Kinetics and mechanism of polymerization of methyl methacrylate initiated by stibonium ylide

Homopolymerization of methyl methacrylate (MMA) was carried out in the presence of triphenylstibonium 1,2,3,4-tetraphenyl-cyclopentadienylide as an initiator in dioxane at 65°C±0·l°C. The system follows non-ideal radical kinetics (R _p ∝ [M]^1·4 [I]^0·44 @#@) due to primary radical termination as well as degradative chain-transfer reaction. The overall activation energy and average value ofk ₂ ^p /k _t were 64 kJmol⁻¹ and 0.173 × 10⁻³ 1 mol⁻¹ s⁻¹ respectively     

Deactivation reactions in the modeled 2,2,6,6‐tetramethyl‐1‐piperidinyloxy‐mediated free‐radical polymerization of styrene: A comparative study with the 2,2,6,6‐tetramethyl‐1‐piperidinyloxy/acrylonitrile system

The competitiveness of the combination and disproportionation reactions between a 1‐phenylpropyl radical, standing for a growing polystyryl macroradical, and a 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO) radical in the nitroxide‐mediated free‐radical polymerization of styrene was quantitatively evaluated by the study of the transition geometry and the potential energy profiles for the competing reactions with the use of quantum‐mechanical calculations at the density functional theory (DFT) UB3‐LYP/6‐311+G(3df, 2p)//(unrestricted) Austin Model 1 level of theory. The search for transition geometries resulted in six and two transition structures for the radical combination and disproportionation reactions, respectively. The former transition structures, mainly differing in the out‐of‐plane angle of the N? O bond in the transition structure TEMPO molecule, were correlated with the activation energy, which was determined to be in the range of 8.4–19.4 kcal mol^?1 from a single‐point calculation at the DFT UB3‐LYP/6‐311+G(3df, 2p)//unrestricted Austin Model 1 level. The calculated activation energy for the disproportionation reaction was less favorable by a value of more than 30 kcal mol^?1 in comparison with that for the combination reaction. The approximate barrier difference for the TEMPO addition and disproportionation reaction was slightly smaller for the styrene polymerization system than for the acrylonitrile polymerization system, thus indicating that a β‐proton abstraction through a TEMPO radical from the polymer backbone could diminish control over the radical polymerization of styrene with the nitroxide even more than in the latter system. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 232–241, 2007     

Measurement of acoustic particle velocities in enclosed sound field: Assessment of two Laser Doppler Velocimetry measuring systems

The performances of two Laser Doppler Velocimetry (LDV) systems adapted for measuring the acoustic particle velocities are assessed in enclosed sound field. This assessment is performed by comparing the acoustic velocities measured by means of LDV to reference acoustic velocities estimated from sound pressure measurements. The two LDV systems are based on a single optical bench which delivers an optical signal called Doppler signal. The Doppler signal, which is frequency modulated, is analyzed by means of two signal processing systems, the BSA (Burst Spectrum Analyser from Dantec) on the one hand, and a system specifically developed for the estimation of the acoustic velocity on the other hand. Once the experimental setup has been optimized for minimizing the errors made on the reference velocities, the assessment is performed and shows that both systems can measure the acoustic velocity in enclosed field in two the frequency ranges [0-4 kHz] and [0-2 kHz] respectively for acoustic velocity amplitudes of 10 mm/s and 1 mm/s.     

Synthesis of graft copolymers with “V‐shaped” and “Y‐shaped” side chains via controlled radical and anionic polymerizations

A combination of nitroxide‐mediated radical polymerization and living anionic polymerization was used to synthesize a series of well‐defined graft (co)polymers with “V‐shaped” and “Y‐shaped” branches. The polymer main chain is a copolymer of styrene and p‐chloromethylstyrene (PS‐co‐PCMS) prepared via nitroxide‐mediated radical polymerization. The V‐shaped branches were prepared through coupling reaction of polystyrene macromonomer, carrying 1,1‐diphenylethylene terminus, with polystyryllithium or polyisoprenyllithium. The Y‐shaped branches were prepared throughfurther polymerization initiated by the V‐shaped anions. The obtained branches, carrying a living anion at the middle (V‐shaped) or at the end of the third segment (Y‐shaped), were coupled in situ with pendent benzyl chloride of PS‐co‐PCMS to form the target graft (co)polymers. The purified graft (co)polymers were analyzed by size exclusion chromatography equipped with a multiangle light scattering detector and a viscometer. The result shows that the viscosities and radii of gyration of the branched polymers are remarkably smaller than those of linear polystyrene. In addition, V‐shaped product adopts a more compact conformation in dilute solution than the Y‐shaped analogy. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4013–4025, 2007     

Synthesis and characterization of liquid crystalline side‐chain block copolymers containing luminescent 4,4′‐bis(biphenyl)fluorene pendants

A series of new liquid crystalline homopolymers, copolymers, and block copolymers were polymerized from styrene‐macroinitiator ( SMi ) and methacrylates with pendent 4,4′‐bis(biphenyl)fluorene ( M1 ) and biphenyl‐4‐ylfluorene ( M2 ) groups through atom transfer radical polymerization (ATRP). The number‐average molecular weights (Mn) of polymers P1 ‐ P4 were 10,007, 14,852, 6,275, and 10,463 g mol^?1 with polydispersity indices values of 1.21, 1.15, 1.31, and 1.22, respectively. All polymers exhibit the nematic phase. The thermal, mesogenic, and photoluminescent properties of all polymers were investigated. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4564–4572, 2007     

Monitoring photopolymerization reactions with optical pyrometry

This article describes the development of optical pyrometry (OP) as a new analytical technique for the continuous monitoring of the progress of both free‐radical and cationic photopolymerizations. The method is rapid, reproducible, and very easy to implement. A temperature profile of a photopolymerization can be obtained. Preliminary studies have shown that the temperatures of some polymerizing monomers can easily reach temperatures in excess of 250 °C. The effects of the mass and reactivity of the monomer, light intensity, structures, and concentrations of the photoinitiators and monomers as well as the presence or absence of oxygen on various free‐radical and cationic photopolymerizations were examined with this method. Coupling of real‐time infrared spectroscopy with OP provides a convenient method for simultaneously monitoring both the chemical conversion and the temperature of a photopolymerization. This combined technique affords new insights into the effects of temperature‐induced autoacceleration on the course of photopolymerizations. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 579–596, 2003     

Calculation of impulsively started incompressible viscous flows

The paper's focus is the calculation of unsteady incompressible 2D flows past airfoils. In the framework of the primitive variable Navier–Stokes equations, the initial and boundary conditions must be assigned so as to be compatible, to assure the correct prediction of the flow evolution. This requirement, typical of all incompressible flows, viscous or inviscid, is often violated when modelling the flow past immersed bodies impulsively started from rest. Its fulfillment can however be restored by means of a procedure enforcing compatibility, consisting in a pre‐processing of the initial velocity field, here described in detail. Numerical solutions for an impulsively started multiple airfoil have been obtained using a finite element incremental projection method. The spatial discretization chosen for the velocity and pressure are of different order to satisfy the inf–sup condition and obtain a smooth pressure field. Results are provided to illustrate the effect of employing or not the compatibility procedure, and are found in good agreement with those obtained with a non‐primitive variable solver. In addition, we introduce a post‐processing procedure to evaluate an alternative pressure field which is found to be more accurate than the one resulting from the projection method. This is achieved by considering an appropriate ‘unsplit’ version of the momentum equation, where the velocity solution of the projection method is substituted. Copyright © 2004 John Wiley & Sons, Ltd.     

Damage and fracture evaluation of granular composite materials by digital image correlation method

This paper presents the applications of digital image correlation technique to the mesoscopic damage and fracture study of some granular based composite materials including steelfiber reinforced concrete, sandstone and crystal-polymer composite. The deformation fields of the composite materials resulted from stress localization were obtained by the correlation computation of the surface images with loading steps and thus the related damage prediction and fracture parameters were evaluated. The correlation searching could be performed either directly based on the gray levels of the digital images or from the wavelet transform (WT) coefficients of the transform spectrum. The latter was developed by the authors and showed higher resolution and sensitivity to the singularity detection. Because the displacement components came from the rough surfaces of the composite materials without any coats of gratings or fringes of optical interferometry, both surface profiles and the deformation fields of the composites were visualized which was helpful to compare each other to analyze the damage of those heterogeneous materials. The project supported by the National Natural Science Foundation of China (10125211 and 10072002), the Scientific Committee of Yunnan Province for the Program of Steel Fiber Reinforced Concrete, and the Institute of Chemical Materials, CAEP at Mianyang     

Modification of Spatial Coherence by Means of Low-Order Zernike-Mode Adaptive Optics

Spatial coherence of the field modified by low-order adaptive optics is analyzed to establish a theoretical basis for the recent idea of using adaptive optics as a spatial coherence modifier. In this context low-order adaptive optics has the ability to correct some of the low-order aberrations specified by Zernike polynomials. The initial field to be modified is assumed to be a spatially partially coherent one resulting from phase disturbance. It is demonstrated, as in the previous study, that low-order adaptive optics serves to enhance the spatial coherence of the resultant field and that the effect of the enhancement becomes stronger as the spatial coherence of the initially partially coherent field increases. Potential applications of low-order adaptive optics as a spatial coherence modifier are briefly discussed.     

Renormalization Effects in the Spectrum of a Coherently Driven Exciton–Biexciton System

Starting from the total Hamiltonian of an excited exciton–biexciton system, nonresonant renormalizations in the electronic spectrum of a coherently driven direct semiconductor are considered. Stringent group-theoretical inclusion of the particle spin in the Hamiltonian allows one to account for the dependence of different renormalization effects on polarizations of the incident laser fields. On the example of circularly polarized driving and probing pulses it is shown that the kind of observed renormalization is defined by the pump-and-probe polarization geometry. Thus, the exciton optical Stark effect must appear in the case of co-circular pump-and-probe, whereas a mixing of the polariton and biexciton spectra is possible only in the case of counter-circular pump-and-probe. The polariton--biexciton dispersion renormalization may manifest itself as synchronous splittings of the exciton--polariton and biexciton spectra under resonant pumping at a frequency of the polariton--biexciton transition, or in their shifts in opposite directions under near-resonant pumping. The mechanisms of both kinds of renormalization effects are analyzed, and the dependence of their characteristics on the pump parameters and microscopic parameters of the exciton–biexciton–photon system is established. An evaluation of the characteristics shows that the effect of polariton–biexciton dispersion renormalization dominates in the spectra of semiconductors with stable biexciton formation. Results of the theoretical study provide an adequate explanation of available experimental data.