聚2,6-萘二甲酸乙二醇酯β松弛的热释电研究

本文用短路热释电方法研究了聚萘酯(PEN)的β松弛过程。极化场强和电极效应的实验结果表明,PEN的TSC图谱中50℃的β松弛过程是偶极松弛过程。并且此松弛峰电流值随样品结晶度的增加而降低。用“初始升高法”计算得到其松弛活化能约为0.34eV,且不受结晶度变化的影响。这些实验结果说明β松弛是非晶区小链段的局部运动。     

热释电研究聚碳酸酯掺杂染料体系的玻璃化转变

采用热刺激电流 /松弛谱图分析法 (TSC/RMA)研究了聚碳酸酯掺杂染料体系 (TDAA/PC)的玻璃化转变 ,发现染料含量增加 ,体系的玻璃化转变温度 (Tg)随之降低 ,玻璃化转变的温度范围变宽 .在TDAA掺杂质量比达到 4wt%时 ,其玻璃化转变 (协同松弛 )延伸至 95℃ ,温度范围增加到 3 5℃ .在较大的温度范围内存在协同松弛 ,说明在低于Tg 数十度的温度时 ,染料发色体的极化松弛仍然主要受聚合物玻璃化转变的控制 .     

热释电流法研究聚对苯二甲酸乙二醇酯的Sub-T_g存放

测量了一系列在T相似文献   

聚偏氟乙烯共混体系的压电性及其分子运动——Ⅱ.PVDF与 P(VDF-HFE)以及PVDF与P(VDF-TFE)的共混体系

本文研究了 PVDF-P(VDF-HFE)以及 PVDF-P(VDF-TFE)共混体系的压电、介电、力学松弛谱。其松弛转变过程基本与 PVDF 的相似。α,β,γ压电松弛峰分别位于40～120℃,-40℃,-85℃附近。实验结果表明后一体系的压电性大于前一体系的。同时,PVDF-P(VDF-TFE)的压电性也大于PVDF-PMMA 共混体系的。选择第二组分时,以介电常数高,模量小而本身又具有压电性的,更有助于共混薄膜压电性的提高。在同样的极化条件下,经拉伸的 P(VDF-TFE)薄膜,其压电性大于未经拉伸的薄膜,这表明分子的取向对薄膜的压电性也有影响。TSC 表明,42℃的松弛峰与晶区表面捕获的空间电荷有关,对压电性也有一定的贡献。     

聚偏氟乙烯共混体系的压电性及其分子运动II.PVDF与P(VDF-HFE)以及PVDF与P(VDF-TFE)的共混体系

本文研究了PVDF-P(VDF-HFE)以及PVDF-P(VDF-TFE)共混体系的压电、介电、力学松弛谱。其松弛转变过程基本与PVDF的相似。α,βγ压电松弛峰分别位于40～120℃,-40℃,-85℃附近。实验结果表明后一体系压电性大于前一体系的。同时,PVDF-P(VDF-TFE)的压电性也大于PVDF-PMMA共混体系的。选择第二组分时,以介电常数高、模量小而本身又具有压电性的,更有助于共混薄膜压电性的提高。在同样的极化条件下,经拉伸的P(VDF-TFE)薄膜,其压电性大于未经拉伸的薄膜,这表明分子的取向对薄膜的压电性也有影响。TSC表明, 42℃的松弛峰与晶区表面捕获的空间电荷有关,对压电性也有一定的贡献。     

固体氧化物燃料电池电化学阻抗谱差异化研究方法和分解

电化学阻抗谱技术(EIS)在固体氧化物燃料电池(SOFC)中已获得广泛应用。在EIS分析过程中,研究者能够清楚地获得燃料电池内部因纯离子(电子)导电引起的欧姆电阻和因电化学过程、扩散作用引起的极化阻抗的大小,但是对于极化阻抗的构成缺乏进一步解析。本文选用传统的Ni-YSZ阳极支撑电池,通过改变测试温度、阳极运行气氛和阴极运行气氛,设计了一套完整的阻抗差异分析(ADIS)实验。并基于弛豫时间分布法(DRT)和阻抗差异分析法,系统地分析并解释了阻抗谱中各频率段对应阻抗的物理或(电)化学含义,将该类型电池阻抗谱以6个RQ并联电路予以拟合,为之后燃料电池性能稳定性的研究奠定基础。     

从静态应力松弛实验求材料准松弛时间谱的一种数值计算方法

避开繁琐困难的函数求解过程，采用数值计算方法，从常规的静态应力松弛实验，直接求被测材料的松弛单元的表现松弛强度．主松弛时间τ０由单－ＭＡＸＷＥＬＬ模型求得，其他松弛时间分别约取为１０（－２）·τ０，１０（－１）·τ０，１０１·τ０，１０３·τ０。应力松弛万程取５参数模型，记为谱的强度ａｉ（或Ａｉ）通过多元线性回归，由最小二乘法确定．对一种天然橡胶试样在不同温度下的松弛曲线进行处理，回归值与原始实验值吻合良好，不同温度下的松弛单元对总松弛的贡献，反映出温度对松弛过程的活化作用．     

蓖麻油基AB交联聚合物的介电性质

在-180℃至140℃范围内,用几个频率测定了蓖麻油基AB交联聚合物的介电松弛谱。对这些聚合物的多重松弛和相行为的研究表明,试样中的两组份在介电松弛谱上显现出相容的或近似互容的特征。试样中的次级松弛归因于聚氨酯组份中链段的局部运动。提出了一个描述界面极化的方法,计算了界面极化松弛活化能,它们同试样中组份间的相容性,界面相互作用大小以及分子链的柔曲性有关。     

介电松弛谱法用于高分子链动力学行为的研究

介电松弛谱法是研究高分子链松弛运动的一种有效方法.它可反映出分子的特征结构信息,对揭示高分子链动力学行为的本质及规律、调控其凝聚态结构意义重大.本文从介电松弛谱理论出发,总结出几种常用的介电特征参数以及用于解析这些参数的数学模型.通过介电松弛谱中高分子链的弛豫过程的解析,可得出与高分子链运动相关的特征参数,如介电常数、介电松弛强度以及链运动的特征松弛时间,从而判断链松弛运动的尺寸小大,松弛的基团以及链运动的协同过程;还可与Arrenius方程、Vogel-Tammann-Fulcher（VFT）方程、统计学模型建立联系,获得界面构造、分子内部组成、链动力学行为同环境的依存性等信息,为高分子材料的分子设计、开发与应用奠定高分子物理理论基础.     

脉冲极谱

巴克尔和迦特纳(Barker and Gardner)在1958年提出了脉冲极谱分析法,解决了方波极谱法中的毛细管响应问题;并且改进了电路的杂音电平,该法在交流极谱法中为灵敏度最高的一种分析方法。脉冲极谱法是在汞滴生长至一定面积时,在滴汞电极的直流极化电压上迭加一次脉冲极化电压,然后记录由脉冲极化电压所引起的法拉第电流。目前这一种方法已引起世界各国的注意,相信它很快地会被人们应     

湿度及无机填料对低密度聚乙烯热释电流谱的影响

 我们将低密度聚乙烯试样暴露在湿空气中一定的时间,不管在用直流高压极化的前后,甚至在极化后对其经过72h的真空干燥处理,在中温区也存在一个附加的湿致热释电流峰,它可能是由俘获在晶区-非晶区界面的离子热释放所致。 由分析在极化前对含无机填料(经表面处理的高岭土)的低密度聚乙烯试样进行干燥或润湿处理后的热释电流谱表明,聚乙烯中的无机填料与吸收的水分子都可作为电子的受主,前者为电子深陷阱,后者为电子浅陷阱。     

湿度及无机填料对低密度聚乙烯热释电流谱的影响

我们将低密度聚乙烯试样暴露在湿空气中一定的时间,不管在用直流高压极化的前后,甚至在极化后对其经过72h的真空干燥处理,在中温区也存在一个附加的湿致热释电流峰,它可能是由俘获在晶区-非晶区界面的离子热释放所致。 由分析在极化前对含无机填料(经表面处理的高岭土)的低密度聚乙烯试样进行干燥或润湿处理后的热释电流谱表明,聚乙烯中的无机填料与吸收的水分子都可作为电子的受主,前者为电子深陷阱,后者为电子浅陷阱。     

序列结构对苯乙烯/丁二烯共聚物热释电流峰的影响

本文研究聚合方式对苯乙烯/丁二烯共聚物热释电流峰(TSC)的影响。共聚物试样有三个电流峰(β、α和ρ峰)。实验结果表明:聚合方式对β峰(丁二烯局部运动)基本没有影响,但对α峰(丁二烯相的T_g转变)的位置有明显的影响,而且两步法试样有两个α峰;嵌段共聚物试样在高温还有一肩部(苯乙烯相的T_g转变),无规共聚试样没有肩部。由共聚物的序列结构能圆满解释TSC结果,而序列结构决定于聚合方式。因此,本工作将苯乙烯/丁二烯共聚物的序列结构与性能联系起来。     

Study of the molecular mobility of collagen

The dielectric relaxations of a biopolymer, collagen, have been studied by means of the thermally stimulated current (TSC) technique. To investigate effects of water on TSC spectra, complementary measurements by differential scanning calorimetry (DSC) have been performed. In dehydrated collagen, three spectral bands were recorded in the temperature range of -180-60°C, labelled α, β₁, and γ in the order of decreasing temperature. The TSC spectrum of hydrated collagen exhibits a supplementary band labelled β₂. By using the fractional polarization method, the γ and β₁ modes have been attributed to localized movements of nonpolar (apolar) sequences and polar sequences, respectively. The α mode has been associated with delocalized movements of the collagen macromolecules. Finally the β₂ mode has been attributed to reorientations of bound water molecules inside the collagen fibers. © 1995 John Wiley & Sons, Inc.     

TSC STUDIES ON SUB-Tg STORAGE OF POLYETHYLENE TEREPHTHALATE

The Thermally Stimulated Current (TSC) spectra of a series of Sub-T_θannealed polyethylene terephthalate (PET) specimens have been measured. It is found that there is only one peak at 80℃above room temperature, which related to the thermo-relaxation of frozen-in dipoles. The activation energy of such dipole motion has been calculated. The relation between the maximum current and the storage time can be explained by the free volume theory and agrees with the results from the excess thermodynamic properties. Compared with Differential Scanning Calorimeter (DSC) and tensile stress-strain method, TSC is a simpler and more sensitive method in studying Sub-T_θannealed polymers.     

THE EFFECT OF PHOTO-CROSSLINKING ON THE ORIENTATION STABILITY OF POLYVINYL ALCOHOL CONTAINING 4-NITRO-4′-ALKOXYSTILBENE AND CINNAMYL PENDENT GROUPS*

Crosslinking is one of the effective routes for improving the orientation stability of poledpolymer films. The derivative of polyvinyl alcohol containing 4-nitro-4'-alkoxystilbene andphoto-crosslinkable cinnamyl groups as side chains has been synthesized. The in-situ simul-taneous photo-crosslinking poling of synthesized polymer films has been performed. Thesecond order nonlinear optical coefficient d_(33) of poled film is 11 pm/V. The SHG mea-surements show that the break-over temperature of SHG signal is raised obviously afterirradiation, its orientation stability is doubled as compared with that of non-crosslinkingsamples.     

Some analytical applications of aromatic sulfonyl haloamines: Determination of thiocyanate and cyanide ions in metal complexes and salts and thiosemicarbazide in metal complexes with bromamine-T

A simple, rapid, and accurate method for the determination of thiocyanate and cyanide ions in metal complexes and salts, and thiosemicarbazide (TSC) in Zn, Cd, Hg, Ni, Pt, and Pd metal complexes with excess of bromamine-T has been developed. The oxidation involves eight- and two-electron changes, respectively, with NCS^? and CN^? ions and a 12-electron stoichiometry per TSC molecule, in 0.1–0.2 N NaOH medium. The proposed method could be employed for computing the number of thiocyanate, cyanide, and TSC ligands in the respective complexes. The aromatic sulfonyl haloamine, bromamine-T, has been prepared and characterized by uv, ir, and FT NMR ¹H and ¹³C spectral data and its mass spectrum.     

Thermoluminescence from photoexcited polyethylene terephthalate

Thermoluminescence from polyethylene terephthalate (PET) has been investigated. A correlation was found between thermoluminescence (TL) and thermally stimulated current (TSC). The apparent activation energy was estimated at 0.23–0.50 eV for both TSC and TL from ?170 to 0°C. This activation energy presumably indicates the trap depth, which is decreased by molecular motions, since both TSC and TL are quenched efficiently with visible light, but not with infrared light of energy of the magnitude of thermal activation energy. The spectrum of TL glow curves agrees with the photoluminescence spectrum at ?185°C, which is composed of an excimer and a monomer fluorescence and also a structured phosphorescence at wavelengths longer than 400 nm.     

Thermally stimulated current and differential scanning calorimetry spectroscopy for the study of polymer nanocomposites

The thermally stimulated discharge current (TSC) and differential scanning calorimetry (DSC) spectroscopy have been recorded in 25 μm thick samples of pristine polycarbonate (PC) and zinc oxide nano particle-filled polycarbonate. Polycarbonate (PC)/zinc oxide (ZnO) nanocomposites of different mass ratio (e.g., 1, 3, and 5%) were prepared by sol–gel method, followed by film casting. The glass transition temperature of nanocomposite samples increases with increase in concentration of ZnO nano fillers. It is due to the strong interaction between inorganic and organic components. The TSC peaks of nanocomposite and pristine PC indicate the multiple relaxation process. It has been observed that the magnitude of TSC decreases with increase in concentration of nanofillers. The TSC characteristics of 5% filled nanocomposites shows exponential increase of current at higher temperature region. This increase in current is caused by formation of charge-transfer complex between inorganic phase (e.g., ZnO) and organic phase (e.g., PC). Thus, the nano material like zinc oxide transfers the charge carriers from inorganic phase to organic phase rapidly and resultant current increases exponentially. This current is known as leakage current or breakdown current. TSC peak height is observed as a function of the polarizing field. The height of TSC peak increases as the field increases in pristine PC, while TSC peak height is suppressed in nanocomposite samples. This indicates the amount of space charge is smaller in the nanocomposites with a proper addition of ZnO nano fillers than in the pristine PC.