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 ℃.     

调制差示扫描量热法研究玻璃化转变温度

对比了DSC与MDSC试验技术的差别， 列举了MDSC的优点，MDSC不但可以给出普通DSC的所有信息，而且给出更多的普通DSC无法提供的信息。MDSC特别适合于复杂转变、弱的转变分析，可以寻找出隐藏在熔融及结晶过程中的玻璃化转变。MDSC对于试验条件的选择比较苛刻，在选择好基本的试验参数的前提下，还需要设置调制周期、调制振幅等参数。     

热致液晶共聚酯的熔融行为及结晶结构研究

采用ＤＳＣ及ＷＡＸＤ手段对含对羟基苯甲酸热致液晶共聚酯的相变行为及结晶结构进行了初步研究。结果表明，聚合物中存在两种同属于正交晶系的不同堆积形态结晶结构，在相变上表现为双重熔融峰。     

聚乙交酯-丙交酯-己内酯三元无规共聚物及其电纺膜的制备与表征

以左旋丙交酯、乙交酯和己内酯为原料,辛酸亚锡为催化剂,在真空条件下经本体熔融开环聚合,制备了三元无规共聚物(P),其结构和性能经1H NMR,IR,DSC和粘度表征。实验结果表明:P的玻璃化转变温度可通过单体的投料比调控;采用静电纺丝法可方便地获得共聚物亚微米纤维膜。     

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。     

含三氟甲基聚酰亚胺的合成与性能研究

通过在4,4′-二氨基二苯醚(4,4-′ODA)单体中引入三氟甲基合成了一种新型二胺单体2-三氟甲基-4,4′-二氨基二苯醚(3FODA),该单体具有良好的溶解性和高的反应活性,使用3FODA替代4,4′-二氨基二苯甲烷(MDA)制备了PMR热固性聚酰亚胺树脂.树脂溶液高浓度低粘度,具有室温下良好的储存稳定性;树脂具有很好的加工性能,成型后的模压件显示了优异的热性能和耐热氧化稳定性,玻璃化转变温度在336~379℃之间;此外树脂具有较好的电性能和较低的吸水率.     

热重-傅立叶变换红外光谱联用法研究超支化聚氨酯/丙烯酸酯的热性能及热分解机理

采用热重分析仪(TG)和差示扫描量热仪(DSC)对自制的超支化聚氨酯(HPU)和UV固化超支化聚氨酯丙烯酸酯(HPUA)在不同气氛下的热失重行为和玻璃化转变温度(Tg)进行分析,在此基础上,结合热重红外联用仪(TG-FTIR)探究了HPU和HPUA的热分解机理。热重分析结果表明:HPU和HPUA在氮气气氛下具有相似的热分解行为,均有3段热分解温度;在空气气氛下的热分解与氮气气氛下的热分解相比,其分解行为相似,但前者的分解更迅速。DSC分析表明:接入丙烯酸羟乙酯(HEA)后,HPUA的Tg明显低于HPU。热红联用对热分解机理的分析表明:空气气氛下的分解比氮气气氛下更迅速,降解更完全。HPU的3段热分解分别为:醇的降解、氨基甲酸酯键的降解、脲基键的降解;HPUA的3段热分解分别为:丙烯酸羟乙酯的降解、氨基甲酸酯键的降解、脲基键的降解。     

关于影响高分子材料玻璃化转变温度因素的教学分析

从《高分子物理》考试试题实例出发,抓住聚合物材料的"结构决定性能,并最终决定用途"这条主线,详述了链结构因素(主链和取代基)和分子间作用力对聚合物玻璃化转变温度(Tg)的影响,并结合不同高分子材料的用途进行分析,使学生真切了解到材料结构与性能及用途之间的关系。这种理论联系实际的案例教学法有利于加深学生对高分子材料的感性认识,引发学生学习的广泛兴趣,促使教师进行自我教育和提高业务水平,从而取得良好的教学效果。     

最快结晶速率温度与结晶参数的关系

以经典的结晶速率与温度的关系为基础,对T_(c,max)与结晶参数的关系进行了研究.结果表明,T_(c,max)同平衡熔融温度(T_m)的比值仅与成核参数(φ)同扩散活化能(E_d)之比有关.高聚物的结晶过程可用二次成核模型近似.当结晶速率与温度的关系采用下式时 G=G_0exp[-E_d/RT-φT_m~2/T~2(T_m-T)]T_(c,max)与结晶参数的关系为 T_(c,max)=2/3T_m[1-(1+9α)~(1/2)cos(1/3)arccos1/(1+9α)~(3/2)+240°]或 α=φR/E_d=T_(c,max)(T_m-T_(c,max)~2/T_m?2(3T_(c,max)-2T_m)     

聚丙烯-聚乙烯嵌段共聚物和相应共混物的热分析

用DSC研究了预期为聚丙烯-聚乙烯两嵌段共聚物(PP-PE)和相应共混物(PP+PE)在热学性能上的差异。经用不同分子量的PP和PE及其共混物进行试验后发现,由于PP和PE在结晶时出现过冷的难易不同。在共混物降温热分析曲线上,当降温速率较快时仅出现一个放热峰,而降温速率较慢时出现PP和PE各自的结晶放热峰,从而解释了文献中的不同结果。并发现共混物的PP和PE熔融、结晶温度均较组分相同的嵌段共聚物的相应温度为高;嵌段共聚物中PP和PE的△H_f值均低于均聚物的△H_f值,而PE的值降低尤甚。我们认为这与嵌段间的共价键限制嵌段活动和结晶过程有关,从而确认DSC热分析可以作为识别是否为嵌段共聚物的一种方法. 本工作的结果表明,所研究的PP-PE试样具有嵌段结构。     

热分析技术在药物研究中的应用

本文综述了热分析法在药物研究中的应用及发展趋势。由于热分析技术的发展和热分析仪的不断改进及自动化程度的提高,热分析法在药品检验、新药开发、剂型研究以及药物的热分解动力学研究等方面发挥越来越大的作用。     

差热分析测定水煤浆的燃烧特性

水煤浆具有燃烧效率高、燃烧温度低、环境污染少等特点,是当前国内、外广泛研究的课题之一,具有广阔的发展前途。通常水煤浆含有30—35%的水,0.1—1%的添加剂,这大量水和少量添加剂的存在对水煤浆的燃烧过程所产生的影响以及它与煤粉的直接燃烧的差别是我们共同关心和感兴趣的问题。本文利用差热分析仪直接测定两种煤粉及由三种不同添加剂制得的水煤浆在空气流中燃烧时的特性。     

热分析法观测Na2CrO4熔点

在现有文献中收录的Na2CrO4熔点数据各不相同，有792℃、392℃，两者相差400℃左右。利用热分析法观测Na2CrO4熔点，确定其熔点应为792℃。并且在419．6℃存在着一个可逆的固－固相变，转变焓为148．6J.g^-1。     

热分析法研究聚全氟乙丙烯非等温裂解反应动力学

本文从非等温差示扫描量热(DSC)曲线研究聚(?)氟乙丙烯(FEP)在空气中热裂解过程分为两个阶段的机制及其微分动力学方程。利用峰形指数确定的两个阶段的裂解反应级数,用多项式回归了相应的裂解活化能,指前因子随裂解率变化的规律及其补偿效应。     

Kinetic Studies of Bulk Ge22Se78−xBix (x=0, 4 and 8) Semiconducting Glasses

Results of phase transformations, enthalpy released and specific heat of Ge₂₂Se_78–xBi_x(x=0, 4 and 8) chalcogenide glasses, using differential scanning calorimetry (DSC), under non-isothermal condition have been reported and discussed. The glass transition temperature, T _g, is found to increase with an average coordination number and heating rates. Following Gibbs—Dimarzio equation, the calculated values of T _g (i.e. 462.7, 469.7 and 484.4 K) and the experimental values (i.e. 463.1, 467.3 and 484.5 K) increase with Bi concentration. Both values of T _g, at a heating rate of 5 K min^–1, are found to be in good agreement. The glass transition activation energy increases i.e. 102±2, 109±3 and 115±8 kJ mol^–1 with Bi concentration. The demand for thermal stability has been ensured through the temperature difference T _c–T _g and the enthalpy released during the crystallization process. Below T _g, specific heat has been observed to be temperature independent but highly compositional dependent. The growth kinetic has been investigated using the Kissinger, Ozawa, Matusita and modified JMA equations. Results indicate that the crystallization ability is enhanced, the activation energy of crystallization increases with increasing the Bi content and the crystal growth of these glasses occur in 3 dimensions.This revised version was published online in November 2005 with corrections to the Cover Date.     

线性分析法来解热脱附动力学参数

TPD方法是研究表面常规手段之一.对于如何从实验结果获得正确的脱附动力学参数,已有不少工作发表。然而,现有方法均存在一定的适用范围,尤其是重叠谱解叠,仍然没有很好地解决。本文介绍的线性分析法,不仅适用于简单的一级和二级脱附TPD谱的解析,而且也适用于重叠谱解叠,从而为实验上确定动力学级数和复杂谱解叠提供了依据。     

DENSITY, EQUILIBRIUM HEAT OF FUSION AND EQUILIBRIUM MELTING TEMPERATURE OF NYLON 1010

The density, equilibrium heat of fusion and equilibrium melting temperature of Nylon 1010 were determined by means of infrared spectrum, differential scanning calorimetry, wide angle X-ray diffraction and density measurement techniques. According to Starkweatber' s method crystalline density ρ_c and amorphous density ρ_a were estimated to be 1.098 and 1.003 g/cm~3 respectively by extrapolating the straight lines of the IR absorbanee against density to zero intensity. Owing to the less intense in absorbance and less sensitive to the change in crystallinity of the amorphors band the thus obtained ρ_c was too low in value. Thereby the value of the ratio ρ_c /ρ_a is far less than generally accepted mean value for most crystalline polymers. Accordingly, traditional X-ray diffraction method was used through determining thc crystalline dimension(a=4.9, b=5.4, c=27.8, α=49°β=77.0°, γ=63.5°), and a rather correct value of ρ_c or the crystal density 1.13 g/cm~3 was obtained. The equilibrium heat of fusion △H_m~0 was estimated to be 244.0 J/g piotting △H_m 's of specimens with different crystallinity against their corre sponding specific volumes _(sp), and extrapolating to completely crystalline condition (_(sp)~c= 1/ρ_c) As to the equilibrium melting temperature T_m~0, because of the easiness of recrystallization of melt crystallized Nylon 1010 specimen, the well-known Hoffman's T_m-T_c method failed in determining this value and an usually rarely used Kamide double extrapolation method was adopted. The so obtained value of T_m~0 487 seems to be fairly reasonable.     

Structure and Morphology of a Polyether/Polyacrylate Semi-interpenetrating Polymer Network

In this study NMR and DSC are used to probe the structure, thermal characteristics and morphology of a network formed from a diepoxide/acrylate system. Separate chemistries are employed to polymerize the diepoxide and acrylate components. The cationic polymerization of the diepoxide exhibits excellent selectivity in producing a crosslinked polyether network without affecting the acrylate monomer. Subsequent photoinitiated free-radical polymerization of the acrylate produces a phase separated, semi-interpenetrating polymer network (SIPN).This revised version was published online in November 2005 with corrections to the Cover Date.     

Flow injection analysis as a tool for enhancing oceanographic nutrient measurements—A review

Macronutrient elements (C, N and P) and micronutrient elements (Fe, Co, Cu, Zn and Mn) are widely measured in their various physico-chemical forms in open ocean, shelf sea, coastal and estuarine waters. These measurements help to elucidate the biogeochemical cycling of these elements in marine waters and highlight the ecological and socio-economic importance of the oceans. Due to the dynamic nature of marine waters in terms of chemical, biological and physical processes, it is advantageous to make these measurements in situ and in this regard flow injection analysis (FIA) provides a suitable shipboard platform. This review, therefore, discusses the role of FIA in the determination of macro- and micro-nutrient elements, with an emphasis on manifold design and detection strategies for the reliable shipboard determination of specific nutrient species. The application of various FIA manifolds to oceanographic nutrient determinations is discussed, with an emphasis on sensitivity, selectivity, high throughput analysis and suitability for underway analysis and depth profiles. Strategies for enhancing sensitivity and minimizing matrix effects, e.g. refractive index (schlieren) effects and the important role of uncertainty budgets in underpinning method validation and data quality are discussed in some detail.