VDF/TrFE铁电共聚物极化分布与退极化过程的激光强度调制方法研究

建立起激光强度调制法测量装置及其测量与数据处理方法,研究了VDF/TrFE铁电共聚物的极化分布和退极化过程.发现25μm厚的VDF(80)/TrFE(20)薄膜在距表面8μm左右薄层热电系数显示极大值,而12μm厚的则在中心处,两者的热电系数皆以两表面呈对称分布.在145℃热处理产生退极化.随着时间的增长,热电系数减小,退极化由试样的一面向另一面逐渐进行,2h后由强电场形成的极化基本消失.直流极化30μm厚的VDF(70)/TrFE(30)薄膜,热电系数分别在离两表面6,8μm处达恒定值,基本以两表面呈反 关键词：     

偏氟乙烯/三氟乙烯铁电共聚物的非晶介电弛豫

用溶液成膜、液氮淬火、熔融慢冷和热处理4种方法制得不同结晶度的VDF/TrFE共聚物试样。在已改进的介电弛豫谱仪(精度由原来的1％提高到2‰)上测得复数介电常数。从结晶度为20％的淬火试样室温以下的介电频率谱中发现了非晶介电弛豫,并由此得到了玻璃化温度与共聚物组分含量的关系。 关键词：     

Ge-As-S体系玻璃中光学二次谐波发生及其极化机理分析

采用Maker条纹法,在电子束辐射极化条件下的Ge-As-S体系玻璃中观察到二次谐波发生效应 .通过热诱导去极化电流法(TSDC)进行极化机理分析得出,极化区域位于玻璃表面很薄的一 层区域内,与理论计算结果相符. 关键词： Ge-As-S体系玻璃 电子束辐射 Maker条纹 二次谐波发生 TSDC     

聚对苯二甲酸丁二醇酯/聚(对苯二甲酸丁二醇酯-e-己内酯)二元结晶共混体系的相容性和结晶行为

聚对苯二甲酸丁二醇酯(PBT)/聚(对苯二甲酸丁二醇酯-e-己内酯)(PBT-PCl)是一个新制备的具有分子间排斥相互作用的A/AxB1?x型两元结晶共混体系. 根据两元平均场模型,报道对苯二甲酸丁二醇酯(BT)与"-己内酯(CL)结构单元的相互作用参数为0.305. DSC研究发现,此共混物呈现了与典型的共聚物/均聚物共混物不同的结晶特征. PBT-PCL影响PBT链的活动力和晶片堆积;同时PBT-PCL的结晶受到先期结晶的PBT晶粒的阻滞. 尽管拥有相同的BT单元,共混的两组分在组成变化范围内仍没有形     

在玻璃转变温度及其以上温区聚苯乙烯/聚氧化乙烯共混物的动力学弛豫行为

用熔融共混法制备了不同组分的聚苯乙烯(PS)与聚氧化乙烯(PEO)共混物(PS/PEO).在玻璃转变温度T_g及其以上温区,利用相对能量耗散技术研究了该共混物的动力学行为.结果发现,在能量耗散-温度曲线上出现了两个弛豫型的耗散峰(α峰和α′峰).分析表明,α峰是与PS玻璃转变有关的特征耗散峰; α′峰则对应于一种“液-液转变”.两者的弛豫时间τ都不满足Arrhenius关系.此外,还研究了组分对这两个弛豫型耗散峰的影响,并给予了定性的解释. 关键词： 相对能量耗散 玻璃转变 力学弛豫     

PET与SAN/PAN复合膜界面的 FTIR-ATR研究

应用傅里叶衰减全反射红外光谱(FTIR-ATR)技术对聚对苯二甲酸乙二酯(PET)表面形成不同厚度的超薄苯乙烯-丙烯腈共聚物(SAN)和聚丙烯腈(PAN)的共混物膜及其SAN/PAN共混物膜的厚度、界面层PET亚甲基的构像变化等进行研究,结果表明PET表面共混物膜的厚度随共混物混合液中SAN含量的增加而增加,界面层成膜物质与基材的分子链段间发生了相互渗透和扩散,分子链的极性越相近,越容易成膜.对PET红外光谱吸收峰的A1340/A1410进行定量研究表明,在成膜过程中,PET分子链的亚甲基构像由反式向旁式转变,引起界面层PET的结晶度降低.FTIR-ATR是分析复合膜界面层结构信息的有效方法.     

典型高分子材料的固体核磁共振研究

本论文通过固体核磁共振（NMR）谱及动力学参量的测量,并结合X-射线衍射技术和DSC测量等研究了两种典型高分子材料的相结构、链的运动以及相与相之间的关系.  乙烯-醋酸乙烯共聚物( EVA) 是最主要的乙烯共聚物之一. 研究发现,EVA的相组成非常复杂,共有5个不同的组分. 除了PE中所观察到的常规单斜晶相和刚性的正交晶相外,我们发现还存在第三个晶相分量－运动性较强的晶相（SOCP,可能是转动相）. 它不仅拥有自己的熔点,而且它的化学位移和分子运动性不同于刚性正交晶相（LOCP）. 另一方面,非晶相也由两种不同的分量组成：运动受限的各相异性的非晶界面相和高度可动的橡胶型的非晶相. 我们进一步详细研究了EVA中的晶区链动力学和非晶区的低温冻结行为. 实验发现,在正交晶相中,高分子链以180° flip-flop方式运动,同时伴随沿链方向的平移型跳跃运动,并引起正交晶相和非晶相之间的长程链扩散,通过NOE的测量证实了这种相间链扩散的存在,并进一步通过实验证实这种相间链扩散是一种受限扩散而不是自由扩散. 同时非晶相的两个组分具有不同的低温冻结行为：当温度低于-弛豫转变温度时,橡胶型的非晶相中的长程分子运动被冻结,但仍存在分子的局域运动;而界面非晶在低温时冻结成一种有序取向结构,并用质子自旋扩散实验证实该有序结构与正交晶相相邻近.  少量纳米级片层状粘土分散在聚合物中就可赋予材料许多优异的性能,我们用固体NMR技术对EVA/REC复合材料的结构和其中粘土的分散性质进行研究,发现上述复合材料中所形成的晶体类型不仅依赖于各组分的性质还依赖于所形成的复合材料的类型.  偏氟乙烯/三氟乙烯共聚物（P（VDF-TrFE））是最主要的铁电高聚物之一. 我们利用变温固体¹⁹F MAS NMR 谱及弛豫数据的测量详细研究了电子辐照对P(VDF-TrFE)共聚物的分子结构、构型、运动性以及相变等的影响. 发现,电子辐照不仅改变了分子链段的构型和运动性,同时也改变了局部分子化学结构. 电子辐照促使铁电相向顺电相(或者非晶相)转变,与此同时诱发了富含VDF和含-TrFE链段从全反式的构型到混合的反式-旁式构型的转变. 电子辐照加剧顺电区域中的分子运动而在高温熔融态中(>100 ℃）,分子的运动反而受限.     

SMMA/SMA共聚物共混物的自由体积的热动态特性与相分离行为的PALS研究

基于自由体积理论，利用正电子湮灭寿命谱仪(PALS)分别研究在不同升温速率条件下，聚苯乙烯-甲基丙烯酸甲酯共聚物(SMMA)和聚苯乙烯-马来酸酐共聚物(SMA)混合物(30/70)的自由体积参数的温度依赖性，探索相容共混物相行为的热动态特性.在PALS实验中，在玻璃化转变温度T_g以上，当结构松弛的弛豫时间与等温停留时间相当，发现在某一段温度范围内，共混物的自由体积参数随着温度的变化明显地偏离线性关系.从自由体积孔的浓度I₃值在该段的变化趋势，初步推断共混物在该温 关键词： 正电子湮没 正电子素 聚合物共混物 相分离     

硼酸铅玻璃的光学二次谐波产生

对硼酸铅玻璃体材料样品进行热辅助的平板电场极化(简称热极化)后,通过观察其光学二次谐波(SHG)信号的强弱,得到了不同组分的样品的最佳极化温度,发现其最佳极化温度与玻璃化温度满足一定的关系;同时得到了不同组分的样品在各自的最佳极化温度条件下极化后的二次谐波信号强度与组分的关系;经过对一种组分的样品进行细致研究,发现样品的二次谐波信号强度随着极化电压的增大而增大,并满足幂函数关系.利用有效偶极子释放模型解释了样品的二次谐波信号强度与极化电压之间的超平方关系 关键词： SHG 玻璃 极化     

红外光谱法测定聚(乳酸-苯丙氨酸)共聚物的含量

分别以苯丙氨酸和乳酸为原料合成了3-苯甲基-2,5-吗啉二酮(PMD)与丙交酯(LA),以PMD和LA作为聚合单体经开环聚合分别得到PMD均聚物(PPMD)、丙交酯均聚物(PLA)及聚(乳酸-苯丙氨酸)共聚物。对合成的均聚物进行红外分析,确定1 671.53和870.82 cm-1处的吸收峰分别为PPMD和PLA的特征峰。根据以上两种特征吸收峰并以朗伯-比耳定律为理论依据,建立了利用红外光谱法测定聚(乳酸-苯丙氨酸)共聚物含量的方法。实验测定的标准工作曲线为y=0.055 67x+0.1091,r=0.999 3。利用该标准工作曲线定量测定了共聚物组分含量,其结果与1H NMR测定值一致,相对误差在2％以内,证明红外光谱法可方便、快捷地测定聚(乳酸-苯丙氨酸)共聚物组分含量,且适用于其他聚(乳酸-氨基酸)共聚物的含量测定,具有一定的实用性及推广性。     

Tetramethylpolyarylate-polyarylate block copolymer: Synthesis and miscibility with polyarylate and poly(styrene-co-acrylonitrile)

Abstract

Tetramethylpolyarylate-polyarylate (TMPAr-PAr) block copolymers of various block lengths were synthesized by the coupling reaction of hydroxy-terminated TMPAr and hydroxy-terminated PAr using triphosgene. The phase behavior of these block copolymers are discussed based on the thermal properties observed by differential scanning calorimetry (DSC). The thermal properties of binary blends of these block copolymers with PAr homopolymer or poly(styrene-co-acrylonitrile) whose acrylonitrile content is 9.5 wt% (SAN 10) were observed by DSC. The compatibilizing effect of the microphase-separated TMPAr-PAr block copolymer in PAr/SAN 10 blends was observed from thermal properties and morphology.     

Thermal Behaviors of Confined Triphenylmethyl Chloride Crystals in Various Molecular Weight Polystyrene

The thermal behaviors of polystyrene (PS)/triphenylmethyl chloride (TPCM) blends with different polymer molecular weights were investigated through differential scanning colorimetry (DSC). It was shown that when solvent content was lower than a critical composition, there was only a single amorphous phase in the blends. With increasing polymer concentration, both T_g and T_m could be detected in DSC curves, revealing that the blends were heterogeneous. The constant T_g of the amorphous phase indicated that the composition of the amorphous phase in the blends did not depend on the solvent concentration, and the T_m depression with decreasing PS content showed the decrease of TPCM crystallite size owing to geometric constraint by the polymer chains. On the basis of the Flory–Huggins theory, the interaction parameters between PS and TPCM in the blends were obtained; they showed that the PS/TPCM blends were not thermodynamically miscible with low polymer content. The Hoffmann-Weeks equation indicated that the crystals corresponding to the lower melting point were unstable. The unstable crystals in the blends were located in the interfacial regions between the crystalline solvent molecules and the amorphous phase. The heat capacity of the blends confirmed the geometric constraint on the crystallization of TPCM in the blends.     

BLENDS OF THERMOTROPIC LIQUID CRYSTALLINE POLYESTER AND POLY(ETHYLENE TEREPHTHALATE)

Two kinds of blends of thermotropic liquid crystalline polymers (LCPs) and poly(ethylene terephthalate) (PET) were prepared by solution and melt blending, respectively. Crystallization behavior of the blends was observed by differential scanning calorimetry (DSC). The LCP in both blends considerably decreased the cold crystallization temperature of PET and increased the crystallization rate in the low-temperature region, but did not show any significant effect on crystallization in the high-temperature region. Phase behavior of samples prepared by melt blending was investigated with the scanning electronic microscope (SEM). It was found that LCP/PET blends display a biphasic structure with an aromatic unit-rich phase as a dispersed domain, and a highly oriented fibrous structure was formed on the fracture surface of the blends. During the melt blending process, PET reacted with LCP through transesterification, as indicated by both DSC and SEM measurements.     

Relationship between Microstructure and Mechanical Properties of Ethylene-Octene Copolymer Reinforced and Toughened PP

Polypropylene (PP)/ethylene-octene copolymer (POE) blends with 10–50wt% POE composition were prepared using a twin-screw extruder in the melt state. Mechanical properties of PP and PP/POE blends were tested and the effect of POE content on the crystalline morphology and structure, melting and crystallization behavior, compatiblilty, phase morphology, and the interface cohesiveness of the blends were investigated by polarizing optical microscope (POM), wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), and scanning electron microscopy (SEM). The relationship between mechanical properties and microstructure of the PP/POE blends is discussed. The results showed that POE had a dual function of both reinforcing and toughening PP in the range from 10–40wt%, which was attributed to the integrated functions of the degree of crystallinity of the PP phase, phase morphology, and interface cohesiveness of the blend.     

Interfacial activity of styrene-butadiene block copolymers in low-density polyethylene/polystyrene blends

The effect of molecular structure of styrene-butadiene (SB) block copolymers on their interfacial activity in low-density polyethylene/polystyrene (LDPE/PS) (4/1) blends was studied. It was found that addition of some SB copolymers, which are localized in brittle PS particles, leads to a decrease in the blend impact strength in spite of the fact that these SB improve the toughness of both the blend components. Comparison with our previous results showed that the distribution of SB copolymers between the interface and bulk phases and their supermolecular structure in LDPE/PS (4/1) blends strongly differs from those in LDPE/PS (1/4) blends.     

Crystalline and relaxation properties of ethylene copolymer films inserted between two steel sheets

The relaxation and crystalline properties of ethylene vinyl acetate (EVA) co-polymers inserted in steel/polymer/steel assemblies were studied. To investigate the properties of the interfacial region, polymers of different thickness inserted in the assemblies were analyzed. The studied EVA copolymers are semicrystalline polymers. The relaxation properties of the amorphous phase were investigated by dynamic mechanical measurements performed on the steel/polymer/steel assemblies, and the crystalline properties were studied by differential scanning calorimetry (DSC). The results indicate that, for low polymer thicknesses, the mobility of the amorphous phase is significantly reduced. Significant changes in the crystalline organization also were observed when the polymer thickness decreased, with the presence of more numerous disorganized crystals for thin EVA layers. These crystals can act as physical ties that reduce the mobility of the neighboring amorphous chains. These results indicate the formation of an interphase layer of reduced mobility.     

Dielectric Relaxations in Structurally Disordered Materials

Chain mobility in multiphase polymeric materials is studied by thermally stimulated depolarization currents and dielectric spectroscopy in poly(styrene)-b-poly(butadiene)-b-poly(c-caprolactone) triblock copolymers and poly(carbonate)/poly(c-caprolactone) blends. The variation in the relaxation time distribution of the dielectrically active components and in the number of orientable dipoles in the amorphous phases of these materials is interpreted as the result of the existence of a rigid amorphous phase constrained by the crystalline regions or in the case of the blends by a phase segregation which takes place when the crystallization process of the blend components advances. The mean relaxation times for the secondary and segmental motions are not affected when the phases are segregated.     

POLY(3-HYDROXYBUTYRATE)-BASED COPOLYMERS AND BLENDS: INFLUENCE OF A SECOND COMPONENT ON CRYSTALLIZATION AND THERMAL BEHAVIOR*

Isotactic poly(3-hydroxybutyrate) (P3HB) is an aliphatic polyester obtained by bacterial fermentation. This truly biodegradable polymer has been widely investigated, mainly with the aim to replace conventional plastics, which cause environmental pollution. To improve its properties, extensive studies have been conducted to modify it properly by copolymerization or blending with other polymers. Macroscopic properties of polymers, particularly of polymer blends, are strongly affected by their microstructure, especially by the allocation of different phases and their level of dispersion and adhesion. In nonreactive blends, the adhesion level is mainly determined by the similarity between the chemical structure of the components, and the arrangement of the phases is remarkably controlled by the crystallization conditions. The superstructure of the crystalline phases accounts for the mechanical resistance of the blend, but the composition and the distribution of the amorphous phases also play an important role, especially with respect to toughness properties. This article reviews data on thermal properties and the crystallization process of P3HB and its copolymers, both alone and in the presence of other polymers. In particular, copolymers of 3-hydroxybutyrate with 3-hydroxyvalerate and with 4-hydroxybutyrate and blends of P3HB and the copolymers with atactic poly(3-hydroxybutyrate), poly(vinyl acetate), poly(vinyl alcohol), poly(ethylene oxide), poly(methylene oxide), poly(epichlorohydrin), and poly(methyl methacrylate) are considered. Major attention is directed toward the influence of miscibility and composition on solidification kinetics and crystal structure with the objective to provide an overview of the current state of the art.

     

Phase behavior of binary blends of symmetric polystyrene-polybutadiene diblock copolymers studied using SANS

Binary blends of compositionally symmetric diblock copolymers are investigated using small-angle neutron scattering. The study focuses on the miscibility of blends of polystyrene-polybutadiene diblock copolymers as a function of chain length ratio and blend composition, and the results are related to the theoretical phase diagram put forward by M.W. Matsen (J. Chem. Phys. 103, 3268 (1995)). Three different low molar mass copolymers were blended with a high molar mass copolymer. We find very good coincidence with the theoretical phase diagram obtained. Only for blends having a chain length ratio of 0.06, theory predicts that a larger amount of short copolymers can be dissolved in the matrix of long copolymers, and vice versa. With the latter blends and volume fractions of short chains between 0.11 and 0.70, the second-order Bragg-peaks do not vanish, which indicates that the lamellae are asymmetric. Received: 9 February 1998 / Revised: 20 April 1998 / Accepted: 24 April 1998