高温比热容测试常见问题及误差分析

介绍了同步热分析仪(STA449F3)测试高温比热容过程中的常见问题及误差分析. 采用差示扫描量热三步法测试高温比热容. 试验结果表明, 提高仪器的稳定性和升温速率可减小比热测试值与理论值之间的误差. 此外, 将常规一段升温测试分割成若干个窄温区间, 提高了高温比热容测试的准确性.     

(Nd,Pr)12.8Dy0.2Fe77.4Co4B5.6铸锭PPMS和DSC居里温度测量比较研究

为充分拓展DSC测量功能、探寻居里温度的简便测量方法、尤其是探寻高温居里温度的耐久测量方法,对真空电弧熔炼(Nd,Pr)12.8Dy0.2Fe77.4Co4B5.6铸锭,先通过PPMS测量升温速率3 K·min-1时样品的M-T曲线,并用外推法得到居里温度为648.3 K;然后采用DSC分别以3,10,20,30,40 K·min-1速率测量样品的升、降温曲线,分析升、降温曲线上对应吸、放热峰的起始点、峰值、终止点的特征温度值;再分别用最小二乘法拟合特征温度与升降温速率的直线方程,计算升降温速率分别为0和3 K·min-1时特征温度值,并与PPMS测量的居里温度值进行比较。结果表明:由DSC升温曲线起始点的特征温度拟合直线方程计算的升温速率为3 K·min-1的特征温度值为649.1 K,与PPMS外推法得到的居里温度相对差值最小为0.12%,具有足够的精确度。     

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.     

热解过程中生物质半焦比热容的测定

采用热重-差示量热扫描法(TG-DSC)测量了生物质和一次热解焦炭及不同转化率下半焦的比热容,建立了计算半焦比热容的数学模型并与实验测量结果进行了对比。结果表明,生物质样品和热解焦炭的比热容在60~200℃随温度升高而线性增大。生物质焦炭的比热容低于生物质样品的比热容,从60℃时的1.2 J/(g·K)增大到200℃附近的1.8~2.0 J/(g·K)。生物质半焦比热容随热解转化率的提高而降低。由半焦比热容数学模型计算得到的结果在接近150~200℃时与实验测定的半焦比热容数值基本一致。     

甘氨酸间硝基苯甲酸晶体比热容的测定——差示扫描量热法(DSC)

论述用DSC及比热软件测量甘氨酸间硝基苯甲酸(G.mNBA)晶体比热容的方法。以蓝宝石为标样,测量G.mNBA晶体的比热容,其相对平均偏差在0.08%～0.47%之间。     

煤焦分形维数及其对比热容的影响研究

比热容是煤炭热物理性质之一，在煤矿的矿井防火、防止煤与瓦斯突出、井下降温设计及煤炭加工利用(如煤炭的燃烧、气化、焦化、液化等)等方面是关键参数之一，对提高煤炭热能利用率、提高经济效益、减少环境污染等，具有非常重要的意义。比热容的影响因素很多，如煤化程度、水分质量分数、热解温度等，煤焦微观结构的影响也是其中很重要的一方面。分形几何由Mandelbrot 1982年创立，是定量描述自相似或自相关等不规则形体的工具。研究表明，煤焦微观结构具有分形特征。在煤焦分形的研究中，常用的实验技术方法为吸附法、小角度X射线散射法和孔度法，采用扫描电子显微镜和数字图象处理方法研究煤焦的分形结构，能更加深入地理解其分形维数与性能的关系。     

1,1-二氨基-2,2-二硝基乙烯的比热容、热力学性质及绝热至爆时间研究

应用Micro-DSCⅢ微热量仪的两种连续比热容测定模式对1,1-二氨基-2,2-二硝基乙烯(FOX-7)比热容进行了测定. 得到298.15 K时FOX-7的标准摩尔比热容分别为176.56和176.02 J•mol^－1•K^－1, 相对偏差为0.31%. 运用Gaussian 03W程序的DFT-RB3LYP/6-311＋＋G**方法对FOX-7在283～353 K温度范围内进行了比热容理论计算, 结果为147.11～170.54 J•mol^－1•K^－1, 与Micro-DSCⅢ微热量仪测定值偏差在13.27%～15.46%之间. 用测得的比热容方程计算了298.15 K为基础的FOX-7的热力学函数并得到了绝热至爆时间.     

指数升温脱附研究

本文采用分子筛吸附苯或正已烷, 进行指数程序升温脱附。结果表明, 活化能与脱附最大速率所对应的温度(T_m)有线性关系, 即E_d=KT_m。对指数升温条件下得到的脱附图谱与各个脱附动力学参量之间的关系进行了数学分析, 并将分析结果与线性升温所得的结果相比较。各对应的动力学参数的数值基本相同。我们推导得到的指数升温基本方程与目前通用的线性升温基本方程~[2]相比较, 如果温度的测量精度相同则指数升温计算方法的精度比线性升温高(2T+△T)倍。实验还说明, 指数升温的曲线比线性升温容易控制。     

苯乙烯—丙烯等规立构嵌段共聚物（iPS—b—iPP）的非等温结…

用ＤＳＣ法研究了苯乙烯－丙烯等规立构嵌段共聚物的非等温结晶动力学。结果表明，冷却速度在５－２０℃／ｍｉｎ范围内，共聚的非等温结晶动力学参数能很好地符合Ａｖｒａｍｉ动力学学方程，非等温结晶速率常数与冷却速率有关，动力学结晶能力则同时受到冷却速率和共聚物组成比的影响，文中还讨论了在非等温结晶条件下共聚物的结晶成核和生长方式与共聚物组成和结构的关系，联合Ａｖｒａｍｉ方程和Ｏｚａｗａ方程推导的非等温结晶动     

DSC测试中样品内部的温度分布及其对比热测试的影响

由傅里叶导热定律结合Tools-Narayanaswamy-Moynihan(TNM)松弛模型提出了一种计算聚合物样品内温度分布的方法.对PS的计算结果表明温度梯度随样品厚度、升温速率增大而增大,对于1.0 mm的PS以1 K/min降温后再以10 K/min升温时样品内部最大温差为0.882 K.在此基础上提出了不同样品厚度、不同热处理条件下聚合物测定比热的计算方法,结果表明计算结果与实测数据基本一致.     

示差扫描量热法进展及其在高分子表征中的应用

示差扫描量热法(DSC)是表征材料热性能和热反应的一种高效研究工具,具有操作简便、应用广泛、测量值物理意义明确等优点.近年来DSC技术的发展大大拓展了高分子材料表征的测试范围,促进了对高分子物理转变的热力学和动力学的深入研究.温度调制示差扫描量热法(TMDSC)是DSC在20世纪90年代的标志性进展,它在传统DSC的线性升温速率的基础之上引入了调制速率,从而可将总热流信号分解为可逆信号和不可逆信号两部分,并能测量准等温过程的可逆热容.闪速示差扫描量热法(FSC)是DSC技术近年来的创新性发展,它采用体积微小的氮化硅薄膜芯片传感器替代传统DSC的坩埚作为试样容器和控温系统,实现了超快速的升降温扫描速率以及微米尺度上的样品测试,使得对于高分子在扫描过程中的结构重组机制的分析以及对实际的生产加工条件的直接模拟成为可能.本文从热分析基础出发,依次对传统DSC、TMDSC和FSC进行了介绍,内容覆盖其发展历史、方法原理、操作技巧及其在高分子表征中的应用举例,最后对DSC未来的发展和应用进行了展望.本文希望通过综述DSC原理、实验技巧和应用进展,帮助读者加深对DSC这一常用表征技术的理解,进一步拓展DSC表征高分子材料的应用.     

Frequency Dependence of the Dynamic Heat Capacity at the Melting Temperature of Polyethylene Crystals

The dynamic heat capacity of polyethylene was measured in the heating process over two decades of the modulating frequency using the light heating modulated temperature DSC. The dynamic heat capacity exhibited clear frequency dependence from 95°C to the end of the melting of the crystals. Frequency dependence of this work was compared with that of the quasi-isothermal measurement. The relaxation time estimated in this work was much shorter than that of the quasi-isothermal measurement. It was found that notable heat exchange between the sample and reference sides occurred between 120 and 135°C. Frequency dependence of the heat exchange was studied.This revised version was published online in November 2005 with corrections to the Cover Date.     

Comparison of simulated and actual DSC measurements for first-order transitions

A system of differential equations modeling a heat flux DSC is solved and the results are compared with those obtained using a TA Instruments Q1000™ DSC.¹ It incorporates a new heat flow rate measurement technique that determines the heat flow rate between the sample and its pan. Two types of first-order transitions are investigated: melting of a pure substance and solidification of a pure substance including super-cooling. In both transitions, the peak shape obtained using the new heat flow rate measurement and predicted by the model is quite different from that measured using conventional DSC. It is shown that the differences are the result of simplifications implicit in the conventional heat flow rate measurement that is based solely on the difference between sample and reference calorimeter temperatures. Heat flow rates measured using the improved measurement agree very well with the model predictions for heat exchange between the sample and its pan.     

A New Theoretical Approach to Steady State of Temperature Modulated Heat Flux DSC

The steady state of temperature modulated heat flux DSC, in which the sample temperature is controlled at a fixed frequency, a fixed amplitude and a constant underlying heating rate, is theoretically investigated for complex heat capacity of the sample, taking accounts of heat capacities of heat paths, heat loss to the environment and mutual heat exchange between the sample and the reference material. Rigorous and general solutions for the temperature difference oscillation are obtained in relation to the sample temperature as a reference oscillation. The results are quite different from those obtained in functions of the heat source temperature as a reference oscillation. From these solutions, application of the technique to heat capacity measurements is discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

差示扫描量热法测定对乙酰氨基酚原料药纯度

建立差示扫描量热(DSC)法测定对乙酰氨基酚原料药纯度的方法。考察升温速率、称样量、坩埚类型对测定结果的影响,确定最佳测定条件:升温速率为1.0℃/min,称样量为2.0~2.2 mg,选用Tzero密封铝坩埚作为样品盘。DSC法测定对乙酰氨基酚原料药纯度为99.91%,测定结果的相对标准偏差为0.03%(n=6),DSC法测定结果与紫外可见分光光度法测定结果(99.85%)基本一致,且DSC法测定结果的相对标准偏差较小。该方法简便、快速、准确,无需标准品,可用于对乙酰氨基酚原料药纯度的测定。     

Effect of heating rate on the separation of various phenomena in the DSC technique

The value chosen for the heating rate plays an important role in the DSC technique. For example, the use of a low heating rate is of great help in determining the kinetic parameters of reactions more clearly. In this paper, the separation of peaks corresponding to heat flux-time curves of two various phenomena is especially studied. These peaks are shown in a typical cure reaction of epoxy resins. After determination of the kinetic parameters, DSC curves are simulated and a good agreement is found between theoretical and experimental curves. The effect of the heating rate on the separation factor of these peaks is studied, as well as its effect on the sensitivity of heat-flux measurement.     

Experimental Evaluation of Procedures for Heat Capacity Measurement by Differential Scanning Calorimetry

Experimental evaluation of the procedures adopted for heat capacity measurements employing differential scanning calorimetry (DSC) has been carried out by taking nickel and sapphire as test samples. Among the various methodologies reported in literature, the absolute dual step method was chosen for this purpose due to its simplicity and minimum number of measurements required. By proper temperature and heat flux calibration employing indium as reference, it was possible to obtain the calibration factor independent of temperature. This was ascertained by analysing other pure metals namely Sn, Zn, Cd, and Pb and determining their melting temperatures and heats of melting. Various operator- and sample-dependent parameters such as heating rate, sample mass, the structure of the sample, reproducibility and repeatability in the measurements were investigated. Heat capacities of both nickel and sapphire have been determined using the above method. Further, the heat capacity of nickel has also been determined using the widely employed three-step method taking sapphire as the heat flux calibration standard. Both methods yielded the comparable heat capacity values for nickel. Based on the parameters investigated and their influence, it could be concluded that reasonably precise and accurate heat capacity measurements are possible with DSC. One advantage of this method is the elimination of a separate calibration run using a reference material of known heat capacity. This revised version was published online in August 2006 with corrections to the Cover Date.     

Heat capacity measurement by modulated DSC at constant temperature

The mathematical equations for step-wise measurement of heat capacity (C _p ) by modulated differential scanning calorimetry (MDSC) are discussed for the conditions of negligible temperature gradients within sample and reference. Using a commercial MDSC, applications are evaluated and the limits explored. This new technique permits the determination ofC _p by keeping the sample continually close to equilibrium, a condition conventional DSC is unable to meet. Heat capacity is measured at ‘practically isothermal condition’ (often changing not more than ±1 K). The method provides data with good precision. The effects of sample mass, amplitude and frequency of temperature modulation were studied and methods for optimizing the instrument are proposed. The correction for the differences in sample and reference heating rates, needed for high-precision data by standard DSC, do not apply for this method. Presented in preliminary from at the 22nd NATAS Conference in Denver, CO 9/19-22/93 (Proceedings, pages 59–64, editor K. R. Williams).     

Optimization of Flynn and Levin measurements of polymer thermal conductivity

In this article procedures to measure specifically thermal conductivity of polymers by means of traditional differential scanning calorimetry (DSC) are discussed and an improved procedure minimizing the effect of contact resistances variability has been conceived. A pure substance, namely indium, for which the fusion temperature is known, is added to the polymer sample and used as internal reference in a unique DSC pan. Conductivity is then obtained by measuring the rate of the heat flow through the solid polymer sample during the solid–liquid transition of indium. The present procedure gives uncertainties lower than those expected for thermal conductivity estimations by previous DSC methods, does not require thermal conductivity reference materials nor specimens of various thickness and may be performed routinely with an automatic sample changing device.     

ASTM Kinetics of Oil Shales

Thermal analysis is increasingly being used to obtain kinetic data relating to sample decomposition. In this research differential scanning calorimeter (DSC) was used to determine the combustion kinetics of three (Çan, Himmetoglu and Mengen) oil shale samples by ASTM and Roger &; Morris methods. On DSC curves two reaction regions were observed on oil shale sample studied except Çan oil shale. In DSC experiments higher heating rates resulted in higher reaction temperatures and higher heat of reactions. Distinguishing peaks shifted to higher temperatures with an increase in heating rate. Three different kinetic models (ASTM I-II and Rogers &; Morris) were used to determine the kinetic parameters of the oil shale samples studied. Activation energies were in the range of 131.8-185.3 kJ mol-1 for ASTM methods and 18.5-48.8 kJ mol-1 for Rogers &; Morris method.