分子链大尺度高度取向小尺度接近无规取向态的无规聚苯乙烯

在Ｔｇ以上３０℃对无规聚苯乙烯（ａ ＰＳ）薄膜进行了热拉伸，然后用各种实验方法测定的结果表明，该试样在红外二向色性，光学双折射及广角Ｘ 光衍射（ＷＡＸＤ）方面表现出各向同性；但是在热膨胀、溶剂溶胀以及应力 应变行为方面表现出显著的各向异性．以上结果表明，该试样小区域基本上无取向，而各向异性的性质是和试样中存在的大区域取向相联系的．     

SYNTHESIS OF A NOVEL SELF-ASSEMBLING NLO POLYMERIC FILM*

By covalently binding chromophore NPP, N-(4-nitrophenyl)-(L)-prolinol, to a structurallycontrolled cage-like cross-linking polymer (SCCP), a modified nonlinear optical (NLO) polymeric filmprepared by "in situ poling and sol-gel" process successfully overcame the fundamental problem of NPPchromophores subliming out from the cages of the "doped" NLO polymeric film when heated or placed underUV light. Its d_(33) (coefficient of second harmonic generation) is 2.0×10~(-8) esu. measured by IR dichroism. Themodified film has a low decay of the SHG signal and preserves 94% of the initial value after 50 days at roomtemperature. These properties match that of the "doped" film, indicating that the modified film also retainsthe main advantages of the "doped" film.     

Orientation of the α- and γ-modification of elastic polypropylene at uniaxial stretching

New metallocene catalysts applied to propylene polymerization expand the range of properties of polypropylene (PP), resulting in semi-crystalline materials having crystallinities below 60% up to X-ray amorphous highly elastic ones. To date the origin of the unique elastic mechanical behavior of such low crystalline PP is not completely understood. Therefore, the microscopic orientation of those PPs due to uniaxial stretching was investigated using wide-(WAXS) and small-angle X-ray scattering (SAXS). The aim of this study was to correlate these orientations or changes in the developed fiber textures with the macroscopic stress-strain behavior. This includes efforts to come closer to the main question of the nature of the physical cross-links in these not chemical cross-linked homopolymers, which is the reason for the high elastic behavior. Therefore, high molecular weight metallocene PPs showing different crystallinities (0-36%) were stretched to several elongations and the structural changes during the deformation were recorded by X-ray scattering. Stress-strain measurements show the great potential of these PPs as a thermoplastic rubber material. For quantitative analysis and discussion of the polymer chain orientations, the orientation functions were calculated. Correlations between the orientation functions and the stress-strain curves allow an interpretation of the macroscopic behavior on a microscopic scale. A higher cross-linking density in elongated samples indicates that the network, which is responsible for the elasticity, mainly built up by strain-induced morphology changes and chain orientations.     

Infrared lattice bands of some pearls

From analysis of anisotropical lattice bands properties of 50 reflection spectra both of the CO stretching and bending bands measured from some pearl (Ca⁺⁺CO ₃ ^–– or Ca⁺⁺HCO ₃ ^–– layer) we discussed following subjects.i) Quantized properties present both in reflectivity and in energy. ii) classifications of the Optical Activity. iii) Polar distributions of the CO₃ oscillators in Ca⁺⁺CO ₃ ^–– surface mono-layer. iv) Force constants of these oscillators. v) Step variation of the dipolemoment and their influences to the degree of Optical Activity. vi) Two types of hysteresis loops of the values of Y_N (M_2Jbend ()/M_1Jstret. ()) derived from the oscillators which are at innert-state, at weak active-state and at active-state.     

Transient shear flow behavior of concentrated long glass fiber suspensions in a sliding plate rheometer

In order to eventually predict the behavior of long fiber suspensions in complex flows commonly found in processing operations, it is necessary to understand their rheology and its connection to the evolution of fiber orientation and configuration in well defined flows. In this paper we report the transient behavior at the startup of shear flow of a polymer melt containing long glass fibers with a length (L) >1 mm, using a sliding plate rheometer (SPR). The operation of the SPR was confirmed by comparing the transient shear viscosity (η⁺) for a polymer melt and a melt containing short glass fibers (L < 1 mm) with measurements obtained from a cone-and-plate device, using a modified sample geometry that was designed to avoid wall effects. For the long fiber systems, measurements could only be obtained in the SPR because these systems would not stay within the gap of the rotational rheometer. Transient stress growth behavior of the long fiber systems was obtained as a function of shear rate and fiber concentration for samples prepared with three different initial orientations. Results showed that, unlike short fiber systems (with a random planar initial orientation) that usually exhibit a single overshoot peak followed by a steady state, η⁺ of the long fiber suspensions often passed through multiple transient regions, depending on the fiber concentration and applied shear rate. Additionally, η⁺ of the long fiber suspensions was found to be highly dependent on the initial orientation of the sheared samples. Finally, the initial and final fiber orientations of the long glass fiber samples were measured and used to initiate an explanation of the viscosity behavior. The results obtained in this research will be useful for future assessment of a quantitative correlation between transient rheology and the evolution of fiber orientation.     

Orientation of bromination in bay-region of perylene diimides

We found that the entering position of the bromination in the bay-region (e.g., 1,6,7,12-positions) was precisely determined by the orientation director(s), either individually or cooperatively. In particular, a combination of two directors shows precisely positioning for the third entering bromo with an effect of ‘1+1>2’.     

Simultaneously improving the tensile and impact properties of isotactic polypropylene with the cooperation of <Emphasis Type="Italic">co</Emphasis>-PP and <Emphasis Type="Italic">β</Emphasis>-nucleating agent through pressure vibration injection molding

In this article, crystalline morphology and molecular orientation of isotactic polypropylene (iPP), random copolymerized polypropylene (co-PP) and β-nucleating agent (β-NA) composites prepared by pressure vibration injection molding (PVIM) have been investigated via polarized light microscopy, scanning electron microscopy, wide-angle X-ray diffraction and differential scanning calorimetry. Results demonstrated that the interaction between co-PP and iPP molecular chains was beneficial for the mechanical improvement and the introduction of β-NA further improved the toughness of iPP. In addition, after applying the pressure vibration injection molding (PVIM) technology, the shear layer thickness increased remarkably and the tensile strength improved consequently. Thus, the strength and toughness of iPP/co-PP/β-NA composites prepared by PVIM were simultaneously improved compared to those of the pure iPP prepared by conventional injection molding (CIM): the impact toughness was increased by five times and tensile strength was increased by 9 MPa. This work provided a new method to further enhance the properties of iPP/co-PP composites through dynamic processing strategy.     

聚甲基丙烯酸三氟乙酯单体与分子链在金属有机框架中吸附及取向特性的理论研究

本文结合分子动力学、密度泛函理论和蒙特卡洛方法,研究了光学损耗低的氟化聚合物单体分子甲基丙烯酸三氟乙酯（TFMA）及其分子链在[Zn2(BDC)2TED]n和[Zn2(BPDC)2TED]n两种结构有序的金属有机框架（MOFs）材料中的吸附特性,得到相应的吸附数量和取向程度,以探索提高聚合物材料双折射性的有效途径。通过分析结果得出影响TFMA单体分子在这两种MOF孔道中吸附及取向特性的三个因素：a）由于MOF孔道壁是由金属离子和有机配体组成的极性表面,MOF孔壁与极性分子TFMA之间的静电相互作用对TFMA单体分子在孔道内的吸附和取向有促进作用;b）在受限空间中的聚合物单体分子之间的静电相互作用使其分子间隙更加紧密,同样也对其分子取向有促进作用;c）在这个两种孔洞与聚合物单体分子相对大小不同的MOF中,单体分子和分子链的取向度基本一致,但单体分子在孔径较大的MOF中吸附数量更多。这三个因素的重要影响,为聚合物单体或MOF的选取、对聚合物链取向及双折射性的控制提供理论预测方法。