylonitirle and an asymmetric divinyl monomer (allyl methacrylate) that possesses both a higher reactive methacrylate and a lower reactive allyl. RAFT technique was used to keep a low-propagation chain concentration via a fast reversible chain transfer euilibration and thus the cross-linking was prevented until a high level of monomer conversions. This novel strategy was demonstrated to engenerate a branched architecture with abundant pendant functional vinyl and nitrile groups, and controlled molecular weight as a behavior of controlled/living radical polymerization characteristics. The effect of the various experimental parameters, including temperature, brancher to monomer molar ratio, and chain transfer agent to initiator molar ratio, on the control Of moleculer dimension (molecular weight and polydispersity indices) and the degree of branching were investigated in detail. Moreover, H-1 NMR and gel permeation chromatography confirm the branched architecture of the resultant polymer. The intrinsic viscosity of the copolymer is also lower than the linear counterpart.

2-cyanoprop-2-yl dithiobenzoate mediated reversible addition-fragmentation chain transfer polymerization of acrylonitrile targeting a polymer with a higher molecular weight

The reversible addition-fragmentation chain transfer (RAFT) polymerization of acrylonitrile (AN) mediated by 2-cyanoprop-2-yl dithiobenzoate was first applied to synthesize polyacrylonitrile (PAN) with a high molecular weight up to 32,800 and a polydispersity index as low as 1.29. The key to success was ascribed to the optimization of the experimental conditions to increase the fragmentation reaction efficiency of the intermediate radical. In accordance with the atom transfer radical polymerization of AN, ethylene carbonate was also a better solvent candidate for providing higher controlled/living RAFT polymerization behaviors than dimethylformamide and dimethyl sulfoxide. The various experimental parameters, including the temperature, the molar ratio of dithiobenzoate to the initiator, the molar ratio of the monomer to dithiobenzoate, the monomer concentration, and the addition of the comonomer, were varied to improve the control of the molecular weight and polydispersity index. The molecular weights of PANS were validated by gel permeation chromatography along with a universal calibration procedure and intrinsic viscosity measurements. H-1 NMR analysis confirmed the high chain-end functionality of the resultant polymers.

Chain propagation kinetics on melt grafting reaction

Graft copolymerization in the molten state is of fundamental importance as a probe of chemical modification and reactive compatibilization. However, few grafting kinetic studies on reactive extrusion have been carried out because of the inherent difficulties, as expected. In this work, we have studied chain propagation kinetics on melt grafting using pre-irradiated linear low density polyethylene (LLDPE) and three monomers, acrylic acid (AA), methacrylic acid (MAA), and methyl methacrylate (MMA), as the model system. We measured the apparent chain propagation rate coefficients of grafting (k(p,g)) and homopolymerization (k(p,h)) at an initial stage for the melt grafting by FT-IR spectroscopy and electron spin resonance spectroscopy. It was observed that the convective mixing affected the rate coefficients. The magnitude of k(p,h) and k(p,g) were in the same order, but k(p,h) was slightly larger than k(p,g) The k(p,g) of the three grafting systems increased in the order: LLDPE/MMA < LLDPE/MAA < LLDPE/AA. These results are explained in terms of phase separation, solubility, and inherent reactivity of the monomer.

Kinetics study on melt grafting copolymerization of LLDPE with acid monomers using reactive extrusion method

Graft copolymerization in the molten state is of fundamental importance as a probe of chemical modification and reactive compatibilization. However, few grafting kinetics studies on reactive extrusion were carried out for the difficulties as expected. In this work, the macromolecular peroxide-induced grafting of acrylic acid and methyl methacrylate onto linear low density polyethylene by reactive extrusion was chosen as the model system for the kinetics study; the samples were taken out from the barrel at five ports along screw axis and analyzed by FTIR, H-1 NMR, and ESR. For the first time, the time-evolution of reaction rate, the reaction order, and the activation energy of graft copolymerization and homopolymerization in the twin screw extruder were directly obtained. On the basis of these results, the general reaction mechanism was tentatively proposed. It was demonstrated that an amount of chain propagation free radicals could keep alive for several minutes even the peroxides completely decomposed and the addition of monomer to polymeric radicals was the rate-controlled step for the graft copolymerization.

Monte Carlo simulation of pulsed-laser polymerization in emulsion

The pulsed-laser polymerization in emulsions has been simulated by the Monte Carlo method. Our simulation shows that the best measure of the propagation rate coefficients K-p is the peak maximum of molecular weight distribution for microemulsions when the droplets are small. However, the inflection point at the low-molecular-weight side of the peaks provides the best measure of K-p of bigger droplets. (C) 2000 Elsevier Science Ltd. All rights reserved.

Microelectrode voltammetric measurement of heterogeneous electron transfer rate constants for reduction of 7,7,8 ',8 '-tetracyanoquinodimethane in polymer electrolytes

This paper presents a microelectrode voltammetric determination of heterogeneous electron transfer rate constants (k(s)) and diffusion coefficients (D) of 7,7,8',8 '-tetracyanoquinodimethane (TCNQ) in polyelectrolytes. The diffusion coefficients are estimated using cyclic voltammetry under linear diffusion conditions, and the heterogeneous electron transfer rate constants are obtained under mixed linear and radial diffusion in the polyelectrolyte. k(s) and D increase with increasing temperature, and the activation barriers of the electrode reaction for reduction of TCNQ are obtained. On the other hand, the dependencies of D and k(s) of TCNQ on the size and charge of the counterion are compared in the polyelectrolyte. (C) 1998 Elsevier Science Ltd. All rights reserved.

Deformation, Phase Transformation and Recrystallization in the Shear Bands Induced by High-Strain Rate Loading in Titanium and its Alloys

alpha-titanium and its alloys with a dual-phase structure (alpha+beta) were deformed dynamically under strain rate of about 10(4) s(-1). The formation and microstructural evolution of the localized shear bands were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results reveal that both the strain and strain rate should be considered simultaneously as the mechanical conditions for shear band formation, and twinning is an important mode of deformation. Both experimental and calculation show that the materials within the bands underwent a superhigh strain rate (9 x 10(5) s(-1)) deformation, which is two magnitudes of that of average strain rate required for shear band formation; the dislocations in the bands can be constricted and developed into cell structures; the phase transformation from alpha to alpha(2) within the bands was observed, and the transformation products (alpha(2)) had a certain crystallographic orientation relationship with their parent; the equiaxed grains with an average size of 10 mu m in diameter observed within the bands are proposed to be the results of recrystallization.

Monte-Carlo simulation of surface crack growth rate for offshore structural steel E36-Z35

The Monte- Carlo method is used to simulate the surface fatigue crack growth rate for offshore structural steel E36-Z35, and to determine the distributions and relevance of the parameters in the Paris equation. By this method, the time and cost of fatigue crack propagation testing can be reduced. The application of the method is demonstrated by use of four sets of fatigue crack propagation data for offshore structural steel E36-Z35. A comparison of the test data with the theoretical prediction for surface crack growth rate shows the application of the simulation method to the fatigue crack propagation tests is successful.

Characteristic Dimensionless Numbers in Multi-Scale and Rate-Dependent Processes

For this sake, the macroscopic equations of mechanics and the kinetic equations of the microstructural transformations should form a unified set that be solved simultaneously. As a case study of coupling length and time scales, the trans-scale formulation

Kramers Escape Rate in Nonlinear Diffusive Media

In this paper, we study nonlinear Kramers problem by investigating overdamped systems ruled by the one-dimensional nonlinear Fokker-Planck equation. We obtain an analytic expression for the Kramers escape rate under quasistationary conditions by employing