几种缩聚耐热聚合物单体纯度的差示扫描量热(DSC)测定

利用差示扫描量热法测定了缩聚单体的纯度。对于一种新型聚芳醚砜的单体4,4′—二氯二苯砜的纯度在99.0和99.9mol%时,所得缩聚物的比浓粘度分别可达0.36和0.62。提出了适用于缩聚单体纯度DSC测定法的试验程序。采用封闭坩埚,该法可用于升温时有少量升华(或挥发)的单体的纯度测定。     

DSC测量中校正对热分析结果的影响

介绍了灵敏度及温度校正对基线和实验结果的影响.仪器温度和灵敏度校正可以减小差示扫描量热法(DSC)曲线的漂移,曲线上得到的温度和焓变值更接近理论值,减小了实验误差.所以,定期对仪器进行重新校正是必要的.     

对DSC单峰纯度测定法的评述

指出了当前流行的差示扫描量热法DSC单峰法测样品纯度所基于的假定有一些不确切的地方,并用计算机动态摸拟了DSC实验过程,结果证实了本文的论断。     

邻醌式同系物的DSC研究

丹参(Salvia miltirrohiza)和红根草(S.Prionitis)均含有治疗冠心病有效成分—丹参酮Ⅱ-A等二萜醌类化合物,它们的扩冠作用,抑制血小板聚集,抑菌等活性常与该类化合物的结构、晶型、极性、溶解度、熔点有密切的相关性,如前报所述A环为脂环的化合物其熔化热低于芳环的化合物.丹参中的丹参醌Ⅱ-A(1),丹参醌Ⅱ-B(2)和红根草邻醌(3),其抗菌和抗肿瘤活性强度是3>2>1,为探究其晶型结构与药效的内在联系,本文对该类化     

聚丙烯DSC测试影响因素探究

以聚丙烯注塑成型样品为例,分别以不同温度对样品进行状态调节、不同升温速率消除样品热历史和不同降温速率冷却对样品进行DSC实验,分析其对测试结果的影响。结果表明：以不同温度对样品进行状态调节后进行实验,其第一次升温熔融峰温受状态调节温度影响出现先增大后减小,最大偏差2℃,对随后的降温过程和第二次升温过程无影响;以5℃/min至25℃/min的不同升温速率消除样品热历史进行实验,随着升温速率的增大,其第一次升温外推熔融起始温度随之减小,减小3.7℃,而熔融峰温和外推熔融终止温度随之增大,其中熔融峰温增大1.2℃,外推熔融终止温度增大3.5℃,对随后的降温过程和第二次升温过程无影响;以5℃/min至25℃/min的不同降温速率冷却进行实验,其外推结晶起始温度、结晶峰温、外推结晶终止温度和随后的第二次升温熔融峰温均随降温速率的增大而减小,其中外推结晶起始温度、结晶峰温、外推结晶终止温度减小8～12℃,第二次升温熔融峰温减小1.6℃。     

DSC曲线各特征点的物理意义以及相变热焓的广义Speil公式的推导

按目前差示扫描量热法（DSC）公认的Gray－Speil理论，由于对实际的过程过于简化，以致不能很好地解释DSC曲线上的每个特征点；就相变前后试样的热容量发生改变的普遍情况下，如何定量计算相变潜热，目前尚未有严格的计算理论。本文对差示扫描量热法的基本理论做了一些较深入的探索，通过考虑容器及试样内存在温度梯度这一实际情况，成功地解释了实际DSC曲线上各个特征点具体的物理意义，并就相变前后试样的热容量发生变化且热容量是温度的函数这一普遍情况，推广出广义的Speil公式和热焓计算的普遍法则，得到了与实验更加接近的结果。     

水合醛缩酶热变性的DSC研究

本文采用差示扫描量热法(DSC),研究了水合醛缩酶在含水量h从0.08g/g至2.28g/g范围内的热变性行为。实验结果表明,当h=0.08g/g时,水合醛缩酶样品的温度扫描热谱图呈现了两个吸热峰,其中低温峰很小,高温峰很大。随着h的增大,低温峰变得更小,高温峰则出现了分峰现象。当h=0.22g/g时,低温峰消失,高温峰则分裂成了两个独立的吸热峰。随着h的继续增大,其中前峰的位置不断移向低温,直至h_0.65g/g时,才不再变化。后峰的位置则始终保持不变。当再进行第二次温度扫描时,前峰消失,而后峰却能再现。本文给出了两峰在不同含水量时的转变温度、转变焓和转变焓之和,以及它们与含水量的关系。最后,对上述诸峰的起因作了分析讨论,认为低温峰可能起因于水合醛缩酶结晶的熔化作用,前峰和后峰可能起因于醛缩酶中两种A亚基的热变性。     

高灵敏度DSC技术的突破性进展

差示扫描量热技术(DSC)的发展已有半个世纪的历史.热流型DSC基于Boersma原理(1955年):仪器的热阻与样品无关,因此热流可以定量测定.功率补偿型DSC基于Watson和O'Neill在1963年提出的原理,测量输入到样品和参比之间的功率差.     

β-乳球蛋白B变性的DSC法研究

运用差示扫描量法,研究了牛β-Lg B在含各种浓度GuHC1的磷酸盐溶液中的变性。实验表明,在高蛋白质浓度条件下,GuHC1的存在使β-Lg B既可以冷变性,又可以热变性。两者的焓变有相反的符号。冷变性和复性都是可再生的,而热变性是不可逆的。在热变性过程中牵涉到单体分子间的协同作用,可用热力学模型N_cD→F表示。热变性过程的活化能是285 kJ/mol,表明GuHC1不是通过显著降低活化能而降低β-Lg B的热变性温度和热变性焓的。对于冷变性过程,尤其在3.10mol/L GuHC1溶剂中,可用二态模型ND表示。     

聚乳酸-聚乙二醇单甲醚共混体系的调制DSC分析

采用调制差示扫描量热法(MDSC)研究了聚乳酸(PLA)与聚乙二醇单甲醚(MPEG)共混体系的热性能。研究结果表明,MDSC可有效分辨PLA重结晶和熔融的重叠效应,在测试条件下,PLA的α’-α晶型转变与α晶体的熔融几乎同时进行。随着升温速率的加快和调制周期的延长,当增塑剂的质量分数为15%时,PLA-MPEG共混物分割在不可逆曲线的重结晶焓逐渐升高(最高约28J/g),熔融焓逐渐降低(最低约为3.3J/g);分割在可逆曲线的熔融峰逐渐由多重峰变为单峰,且焓变值逐渐升高(最高约66.1J/g),相应的可逆曲线熔融分割比例达到了95.2%。通过提高升温速率和延长调制周期,可使大部分熔融分割在可逆曲线上,但过快的升温速率和过长的调制周期会导致PLA相转变时的周期数过少,DSC调制功能的分辨率下降,设置测试条件时需综合考虑。     

差示扫描量热仪测定比热容方法的改进

对用常规热流型DSC仪测量物质比热容时的两个误差来源,即实际的升温速率偏离了程序设定的升温速率以及试样铝盘与参比铝盘两者质量的差异造成的影响进行数学分析,导出了计算比热容的改正方程.此方程的第一项HFT为实验热流值与实际升温速率的比值,第二项为测试过程中由于样品盘与参比盘的质量不同所引起的修正项,从而提高了测量结果的精确度.用此方法测量水、苯甲酸和氯化钾的比热容均得到较好的结果.     

DSC Calibration During Cooling. A survey of possible compounds

A number of compounds is investigated for DSC calibration during cooling. Adamantane and Zn show fast reversible transitions and can be applied both for temperature and for heat calibrations. A third compound, namely 4,4’-azoxyanisole, has a liquid crystal to isotropic liquid transition at 409K. This compound can be used for temperature calibration. Heat calibration with this compound is more problematic because of the small heat effect and the construction of the baseline. Other compounds like NaNO₃, In, Hg and Pb, show a slight supercooling. Nevertheless they can be used for heat calibration. The use of large samples of NaNO₃ and In gives the possibility to construct the equilibrium onset temperatures of the cooling peaks, so these two compounds are also appropriate for temperature calibration on cooling. This revised version was published online in July 2006 with corrections to the Cover Date.     

Heating rate effect on the DSC kinetics of oil shales

This research was aimed to investigate the combustion and kinetics of oil shale samples (Mengen and Himmetoğlu) by differential scanning calorimetry (DSC). Experiments were performed in air atmosphere up to 600°C at five different heating rates. The DSC curves clearly demonstrate distinct reaction regions in the oil shale samples studied. Reaction intervals, peak and burn-out temperatures of the oil shale samples are also determined. Arrhenius kinetic method was used to analyze the DSC data and it was observed that the activation energies of the samples are varied in the range of 22.4–127.3 kJ mol⁻¹ depending on the oil shale type and heating rate.     

测定高聚物动力学结晶能力的非等温DSC方法

研究了从非等温ＤＳＣ结晶曲线计算高聚物动力学结晶能力的方法．从高聚物非等温结晶动力学微分方程出发导出了计算高聚物动力学结晶能力的新方程．以含有不同催化剂的聚对苯二甲酸乙二酯为例，对其结晶进行了测试与计算．发现合理地选定最快结晶速率温度是计算动力学结晶能力的关键．本方法所得动力学结晶能力能正确反映高聚物的整体结晶信息     

Application of DSC Method for Thermal Stability and Flammability Assessment of Modified Polyurethanes

Differential scanning calorimetry (DSC) was applied to investigate the thermal behaviour of a series of segmented polyurethanes based on diphenylmethane-4,4'-diisocyanate (MDI), polyoxypropylenediol (POPD) and 3-chloro-1,2-propanediol (CPD)/1,2-propanediol (PD).It has been found that the heat of thermal transition in the range of 250–300°C increases with the amount of CPD, which also causes a decrease of polyurethanes' flammability, characterised by its Limited Oxygen Index (LOI) value. On the basis of obtained results it can be concluded that DSC may be applied for flammability evaluation of segmented polyurethanes.This revised version was published online in November 2005 with corrections to the Cover Date.     

A simple method for determining activation energies of organic reactions from DSC curves

An approximate formula for a rapid and simple estimation of activation energies from DSC curves is given and applied to various homogeneous reactions. The results obtained are compared with the approximate values of the Duswalt method and with the results by the mathematically more demanding method of Borchardt and Daniels (additional application of multiple linear regression). In this connection the efficiency of the new approximation method is demonstrated.     

A study of PBT/PC blends by modulated DSC and conventional DSC

Two poly(butylene terephthalate)/polycarbonate (PBT/PC) blends with different formulations were analyzed by modulated DSC (MDSC) and conventional DSC to determine differences in crystallization behavior. A significant difference (30°C in cold crystallization temperature) between the two samples was detectable by MDSC while no significant difference was seen by conventional DSC. That indicatesthe total heat flow from MDSC is not always equivalent to the heat flow from conventional DSC as we have assumed or seen before. The reason has not been fully understood, but may be related to unusual nucleation and crystallization induced by modulation. Alternative conventional DSC methods were developed and compared to the MDSC results.Dedicated to Professor Bernhard Wunderlich on the occasion of his 65th birthdayThe authors like to thank Drs. Bernhard Wunderlich and Robert Gallucci for helpful discussion, David Shaker and Mary Parsonage for some DSC experiments. Technical support from TA Instruments is also greatly appreciated.     

数据校正法与条件滴定度法提高络合滴定准确度

对于1gK＇_(My)C_M或1gK＇_(MY)C_M -1gK＇_(NY)C_N较小的络合滴定,可以使用单一参比溶液,使全部试样的pMeq均大于或小于该参比溶液的PM值,并使用数据校正法或条件滴定度法校正结果。实验证明,即使1gK＇_(MY)C_M或1gK＇_(MY)C_M -1gK＇_(NY)C_N小至4,仍能得精确结果。     

用非等温DSC基于Harcourt-Esson方程估算含能材料热爆炸临界温度的一种简单方法

用合理假设,由Semenov热爆炸理论和基于Harcourt-Esson速率表达式非等温动力学方程 ,推导了估算含能材料热爆炸临界温度的一种简单方法。该计算式为 ,比较简单。从非等温DSC曲线上onset温度（ ）通过表达式 可得到 ,由方程 可求得 值,随后算出 。该方法计算结果与Zhang-Hu-Xie-Li方法结果相一致。