Vinyl‐terminated side‐chain liquid‐crystalline polyethers containing mesogenic benzylideneaniline moieties

The synthesis of two vinyl‐terminated side‐chain liquid‐crystalline polyethers containing benzylideneaniline moieties as mesogenic cores was approached in two different ways: by chemically modifying poly(epichlorohydrin) with suitable mesogenic acids or by polymerizing analogous glycidyl ester or glycidyl ether derivatives. In all the conditions tested, the first approach led to materials in which the imine group was hydrolyzed. The second approach led to the desired polymers PG2a and PG2b , but only from the glycidyl ether derivatives and when the initiator was the system that combined polyiminophosphazene base t‐Bu‐P₄ and 3,5‐di‐t‐butylphenol. These polymers were chemically characterized by IR and ¹H and ¹³C NMR spectroscopies. The estimated degrees of polymerization ranged from 30 to 36. The liquid crystalline behavior of the synthesized polymers was studied by differential scanning calorimetry, polarized optical microscopy (POM) and X‐ray diffraction. Both polymers behave like liquid crystals and exhibited a single mesophase, which was recognized as a smectic C mesophase, probably with a bilayer arrangement, i.e., a smectic C₂ mesophase. The crosslinking of both polymers was performed with dicumyl peroxide as initiator, which led to liquid crystalline thermosets. POM and X‐ray diffraction confirmed that the mesophase organization mantained on the crosslinked materials. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1877–1889, 2006     

Design,synthesis, and characterization of main‐chain,aromatic polyesters based on 3,4‐ethylenedioxythiophene

A series of new thermoplastic polyesters based on 3,4‐ethylenedioxythiophene (EDOT) with flexible aliphatic spacers have been synthesized and characterized for the first time. The thermal properties of these polyesters based on EDOT are comparable to those of conventional polyesters based on the 1,4‐phenyl unit, indicating that EDOT is a viable replacement for the phenyl units. The glass‐transition and melting‐transition temperatures decrease monotonically with an increase in the spacer length. Theoretical calculations have revealed that the core angle for EDOT is comparable to that of unsubstituted thiophene and hence should be compatible with the formation of the mesophase. This has been confirmed experimentally by the synthesis of a main‐chain, thermotropic, liquid‐crystalline polyester based on EDOT that exhibits fluid birefringence. In fact, this is the first report in which a main‐chain, liquid‐crystalline polymer based on 3,4‐disubstituted thiophene has been successfully designed and synthesized. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3479–3486, 2006     

Effect of glass bead packing on the fibrillation of liquid‐crystalline polymer in polycarbonate

Polycarbonate (PC) was melt blended with small amount of liquid‐crystalline polymer (LCP) and various contents of glass beads (GB) having different diameters. The rheological measurements indicated that the GB addition increased the viscosity ratio and seemed unfavorable to the LCP fibrillation. However, the morphological observation showed that the LCP fibrillation was promoted by the GB addition and varied with the GB packing. With the increased GB packing by increasing the GB content and/or decreasing the GB diameter, LCP deformed from spheres and ellipsoids into stretched ellipsoids at lower shear rates and into long fibrils at higher shear rates. Although higher content of smaller GB jammed into the larger LCP droplets and inhibited the LCP fibrillation, very long LCP fibrils formed at higher shear rates at a high enough packing of GB. The relationship between GB packing and LCP fibrillation revealed two kinds of hydrodynamic effects of GB promoting the LCP fibrillation: at lower GB packing, the shear flow was enhanced by the high local shear between GB, in quantity; and for a high enough GB packing, the shear flow was changed, in quality, into elongational flow, which was more effective for the LCP fibrillation. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1020–1030, 2006     

On the evolution of two-dimensional patterns in an inviscid liquid sheet

We perform an analysis of the pattern formation for a moving sheet of inviscid fluid. The sheet, which is assumed to have an infinite horizontal extent, moves at some prescribed velocity into a passive surrounding gas. The sheet’s thickness is assumed much smaller than the horizontal scale of the fluid motion. By considering a system that is symmetric with respect to the horizontal planes, long scale asymptotics are used to reduce the full governing equations in three dimensions to a set of three coupled nonlinear partial differential equations for the horizontal components of the velocity field and the height of the interface profile. The interfacial conditions consisting of the kinematic and normal stress balance are incorporated into these evolution equations. Investigations are carried out as function of the sole dimensionless parameter, namely the Weber number. A small amplitude stability analysis around the planar gas–liquid interface reveals that wave patterns in the form of traveling plane waves occur subcritically, and are therefore unstable. The reduced evolution equations are solved numerically for fixed values of the Weber number. Since the reduced system of equations is homogeneous, the wave motion is generated by initial conditions. Five initial conditions have been imposed: one-dimensional rolls, two-dimensional squares, two-dimensional hexagons, two-dimensional ridges, and smooth peaks. The ensuing evolution of the liquid sheet’s shape and corresponding flow fields are described by illustrations of the changes in the sheet’s morphology with time.     

甲醇与蓖麻油混合物运动粘度的实验研究

利用改型的乌别洛特毛细管粘度计,本文对243～353K温度范围内对质量配比为98.8:1.2的甲醇与蓖麻油混合物的运动粘度进行了实验研究,运动粘度测量结果的不确定度为1.06%,利用得到的实验数据拟合了甲醇 蓖麻油二元混合物的运动粘度方程.方程与实验数据最大偏差为3.31%,平均偏差为1.11%.     

基于界面跟踪方法的汽蚀模型和算法的有效性验证

针对两相附着汽蚀流动机理,基于界面跟踪方法发展了新的汽蚀模型和算法。所发展的汽蚀模型和算法不仅考虑了液相／气相界面处的压力差,而且考虑了耦合Reynolds-Averaged Navier-Stokes方程求解技术得到的流场压力梯度信息来迭代计算附着汽蚀形状。采用具有试验数据的半球形头部圆柱体汽蚀绕流作为算例来验证所提出的汽蚀模型和算法的有效性。采用不同的网格数和松弛因子数值验证了发展的汽蚀模型和算法的有效性。三种汽蚀数下的数值计算结果得到的压力系数分布与试验数据完全吻合。结果表明所提出的汽蚀模型和算法能够准确模拟出汽蚀发生点和汽蚀长度。     

Formation and magnetic properties of Co–Fe-based bulk metallic glasses with supercooled liquid region

A new Co–Fe-based ferromagnetic bulk metallic glass (BMG) was synthesized by copper mould casting method. The thermal stability and crystallization processes were investigated by differential scanning calorimetry (DSC) and X-ray diffraction (XRD). The soft magnetic behavior was studied by DC magnetic measurements. The high glass formation ability was interpreted in terms of the effective suppression of nucleation and growth of the intermetallic compounds which appear in the multicomponent system during solidification. The high thermal stability indicates that the new Co–Fe-based BMG could be used as high-temperature magnetic material. The low coercivity which was as low as 8 A/m for the as-cast sample was found in the Co–Fe-based metallic glass cylinder with a diameter of 1.5 mm.     

胶束液相色谱／安培电化学检测尿样中的扑热息痛及4－氨基苯酚

用胶束液相色谱／安培检测器检测尿样中的扑热息痛及其主要水解产物４－氨基苯酚。采用１４．５μｍ的碳纤维电极作为工作电极，以高于临界胶束浓度的阴离子表面活性剂十二烷基磺酸钠（ＳＤＳ）作为液相色谱的流动相，尿样直接进样分析，扑热息痛和４－氨基苯酚的检测限分别为０．１３ｎｍｏｌ／Ｌ及０．７３ｎｍｏｌ／Ｌ（Ｓ／Ｎ＝２）。     

An amperometric detector with a tubular electrode deposited on the capillary for capillary liquid chromatography

A procedure is described for the preparation of a tubular electrode by chemical deposition of platinum at the end of a fused-silica capillary. The properties of the electrode were tested under liquid chromatographic conditions, demonstrating that both the static and the dynamic behaviour of the detection system satisfy the requirements of capillary chromatographic separations and compare well with a wall-jet amperometric system and with UV photometric detection. The detection system described is easy to prepare and does not require any time-consuming positioning of the electrode system as it is integrated into the separation part of the apparatus.     

Thermal Analysis of the Conformational Disorder in SCLC Polymers with Rigid Backbone Glass transition studies

Bis [(ω-(4′-cyanobiphenyl)-4-yl)oxy-n-alkyl]norborn-5-ene-2,3-dicarboxylate was polymerised via ring opening metathesis polymerisation (ROMP). Two disubstituted polynorbornene derivatives both of cis configuration with different length of the side-chain were studied. Differential scanning calorimetry (DSC) was used to study the effect of thermal history on the assignment of the glass transition event associated with the biaxial orientation of a smectic phase. Glass transition temperatures, the change of isobaric specific heats at T_g and the enthalpies of isotropisation were calculated. The DSC traces only show the classic step-wise change in T_g in some cases, giving the evidence that the amorphous domains are constrained and highly restricted in movement due to the morphology developed as a result of the biaxial stretching. Based on the literature data of mono- and disubstituted polynorbornene derivatives and our calorimetric experiments, the shape of T_g dependence on number of (CH₂) units is interpreted. The origin of this shape is discussed. This revised version was published online in August 2006 with corrections to the Cover Date.