MECHANICAL PERTURBATION INDUCED MOLECULAR ALIGNMENTS IN A SIDE-CHAIN LIQUID CRYSTALLINE POLYACETYLENE, POLY{10-[4-(4''-METHOXYPHENOXY-CARBOML)PHENOXYCARBONYL]-1-DECYNE}*

A new liquid crystalline polyacetylene containing a phenyl benzoate mesogen (5) is synthesized,whose mesomorphic properties are found to be easily "tunab1e" by simple mechanical perturbation. Thepolymerization of 10- [ 4 - (4' -methoxyphenoxycarbonyl )phenoxycarbonyl] - 1 -decyne (4 ) in itiated by theWCl_6-Ph_4Sn/dioxane complex yields polymer 5 with a M_w of 28400. The molecular structure of 5 ischaracterized by NMR, IR, and UV spectroscopy and its liquid crystalline behavior is investigated by DSC,POM, and XRD analysis. Upon mechanical perturbation, 5 exhibits unusual agitation-induced high-strengthdisclinations, shear-induced inversion walls, and solidification-induced banded textures. Such phenomenahave been observed in the main-chain liquid crystalline polymers with rigid backbones, but have seldom beenreported for the side-chain liquid crystalline polymers with flexible backbones, suggesting that the rigidpolyacetylene backbone of 5 plays a constructive role in inducing the novel molecular alignments.     

DIPOLE POLARIZATION RELAXATION AND MOLECULAR STRUCTURE OF MAIN-AND SIDE-CHAIN LIQUID-CRYSTALLINE POLYMERS

Molecular mobility in thermotropic polyesters and side-chain polymers with different struc-ture of mesogens and spacers has been studied by dielectrical method in dilutesolutions. The results made it possible to establish the multiplicity of dielectric relaxationtransitions which reflects the small- and large-scale types of molecular motion. It was shownthat dielectric relaxation processes occurring in accordance with local mechanism (relaxationtimes 10~(-9)--10~(-7)s. and the activation energy 10--50kJ/mol) are due to the mobility of kineticchain elements of different length within a monomer units. It was found that the dielectricrelaxation process connected with a large-scale form of molecular motion (relaxation times10~(-5)--10~(-6)s. and the activation energy 100kJ/mol) did not depend on the molecular massbut was infiuenced by factors changing the conformational state of the macromolecule. It isestablished tha the cooperative reorientation mobility of associated mesogenic fragments isthe source of the large-scale process.     

Fabrication of high performance thin films from metal fluorocomplex aqueous solution by the liquid phase deposition

The hetro-structured oxide thin films from metal fluorocomplex solution have been prepared by the liquid phase deposition (LPD) method. The Pt/Nb₂O₅ and Au/Nb₂O₅ composite films can be prepared from a mixed solution of niobium source, H₃BO₃, Pt(NH₃)₄Cl₂ and HAuCl₄ aqueous solutions under the ambient temperature and atmosphere. In the case of Au/SiO₂ composite film, (NH₄)₂SiF₆ solution is used as a mother solution. The Pt and Au ionic species are deposited in Nb₂O₅ and SiO₂ matrices. They are reduced to their metallic state after treatment above 200 °C. The size of dispersed particles can be controlled by heat treatment temperature. It is also clear that, gold nanoparticles are also found to interact with SiO₂, although the interaction is smaller than that with Nb₂O₅ showing the size of Au nanoparticles remain smaller in Nb₂O₅ that in SiO₂.     

On-line LC-GC-AED and LC-GC-MS – multidimensional methods for the analysis of PAC in fuels,combustion emissions and atmospheric samples

The composition and concentration of polycyclic aromatic compounds (PAC) in fuels. Theier combustion products and in the atmosphere remains a topic of considerable interest. Despite the wealth of literature on the identification of PAC, speciation at low concentrations remains difficult due to instrument limitation and the complexity of fuel and environmental samples. Consequently on line sample preparation procedures (SPE, SFE, LC, etc.) are becomeing an increasingly important step in the analysis procedure particularly where sample clean-up and fractionation are essential for improving analytical resolution. In this study a normal phase high pressure analytical resolution. In this study a normal phase high pressure liquid chromatography-gas chromatography (LC-GC) system has been developed to provide quantitative analysis of samples, as diverse as coal liquids, petroleum fuels, diesel exhaust particulates, and urban air particulates. Separation and identification of parent and alkylated PAH, hetercycline nitro-and oxy-PAC can be achieved by direct coupling to an atomic emission detector and a bech top mass spectrometer. For both systems the primary LC separation combined with the large sample volume transferred to GC vastly improves detection limits. Furthermore the complimentary nature of the two detectors used enables the positive indentification of many unknowns.     

Thermal behaviour of styrene butadiene rubber/poly(ethylene-co-vinyl acetate) blends

The thermal behaviour of styrene butadiene rubber (SBR)/poly (ethylene-co-vinyl acetate) (EVA) blends was studied by using thermogravimetry (TG) and differential scanning calorimetry (DSC). The effects of blend ratio, cross-linking systems and compatibilization on the thermal stability and phase transition of the blends were analyzed. It was found that the mass loss of the blends at any temperature was lower than that of the components, highlighting the advantage of blending SBR and EVA. The addition of compatibilizer was also found to improve the thermal stability. DSC studies indicated the thermodynamic immiscibility of SBR/EVA system even in the presence of the compatibilizer. This is evident from the presence of two different glass transition temperatures, corresponding to SBR and EVA phases in both compatibilized and uncompatibilized blends.     

接枝和交联对纳米Si02改性NR／PP共混型热塑弹性体的影响

动态硫化制备纳米二氧化硅（SiO2）改性天然橡胶，聚丙烯共混型热塑性弹性体（NR/PPTPE）．研究了马来酸酐，苯乙烯，过氧化二异丙苯（MAH／St／DCP）多单体“就地”熔融接枝、交联对TPE力学性能、耐溶剂性能和耐热变形性能的影响，并用SEM分析了TPE的断面形貌．结果表明：纳米SiO2和MAH／St／DCP的最佳质量分数分别为0．03和0．0375／0．0188／0．00375时，MAH／St／DCP接枝、交联改性NR／PP／纳米SiO：TPE的力学性能、耐溶剂性能和耐热变形性能最佳．MAH／St／DCP“就地”接枝、交联通过细化交联NR分散相、改善交联NR分散的均匀性和增加两相之间的共交联，使NR与PP两相界面结合强度明显提高，NR／PPTPE的综合性能得到明显的改善．     

Electrochemical detector with a 20 nl volume for micro-columns liquid chromatography

Summary A flow-through two electrode wall-jet cell with a platinum measuring electrode and a cell volume of 20 nl has been designed and evaluated. It has been used to detect phenols by reversed phase liquid chromatography using short micro bore columns. The linear dynamic range between the measured current and the concentration is greater than 10³ (1.5×10^–7–5×10^–4 mol/l) and the minimum analyzable amount was found to be 10 pg for pyrocatechol. A negligible broadening in the detector permits the use of micro columns down to 0.5 mm internal diameter, packed with 5 m particles, without any substantial distortion of eluted zones.Presented at the 14th International Symposium on Chromatography London, September, 1982     

Helical unwinding in polymer-dispersed ferroelectric liquid crystals

We demonstrate that ferroelectric liquid crystals dispersed in a polymer matrix can form uniaxially aligned elliptical droplets. The alignment is controlled by mechanical shear during the polymerization of a UV-curable adhesive. The possibility of prealignment makes polymer-dispersed ferroelectric liquid crystals suitable for application in flexible electro-optical displays. In contrast to surface stabilized ferroelectric liquid crystal displays, the electro-optical effect in our system is due to the deformed-helix ferroelectric (DHF) effect.     

Synthesis and Mesogenic Properties of Liquid Crystals Containing Terminal Cyclohexylmethanol,Cyclopentylmethanol, Cyclobutylmethanol and Cyclopropylmethanol Moiety

Four series of compounds 11?50 containing terminal alicyclic rings such as cyclohexylmethyl, cyclopentylmethyl, cyclobutylmethyl, and cyclopropylmethyl rings were synthesized and their liquid crystal behavior studied. The ring size and the length of flexible alkoxy chain influence the phase formation in different ways. While the smaller ring and the shorter alkoxy chain tend to favor the formation of the N phase, the larger ring and the longer alkoxy chain tend to favor the formation of the SmC phase. All the compounds except 11 and 21 exhibit SmA phases. The widest temperature range of the N, SmA, and SmC phases are found in the compounds 41 , 46 , and 20 , respectively, which are 75 °C for 41 , 115 °C for 46 , and 100 °C for 20 .     

Chromatographic study of the thermodynamics of solutions of hydrocarbons in liquid crystal solvents. Evidence for order disturbance by the solutes

Gas-chromatographic experiments were carried out in various phases of the solvents 4-acetoxy-N-[4-methoxy-benzylidene]-aniline, dibutoxyazoxybenzene, lithium stearate, dihexoxyazoxybenzene, and diheptoxyazoxybenzene. The solutes were linear, branched and cyclic alkanes, and substituted benzenes. Excess enthalpies, entropies, and free entropies were calculated from net retention volumes. In the nematic liquid crystalline phases the effect of order disturbance was significant in and but it was, by enthalpy-entropy compensation, not demonstrable in . Differences in flexibility and degree of expansion of the solutes did not result in significantly different values of the excess quantities.