DTA中升温速率及样品热导率对Tg测量值影响的模拟研究

就不同升温速率和实际样品的不同热导率对差热分析(DTA)中高分子材科的玻璃化转变曲线的影响进行了MonteCarlo模拟研究,发现当所有样品刚完成玻璃化转变时,在Tg曲线中该特征点要低于Tg的转变中点.转变中点所对应的样品温度肯定要高于实际的玻璃化转变温度.如果以玻璃化转变曲线的转变中点所对应的样品温度作为该材料的玻璃化转变温度,那么,升温速率越快、样品的热导率越小,所测得的玻璃化转变温度就越大,反之亦然.DTA测得的玻璃化转变温度与升温速率间有很好的线性依赖关系,但与样品热导率间的关系是非线性的.     

用DSC测量葡萄糖溶液部分玻璃化转变温度的新方法

用差示扫描量热仪, 采用经过退火处理的连续扫描法, 以不同浓度(20%、45%)的葡萄糖溶液为研究对象, 研究了退火温度对Tgf(部分结晶的玻璃化转变温度)的影响, 给出了确定Tg′(部分玻璃化转变温度)的新方法. 研究发现, 不同退火温度下的Tgf不同. 在−50 ℃以上退火, Tgf随着退火温度的增大而减小; 在−50 ℃以下退火, Tgf随着退火温度的增大而增大, 都有很好的线性关系. 不同浓度的溶液具有相似的规律. 提出从Tgf确定Tg′的方法: Tgf在−50 ℃上下随退火温度变化线的交点所对应的部分结晶玻璃化转变温度即为Tg′. 使用该方法测得葡萄糖的Tg′为−55 ℃.     

热处理条件对R-PET/LLDPE-g-MA共混物中PET玻璃化转变行为的影响

对回收聚对苯二甲酸乙二酯(R-PET)/LLDPE-g-MA马来酸酐改性的线性低密度聚乙烯共混物进行不同条件的热处理, 采用差示扫描量热仪(DSC)研究共混物基体PET的玻璃化转变行为. 结果表明, 当热处理温度低于PET的玻璃化转变温度(Tg)时, PET的玻璃化转变区域出现热焓松弛现象. 随着热处理温度的增加, PET的Tg逐渐升高; 在50~70 ℃下热处理48 h后, PET的Tg逐渐稳定. 当热处理温度高于PET的Tg而低于100 ℃时, PET的玻璃化转变区域出现2个热流转变, FTIR分析表明, PET分子构象开始发生变化. 当热处理温度为100 ℃时, DSC曲线上PET的玻璃化转变消失, PET的结晶度明显增加, 说明PET开始冷结晶的温度在90~100 ℃之间.     

木糖醇玻璃焓松弛的量热分析

为了考察木糖醇的玻璃化转变和焓松弛行为,寻求碳链长度对线性多元醇玻璃化转变和焓松弛行为的影响,利用差示扫描量热(DSC)技术测定了不同降温速率下木糖醇在玻璃化转变温度(Tg)前后的比热容(Cp),通过曲线拟合获得了TNM(Tool-Narayanaswamy-Moynihan)模型参数,并和其他多元醇类已有研究结果进行对照.结果表明,尽管TNM模型可以很好地重现不同降温速率体系的实验比热容数据,但模型参数并不是材料常数,而是和热历史有关,不同的降温速率对应不同的模型参数.指前因子(A)、非线性参数(x)和非指数参数(β)均随着降温速率的增加而降低,松弛活化焓(△h*)的变化趋势刚好相反.几种线性多元醇玻璃化转变和TNM模型参数的对照表明,玻璃化转变温度,松弛活化焓和动力学脆度(m)都随着烷基碳链长度的增加而增加.虽然非线性参数、非指数参数随碳链长度的增加有降低的趋势,但木糖醇展现出反常变化的情形.     

用正电子湮没谱研究聚酯型聚氨酯的微观结构和自由体积特性

用正电子湮没谱研究了两类分别由聚己二酸丁二醇酯多元醇和聚ε 己内酯多元醇合成的线型聚酯型聚氨酯 (PBU和PCU)在 140～ 36 0K温度范围内的结构转变和自由体积特性 .研究结果表明 ,两类聚氨酯(PU)在 140～ 36 0K温度范围内 ,都存在三个转变点 ,其中较低温度的转变 (约 2 0 0K)对应于PU中软段的玻璃化转变温度 (Tg) ,2 75K处的转变可能与样品吸附少量水分有关 ,较高温度的转变 (约 310K) ,对于PBU而言对应于软段结晶的熔点 ,而对于PCU则与在无序的硬段中混入一定量的软段后形成的相容区的Tg 有关 .当温度低于PU软段的Tg 时 ,两类PU的自由体积尺寸和浓度都随温度升高而增大 .当温度高于软段的Tg 但低于2 75K时 ,自由体积尺寸较快地增加 ,而自由体积浓度保持不变 .温度高于 2 75K并低于软段的熔点或硬段 软段相容区的Tg 时 ,自由体积尺寸增加速度最快 ,自由体积浓度却保持同样的数值 .当温度进一步升高时 ,自由体积尺寸和浓度都随温度增大而增加 .最后研究了这两类PU的自由体积分布与温度的关系 .所有这些实验现象均与大分子链的运动有关 ,并与通过DSC和WAXD表征的材料的形态一致     

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 .     

用调制式差示扫描量热法表征尼龙6和聚乳酸升温热行为

用调制式差示扫描量热法(MDSC)表征尼龙6和聚乳酸升温过程热行为，MDSC把总热流分解成可逆热流ΔHrev和不可逆热流ΔHnon;实验结果表明纯尼龙及其共混体系升温熔融过程中包含了可逆放热峰；共混体系不同，可逆热流ΔHrev不同，都比纯尼龙小；纯尼龙可逆热流ΔHrev随调制周期延长而增大；聚乳酸玻璃化转变区，随老化时间的延长和老化温度的提高，玻璃化转变温度Tg提高，松弛热焓增大。     

基于基团贡献法和分子动力学预测聚间苯二甲酰对苯二胺的玻璃化转变温度

采用基团贡献法(GC)和分子动力学法(MD)模拟了聚间苯二甲酰间苯二胺纤维(MPDI)和聚对苯二甲酰对苯二胺(PPTA)的玻璃化转变温度, 并与实验值进行了对比. 结果表明, 使用基团贡献法和分子动力学法测得的MPDI和PPTA的玻璃化转变温度与实验值接近, 说明基团贡献法和分子动力学法可以用来预测芳香族聚酰胺的玻璃化转变温度. 在此基础上, 采用GC和MD预测了聚间苯二甲酰对苯二胺(PPIA)的玻璃化转变温度. 在MD模拟中, 对密度、 比体积、 回转半径和非键相互作用随温度的变化规律进行了分析. 结果表明, 自由体积理论能较好地解释PPIA的玻璃化转变现象, 其中非键相互作用随温度的变化是玻璃化转变的本质原因. PPIA的玻璃化转变温度介于MPDI和PPTA之间, 有望成为综合性能介于两者之间的另一种高性能聚酰胺.     

高分子链的去拥挤转变及低温流动

简述了拥挤理论的基本原理,运用拥挤理论来说明高分子链间弱相互作用对高分子链所处的状态的影响,特别是对高分子玻璃化转变的影响.在实验中,采用固体核磁共振方法探测高分子的链间邻近度,并比较了不同链间邻近度的高分子样品在玻璃化转变温度以下的压力诱导流行行为,发现即使测试温度比高分子玻璃化转变温度低132℃,高分子链在压力下依...     

碳纳米管改性环氧树脂的导热和阻燃性能

以双酚A二缩水甘油醚(DGEBA)环氧树脂(Epoxy Resin,EP)为基体、甲基六氢苯酐(MHHPA)为固化剂、以多壁碳纳米管(MWCNTs)为添加剂制备了环氧树脂/碳纳米管纳米复合材料。通过对微观结构、玻璃化转变温度(Tg)、热失重、热导率和锥形量热测试结果分析,研究了质量分数少于1.5%的MWCNTs对环氧树脂的导热和阻燃性能影响,结果表明,MWCNTs质量分数为1.5%时,复合材料发生团聚;纳米复合材料随着MWCNTs质量分数的增加Tg值先增加后降低;失重5%时,对应的温度先增加后降低,残炭量增加;样品的热导率呈现先升高后降低的趋势,当MWCNTs质量分数为1%时,复合材料的热导率最大;MWCNTs加入后环氧树脂的总释热量减少,释烟量增加,阻燃性得到一定程度的提高。     

Thermal conductivity behaviour of polymers around glass transition and crystalline melting temperatures

The thermal conductivity of five semi-crystalline and four amorphous polymers was determined within a wide range of temperature, starting at room temperature and going up to temperatures above the polymer melting point (Tm) for semi-crystalline polymers or above the glass transition temperature (Tg) for amorphous polymers. Two transient techniques were employed in the experimental investigation: the hot wire technique for the group of amorphous polymers, and the laser flash technique for the semicrystalline polymers. As expected, the experimental results show that Tg exerts a measureable influence on the thermal conductivity of amorphous polymers. In the case of semi-crystalline polymers, a singular behaviour of the thermal conductivity is observed within the Tm range. In order to explain the anomalous behaviour, the influence of these transition temperatures on the thermal conductivity behaviour with temperature has been analysed in terms of a phonon conduction process and temperature variations of specific heat and modulus of elasticity of the analyzed polymers.     

Thermodynamics and structure of the ordered amorphous phase in polymers

Experimental data are analysed to show that the activation enthalpy and the structural entropy appear to follow empirical relations for structural relaxation of polymeric systems. The relations indicate that melting temperature, glass transition temperature, relaxation time, coefficient of thermal expansion of free volume are interrelated in polymers. The parameters of structural relaxations, measured by mechanical and dielectric spectroscopies, are reviewed for polyethylene, poly(4-methyl-1-pentene) and a liquid-crystalline polynorbornene derivative. The thermodynamic parameters obtained from calorimetric measurements, are reported for zero heating rate extrapolation and they are used in the empirical relation, which combines the Arrhenius and the Vogel-Fulcher formulae.     

酞侧基聚芳醚酮的热学性能

酞侧基聚芳醚酮的热学性能谢红卫，李滨耀（中国科学院长春应用化学研究所长春１３００２２）关键词酞侧基聚芳醚酮，ｐｖＴ行为，导热系数，定压比热容酞侧基聚芳醚酮（ＰＥＫ－Ｃ）具有较高的玻璃化转变温度，其流变加工性能和力学性能已被广泛研究［１～３］，被证明是...     

Glass transition temperature and thermal decomposition of cellulose powder

Cellulose powder and cellulose pellets obtained by pressing the microcrystalline powder were studied using differential scanning calorimetry (DSC), differential thermal analysis (DTA), and thermal gravimetry (TG). The TG method enabled the assessment of water content in the investigated samples. The glass phase transition in cellulose was studied using the DSC method, both in heating and cooling runs, in a wide temperature range from −100 to 180 °C. It is shown that the DSC cooling runs are more suitable for the glass phase transition visualisation than the heating runs. The discrepancy between glass phase transition temperature T _g found using DSC and predictions by Kaelbe’s approach are observed for “dry” (7 and 5.3% water content) cellulose. This could be explained by strong interactions between cellulose chains appearing when the water concentration decreases. The T _g measurements vs. moisture content may be used for cellulose crystallinity index determination.     

Thermal properties of fibres from a new polymer of the polyimideamide group

The paper presents the thermal properties of fibres made of a modified polyimideamide. The effects of as-spun draw ratio and deformation during the fibre drawing stage on the structure, thermal properties, moisture absorption and tenacity of the obtained fibres have been determined. Based on the findings obtained by the DTA and DSC methods, it has been found that the modification of the polymer under investigation causes its glass transition temperature to decrease through the increase of molecular mobility. At the same time, the heat-resistant fibres with the amorphous oriented structure are characterized by a tenacity of 16 cN/tex, good absorption properties and increased porosity. The thermal stability indices of the examined fibres have been determined on the basis of thermogravimetric curves obtained both under air and inert gas. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal stability and flammability of butadiene- acrylonitrile rubber cross-linked with iodoform

Summary The paper discusses the results of thermal analysis and flammability of butadiene-acrylonitrile rubber, Perbunan NT 1845 of Bayer, cross-linked with iodoform. The properties of the iodoform vulcanizate have been compared with those of peroxide vulcanizate. The thermal analysis has been performed in air with use of a derivatograph under air and nitrogen atmosphere as well as dynamic scanning calorimetry (DSC). The flammability of vulcanizates has been determined by the method of oxygen index and in air. The toxicity of the thermal decomposition and combustion products of the vulcanizates under investigation has been also determined. Based on complementary examinations, DTA and DSC curves have been interpreted from the point of view of thermal transitions of the conventionally and non-conventionally cross-linked nitrile rubbers. The glass transition temperature of the cross-linked polymer both in cooling and heating has been determined.     

DSC studies of solid polymeric electrolytes

Relations are demonstrated between the conductivity, phase structure and thermal history of some solid polymeric electrolytes. The results obtained for systems based on commercially available polymers, e.g. (ethylene oxide), and for specially synthesized materials are presented. Special emphasis is placed on the correlation between the crystallinity, glass transition temperature, melting temperature and conduction properties of the polymeric electrolytes.This work was supported financially by the Rector of Warsaw University of Technology according to research program 503/164/220/1.     

Thermal Studies on Chlorinated Atactic Polypropylene

Thermal behavior of chlorinated atactic polypropylene (CAPP) obtained by thermal chlorination of atactic polypropylene was evaluated by thermogravimetric analysis and differential thermal analysis (DTA). It was found that the initial decomposition temperature, integral procedural decomposition temperature, activation energy, and char yield increase with an increase in chlorine content. The thermal stability of CAPP was found to be lower in air than in nitrogen. This has been ascribed to thermooxidative degradation in air. DTA study shows that onset decomposition temperature, glass transition temperature, and polymer melting temperature increase with increasing degree of chlorination. The possible reasons for the phenomena are discussed.     

Thermal stability of Ag-exchanged clinoptilolite rich mineral

Thermal stability of clinoptilolite rich mineral from Western Anatolia, Turkey and its Ag-exchange forms was investigated. Parent mineral of different sizes were heated up to 1000°C with heating rate of 2 and 10°C min^-1 using differential thermal analyzer (DTA) and thermogravimetric analyzer (TG). Ag exchange was conducted both in conventional constant temperature waterbath and microwave at 40, 60 and 80°C. The exchanged minerals were then characteized by scanning electron microscopy (SEM), X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR), DTA and TG. The particle size and heating rate do not have significant effect on the thermal behavior of the parent mineral and no structural changes were observed with Ag exchange, only decomposition temperature was lowered. It was finally concluded that, Ag-exchanged clinoptilolite rich minerals were less thermally stable compared to parent mineral that does not affect their use for possible applications.