Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (C_trs) determined using the Mayo method is equal to 3.8 × 10^?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10^?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the M_n data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007     

Diblock copolymers based on allyl methacrylate: Synthesis,characterization, and chemical modification

Different diblock copolymers constituted by one segment of a monomer supporting a reactive functional group, like allyl methacrylate (AMA), were synthesized by atom transfer radical polymerization (ATRP). Bromo‐terminated polymers, like polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(butyl acrylate) (PBA) were employed as macroinitiators to form the other blocks. Copolymerizations were carried out using copper chloride with N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as the catalyst system in benzonitrile solution at 70 °C. At the early stage, the ATRP copolymerizations yielded well‐defined linear block copolymers. However, with the polymerization progress a change in the macromolecular architecture takes place due to the secondary reactions caused by the allylic groups, passing to a branched and/or star‐shaped structure until finally yielding gel at monomer conversion around 40% or higher. The block copolymers were characterized by means of size exclusion chromatography (SEC), ¹H NMR spectroscopy, and differential scanning calorimetry (DSC). In addition, one of these copolymers, specifically P(BA‐b‐AMA), was satisfactorily modified through osmylation reaction to obtain the subsequent amphiphilic diblock copolymer of P(BA‐b‐DHPMA), where DHPMA is 2,3‐dihydroxypropyl methacrylate; demonstrating the feasibility of side‐chain modification of the functional obtained copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3538–3549, 2007     

不连续双斜向内肋管纵向涡流动显示

利用染色线流动显示方法,显示并分析了不同雷诺数下不连续双斜向内肋管管内流场。流动显示实验结果表明不连续双斜向内肋管管内存在较强的贴近壁面的纵向涡,纵向涡沿流向可持续约一倍管径距离,并且纵向涡的强度随雷诺数的增加而增强。     

The Level-split of the Two-level Entangled Atom in an Optical Field

The behavior of a two-level entangled atom in an optical field with circular polarization is studied in this paper. The interaction of an optical field and one of the entangled atoms is analyzed in detail. A general solution of the SchrAo¨Gdinger equation about the motion of the entangled atom is obtained. The properties of the action are dependent on the initial state of the atom. By detecting the entangled atom out of the field, we can obtain the state of the other atom moving in the field. It is shown that the state of the atom out of the field will influence the energies of the split-levels of the atom in the field.     

Effect of end groups on complexation kinetics between cyclodextrins and guest polymers

α‐Cyclodextrin (α‐CD) has been complexed with various poly(ethylene glycol) (PEG) derivatives in aqueous solution. It has been found that the end groups of PEG derivatives affect the complexation kinetics greatly, but have only a little influence on the thermodynamic behavior. By increasing the hydrophobicity of end groups, the complexation speeds up rapidly. On the other hand, the bulky end groups slow down the threading of polymeric guests into the cavity of CD. By changing the hydrophobicity and the size of end groups, the complexation rate can be adjusted in the range of several orders of magnitudes, which should be quite useful in the design of new supramolecular systems. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2050–2057, 2006     

Plasticity field adjacent to faces of asperities on a rotating roll after initial indentation into a half-space

The plastic deformation field near the horizontal surface of a half space of perfectly plastic material associated with an indenting rotating rigid tooth is studied using slip line theory. The tooth is one of many on a roll surface and indents first into the half-space material and then rotates about the roll center. A slip line field is proposed for the deforming plastic region and a solution scheme is outlined. The emphasis is on determining the shape of the deforming region, especially that of the free surface. The study has a potential application in roughness transfer in metal forming processing.     

一维无序体系电子跳跃导电研究

建立了电子隧穿电导模型,推导了一维无序体系新的直流电导公式.通过计算20000格点无序体系的直流电导率,分析了直流电导率和温度及外场电压的关系,讨论了无序度对直流电导的影响.计算结果表明,无序体系的直流电导率随无序度的增加而减小;外加电场较小时,电导率相对较大,且出现一系列峰值,电压较大时,电导率反而较小;无序体系在低温区出现了负微分电阻特性,电导率随温度的升高而增大,在高温区电导率随温度的升高而减小.计算结果和实验符合很好 关键词： 无序体系 电子隧穿 直流电导率     

双面电弧焊接的传热模型

将等离子焊接(PAW)电弧和钨极氩弧焊(TIG)电弧串接,相对作用于工件的正反面形成双面电弧焊接(DSAW)系统,可以引导焊接电流沿工件厚度方向流过小孔,补偿等离子电弧穿透工件时消耗的能量,以有效地提高等离子弧的穿透能力.综合考虑影响双面电弧焊接正反面熔池几何形状的力学因素,建立了熔池表面变形的控制方程,以此为基础并采用帖体曲线坐标系建立了DSAW焊接传热的数学模型,分析了DSAW,PAW焊接传热的差异,从传热的角度解释了DSAW焊接熔深增加的原因.焊接工艺实验表明,计算结果与实测结果吻合良好. 关键词： 双面电弧焊接(DSAW) 传热模型 熔池表面变形模型     

Isothermal crystallization kinetics of poly(3‐hydroxybutyrate)/layered double hydroxide nanocomposites

Poly(3‐hydroxybutyrate) (PHB)/layered double hydroxides (LDHs) nanocomposites were prepared by mixing PHB and poly(ethylene glycol) phosphonates (PEOPAs)‐modified LDH (PMLDH) in chloroform solution. Both X‐ray diffraction data and TEM micrographs of PHB/PMLDH nanocomposites indicate that the PMLDHs are randomly dispersed and exfoliated into the PHB matrix. In this study, the effect of PMLDH on the isothermal crystallization behavior of PHB was investigated using a differential scanning calorimeter (DSC) and polarized optical microscopy. Isothermal crystallization results of PHB/PMLDH nanocomposites show that the addition of 2 wt % PMLDH into PHB induced more heterogeneous nucleation in the crystallization significantly increasing the crystallization rate and reducing their activation energy. By adding more PMLDH into the PHB probably causes more steric hindrance of the diffusion of PHB, reducing the transportation ability of polymer chains during crystallization, thus increasing the activation energy. The correlation among crystallization kinetics, melting behavior and crystalline structure of PHB/PMLDH nanocomposites can also be discussed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 3337–3347, 2006     

Error estimation,adaptivity and data transfer in enriched plasticity continua to analysis of shear band localization

In this paper, an adaptive FE analysis is presented based on error estimation, adaptive mesh refinement and data transfer for enriched plasticity continua in the modelling of strain localization. As the classical continuum models suffer from pathological mesh-dependence in the strain softening models, the governing equations are regularized by adding rotational degrees-of-freedom to the conventional degrees-of-freedom. Adaptive strategy using element elongation is applied to compute the distribution of required element size using the estimated error distribution. Once a new mesh is generated, state variables and history-dependent variables are mapped from the old finite element mesh to the new one. In order to transfer the history-dependent variables from the old to new mesh, the values of internal variables available at Gauss point are first projected at nodes of old mesh, then the values of the old nodes are transferred to the nodes of new mesh and finally, the values at Gauss points of new elements are determined with respect to nodal values of the new mesh. Finally, the efficiency of the proposed model and computational algorithms is demonstrated by several numerical examples.