Shape Hessian for generalized Oseen flow by differentiability of a minimax: A Lagrangian approach

The goal of this paper is to compute the shape Hessian for a generalized Oseen problem with nonhomogeneous Dirichlet boundary condition by the velocity method. The incompressibility will be treated by penalty approach. The structure of the shape gradient and shape Hessian with respect to the shape of the variable domain for a given cost functional are established by an application of the Lagrangian method with function space embedding technique. This work was supported by the National Natural Science Fund of China (No. 10371096) for ZM Gao and YC Ma.     

TERAHERTZ QUALITY CONTROL OF POLYMERIC PRODUCTS

We report on experiments that evaluate the potential of terahertz (THz) time-domain spectroscopy (TDS) for quality control of polymeric compounds. We investigate specimens out of a polyethylene compound with silver-coated titanium dioxide nanospheres and a glass-fiber reinforced epoxy composite. We further examine an industrial polymer product produced by injection molding. Our data demonstrates that THz imaging is a powerful tool for contactless quality control in the polymer industry.     

基于任意形状颗粒集合二值图像的体积估算模型

基于任意形状颗粒集合的二值图像,提出了估计其体积(或质量)的方法.首先利用发光背景台面获取的颗粒灰度图像变换为相应的二值图像,得到颗粒的边界轮廓.然后再基于其边界信息,定义与颗粒形状特征相关的描述量,并将其无量纲化.将由此定义的无量纲参变量作为回归变量建立一个多元线性回归(multiple linear regression)模型用以估计颗粒集合的扁平度,进而估算颗粒体积.回归变量的系数由随机采样的501个样本颗粒(尺寸范围为4.75～25 mm)用误差最小平方和求得.将模型应用于由具有相似统计分布特征的其他颗粒集合,并将得到的体积估计值与其体积真实值相比较,实验结果显示模型的相对误差在±2%以内.     

Synthesis of optically active poly(N‐propargylsulfamides) with helical conformation

A novel chiral N‐propargylsulfamide monomer ( 1a ) and its enantiomer ( 1b ) were synthesized and polymerized with (nbd)Rh⁺B^?(C₆H₅)₄ as a catalyst providing poly(1) (poly( 1a ) and poly( 1b )) in high yields (≥99%). Poly(1) could take stable helices in less polar solvents (chloroform and THF), demonstrated by strong circular dichroism signals and UV–vis absorption peaks at about 415 nm and the large specific rotations; but in more polar solvents including DMF and DMSO, poly(1) failed to form helix. Quantitative evaluation with anisotropy factor showed that the helical screw sense had a relatively high thermal stability. These results together with the IR spectra measured in solvents showed that hydrogen bonding between the neighboring sulfamide groups is one of the main driving forces for poly(1) to adopt stable helices. In addition, copolymerization of monomer 1a and monomer 2 was conducted, the solubility of poly(1) was improved drastically. However, the copolymerization had adverse effects on the formation of stable helices in the copolymers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 500–508, 2007     

Alternating copolyfluorenevinyles with polynuclear aromatic moieties: Synthesis,photophysics, and electroluminescence

Three new copolymers, namely poly(fluorenevinylene‐alt‐naphthalenevinylene) ( N ), poly(fluorenevinylene‐alt‐anthracenevinylene) ( A ) and poly(fluorenevinylene‐alt‐pyrenevinylene) ( P ), were synthesized by Heck coupling of 9,9‐dihexyl‐2, 7‐divinylfluorene with a polynuclear aromatic dibromide. The 9,10‐disubstituted anthracene was obtained exclusively for A while N and P were obtained as a mixture of two isomers with predominant the 1,4‐disubstituted naphthalene and 1,8‐disubstituted pyrene, respectively. The polymers were soluble in common organic solvents and decomposed above 370 °C. Their glass transition temperature increased from 58 to 110 °C by increasing the number of the phenyl rings of the polynuclear aromatic moiety. Rather high‐efficiency blue and blue‐greenish photoluminescence (PL) of these copolymers in solution was largely decreased in their films, indicating the presence of concentration quenching in the solid state. The OLED using these polymers demonstrated green EL in the case of copolymers N and A , and red EL in the P derivative with η_EL = 0.26–0.31%. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4661–4670, 2007     

Cationic poly(methacryl oxyethyl trimethylammonium) and its poly(ethylene glycol)‐grafted analogue as capillary coating materials in electrophoresis

Cationic polyelectrolytes were synthesized and used as semipermanent coating materials for capillaries in electrophoresis. The polyelectrolytes used were a homopolymer of poly(methacryl oxyethyl trimethylammonium chloride) (PMOTAC) and its poly(ethylene glycol) (PEG)‐grafted analogue. Two PMOTAC polyelectrolytes, with molar masses of 85,000 and 300,000 g/mol, and PEG‐grafted PMOTAC with a molar mass of 280,000 g/mol were synthesized and then characterized by size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) spectroscopy. Attachment of the polyelectrolytes to the wall of the fused silica capillary for electrophoresis caused the electroosmotic flow (EOF) to reverse. The polyelectrolyte coatings were tested over the pH range 2–11 at different buffer ionic strengths, and the most stable and strongest anodic EOFs were obtained at acidic pH values with low ionic strength buffers. Between runs the capillary is merely rinsed for 2 or 3 min with the background electrolyte solution. With the PMOTAC coatings at pH values ≤5, the RSDs of the EOFs were less than 2.9% after 60 injections. The effects of the molar mass of the polycation and of PEGylation of PMOTAC on the interactions between the polycations and basic proteins were studied at acidic pH values. The differences in the effective electrophoretic mobilities, resolution values, and plate numbers of the proteins with the different coatings were due to the EOF, as demonstrated through calculations of reduced mobilities, relative resolution values, and relative plate numbers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2655–2663, 2007     

Synthesis of grafted poly(p‐phenyleneethynylene) with energy donor–acceptor architecture via atom transfer radical polymerization: Towards nonaggregating and hole‐facilitating light‐emitting material

In this contribution, we demonstrate a new effective methodology for constructing highly efficient and durable poly(p‐phenyleneethynylene) (PPE) containing emissive material with nonaggregating and hole‐facilitating properties through the introduction of hole‐transporting blocks into the PPE system as the grafting coils as well as building the energy donor–acceptor architecture between the grafting coils and the PPE backbone. Poly(2‐(carbazol‐9‐yl)ethyl methacrylate) (PCzEMA), herein, is chosen as the hole‐transporting blocks, and incorporated into the PPE system as the grafting coils via atom transfer radical polymerization. The chemical structure of the resultant copolymer, PPE‐g‐PCzEMA, was characterized by NMR and gel permeation chromatography, showing that the desirable copolymer was obtained with the narrow polydispersity. The increased thermal stability of PPE‐g‐PCzEMA was confirmed by thermogravimetric analysis and differential scanning calorimetry along with its macroinitiator. The optoelectronic properties of this copolymer were studied in detail by ultraviolet‐visible absorption, photoluminescence emission and excitation spectra, and cyclic voltammogram (CV). The results indicate that PPE‐g‐PCzEMA exhibits the solid‐state luminescent property dominated by individual lumophores, and also the energy transfer process from the PCzEMA blocks to the PPE backbone with a relatively higher energy transfer efficiency in the solid‐state compared to that of the solution state. Additionally, the hole‐injection property is greatly facilitated due to the presence of PCzEMA, as confirmed by CV profiles. All these data indicate that PPE‐g‐PCzEMA is a good candidate for use in optoelectronic devices. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3776–3787, 2007     

Thermally stimulated current and DSC studies of the broadened glass transition in liquid crystalline polymers

The high sensitivity of the thermally stimulated current, thermal sampling (TS) method is emphasized in a study of the breadth of the glass transition in several liquid-crystalline polymers (LCPs). Differential scanning calorimetry (DSC) was performed on all samples to further quantify the glass transition regions. For “random” copolyester LCPs with widely varying degrees of crystallinity, including highly amorphous samples, very broad glass tran-sition regions were observed. One semicrystalline alternating copolyester and a series of semicrystalline azomethine LCPs were studied as examples of structurally regular polymers. These exhibited relatively sharp glass transitions more comparable to ordinary isotropic amorphous or semicrystalline polymers. The broad glass transitions in the random copolyesters are attributed to structural heterogeneity of the chains. In one example of a moderate-crystallinity random copolyester LCP (Vectra), glass transitions ranging up to ca. 150°C in breadth were determined by the thermal sampling (TS) method and DSC. In other lower crystallinity copolyester LCPs, the main glass transition temperature as determined by DSC was comparable to that determined by TSC although cooperative relaxations of a minor fraction of the overall relaxing species were detected well below the main T_g, by the TS method and not by DSC. Rapid quenches from the isotropic melt to an isotropic glass were possible with one LCP. The anisotropic and isotropic glassy states for this LCP were found to have the same breadth of the glass transition as was determined by the TS method, although TSC and DSC show that T_g is shifted downward by ca. 15°C in the anisotropic glass as compared to the isotropic glass. © 1993 John Wiley & Sons, Inc.     

A tentative approach to the direct simulation of drag reduction by polymers

An efficient technique for drag reduction uses dilute solutions of a few p.p.m. of polymers. A possible reduction in drag of up to 80% is achieved. Several experimental observations have been made which tend to indicate that the polymers modify the turbulence structures within the buffer layer. Flow visualisations have shown that the changes consist of a weakening of the strength of the streamwise vortices. Existing literature reveals no attempts of numerical simulation of this phenomenon. In this paper an approach is pursued by using a constitutive equation which relates the elongation viscosity to the local properties of the flow. According to this model this viscosity is large in zones where the amount of strain rate is greater than the amount of vorticity, and is zero when the vorticity exceeds the strain rate. Simulations have been performed in a “minimal channel” to give good resolution with a limited number of grid points. The accuracy of the method is tested by comparison with the results of other techniques. For simulations with polymers, quantitative comparisons cannot be made, but the results reproduce the qualitative outputs of the experiments. The mean streamwise velocity is modified in the buffer layer; the peak of the streamwise turbulent intensity, in wall units, increases and its maximum moves far from the wall; and the vertical turbulent intensity is largely reduced in the wall region. An interesting outcome from both the simulation and the experiments is that the strength of the longitudinal vortices is reduced when the polymers are present.