差示扫描量热法和调制差示扫描量热法测定聚乳酸热学性质比较

<正>差示扫描量热法(DSC)是一种通过记录物理化学变化过程中待测物本身吸热放热的信息,分析得出材料热性能的重要方法~([1-4])。DSC具有样品易制备、分析快速、温度范围宽、定量能力强、适用于固体和液体等优点,广泛应用于高分子材料~([5-6])、石油化工~([7])、医药以及无机等领域~([8-9])。与传统DSC仅给出总热流信号不同,调制差示扫描量热法(MDSC)在传统的DSC升温程序上叠加正弦调温程序,在得     

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。     

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。     

调制差示扫描量热法在高分子材料中的应用

调制差示扫描量热法(MDSC)是在传统线性变温基础上叠加一个正弦震荡温度程序,将总热流量分解为可逆热流(热容成分)和不可逆热流(动力学成分),同时具有较高的灵敏度和分辨率,在研究高分子材料复杂相变时具有独特的优势。近年来,MDSC在研究高分子材料的玻璃化转变、结晶-熔融、热容变化等领域得到了较为广泛的应用。本文对MDSC近年来在高分子材料中的最新研究应用做了详细介绍。     

DMSO对鸡蛋白溶菌酶溶液变性的影响

利用差示扫描量热(DSC)和温度调制差示扫描量热(MDSC)研究了鸡蛋白溶菌酶在纯水及二甲基亚砜(DMSO)/水混合溶剂中的热变性过程, 探讨了酶的浓度、扫描速率和共溶剂的含量对热变性行为的影响规律. 在纯水溶液中, 溶菌酶的变性焓(△Hm)随酶浓度的增大而增大. 而在DMSO/水混合溶剂中, 变性温度(Tm)随DMSO体积分数的增大向低温方向移动, 变性峰变低变宽; 当DMSO体积分数达到70%后, 热变性曲线变成了一条光滑的直线. 另外, 在纯水溶液中溶菌酶的MDSC图除了出现DSC中可观察到的主吸热峰(I)外, 在峰(I)的前面还出现一个小而对称的吸热峰(II), 并且当体系中有DMSO存在时也未能观察到此峰. 当溶菌酶浓度增大时, Tm(II)移向低温, △Hm(II)减小, Tm(I)与Tm(II)之间的距离变长. 吸热峰(II)的出现被认为是由于水溶液中溶菌酶二聚体的可逆离解造成的.     

Al-4.5Cu和Mullite增强Al-4.5Cu复合材料时效析出行为的DSC研究

用差示扫描量热法（DSC）对Al-4.5Cu合金和莫来石（Mullite)短纤维增强Al-4.5Cu复合材料的时效析出行为进行了研究；结果表明Al-4.5Cu合金和Mullite增强Al-4.5Cu复合材料固溶淬火试样的DSC扫描曲线存在较大不同，溶质原子富集区（GP）形成和溶解的信息在基体合金的DSC曲线上清晰可见，但在复合材料的DSC曲线上则很难确认，表明纤维推延或抑制了GP区的形成；中间沉淀析出相θ″和θ′的析出过程由于纤维的引入而得到明显加快，峰值温度降低，活化能减小，时效析出过程加快；但是，扫描参数选择不当时，容易对析出相的析出过程产生错误判断，应引起重视。     

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.     

联合载体用于改善白藜芦醇固体分散体性能

通过载体聚乙烯吡咯烷酮(PVPk29/32)和羟丙基甲基纤维素(HPMC),采用溶剂法制备白藜芦醇(Res)二元及三元固体分散体。 用傅里叶变换红外光谱(FTIR)、调制式差示扫描量热(MDSC)和X射线粉末衍射(XRD)等技术手段来表征Res二元和三元固体分散体并考察其溶出度。 FTIR结果显示,Res与PVPk29/32及HPMC均存在氢键相互作用;溶出结果表明,二元和三元固体分散体均能提高药物的溶出度。 而XRD和MDSC结果表明,三元固体分散体的相容性优于二元固体分散体;3个月的加速实验(40 ℃,75%RH(relative humidity))中,XRD、MDSC及体外溶出结果表明,Res三元固体分散体的稳定性优于Res二元固体分散体。 HPMC的加入可以改善Res三元固体分散体的溶出及稳定性。     

用α-Al2O3研究比热测试与MDSC条件的相关性

通过α-Al2O3的比热测试,研究了调制式差示扫描量热法(MDSC)测量比热(Cp)与温度(T)、线性升温速率(β)、温度调制振幅(AT)和调制周期(ρ)的相关性,并对测试误差进行校正.实验结果表明:Cp随T提高和ρ延长而增大;但β和AT对Cp影响不大;ρ=30 s时实测值(Cpms)与文献值(Csptd)的相对误差(Erms)最小,在温度为100~200℃范围小于3%;导出了对Cpms进行修正的多项式校正参数,在ρ为20~50 s、温度为100~200℃范围,修正后的比热(Cpmd)与文献值的相对误差(Ermd)小于1.5%.     

高聚物的非等温结晶动力学——从不同速率的升温或降温DSC曲线解析结晶动力学参数

根据等温DSC法,测定结晶动力学参数在实验上存在着一定的局限性,结晶太快或太慢都难于获得可靠的结果,这就限定了能测定的温度区间。可见,等温DSC法测定结晶动力学参数具有获得的信息量少,结晶起始点难以确定,费时等缺点。这些缺点可通过等速变温DSC法来克服。然而,通过等速变温DSC法测定结晶动力学参数的方法至今还不完善。例如Ozawa曾基于Evans理论把Avrami方程推广于非等温结晶,从Ozawa方程通过等速变温DSC曲线可得到表征结晶机理的函数Avrami ＄数。和冷却结晶函数。Ozawa方法的不足是从其冷却结晶函数不能解析出表征结晶速率的参数。     

Experimental investigation into the heat capacity measurement using an modulated DSC

Experiments using a commercial modulated DSC (MDSC) for the measurement of specific heat capacity of a sample have been carried out. It is found that because the amplitude of heat flow of MDSC is a complicated non-linear function of various experimental conditions such as the modulation frequency and the heat capacities of a sample and pan, the methodology of heat capacity determination using an MDSC in a single run has not been justified. The experimental results, on the other hand, agree with the theoretical equation of one of the authors. It is therefore concluded that the capabilities of MDSC should be further examined.     

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.     

Physical Aging of Maltose Glasses as Measured by Standard and Modulated Differential Scanning Calorimetry

The physical aging characteristics of maltose glasses aged at two temperatures below the glass transition temperature, T_g, (T_g-10°C and T_g-20°C) from 5 to 10 000 min were measured by standard differential scanning calorimetry (SDSC) and modulated differential scanning calorimetry (MDSC). The experimentally measured instrumental T_g, the calculated T_g, and the excess enthalpy values were obtained for aged glasses using both DSC methods. The development of excess enthalpy as a function of aging time, as measured by both SDSC and MDSC, was fit using the Cowie and Ferguson and Tool-Narayanswamy-Moynihan models. The change in the T_g values and the development of the excess enthalpy resulting from physical aging measured by the two DSC methods are discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Obtaining Modulated Temperature DSC Curves Through a Non-conventional DSC Method

The DSC curve obtained in conventional equipment usually only shows the resultant thermal effect due to simultaneous phenomena, which may occur during isothermal or dynamic analyses. This does not allow one to identify the processes properly and may cause an erroneous interpretation of the resulting curves. Modulated DSC equipment enhances the operating conditions and the analysis capacity of conventional DSC by superimposing a sinusoidal temperature modulation on the linear temperature control. Thus reversing and non-reversing heat flow curves are obtained, which are, respectively, the heat capacity and kinetic components of the DSC curve. Therefore, events that are related to these components can be separately analyzed. A method to obtain curves similar to the MDSC reversing and non-reversing components was developed using conventional DSC equipment in a non-conventional way. It was applied to analyze samples of poly(ethylene terephthalate) (PET) taken from bottles of mineral water. The second PET crystallization step that occurs during its melting was quantified and an apparent initial crystallinity was obtained from the resulting data. This revised version was published online in August 2006 with corrections to the Cover Date.     

Effect of soft segment length on the thermal behaviors of fluorinated polyurethanes

Differential scanning calorimetry (DSC) and temperature modulated DSC (MDSC) have been applied to investigate the thermal behaviors of fluorinated polyurethanes (FPU), which were obtained using 2,2,3,3-tetrafluoro-1, 4-butanediol as the chain extender and based on various soft segments—polytetramethyl oxides (PTMO) with molecular weights of 650, 1000, 1400 and 2000. An exothermic peak and/or multiple melting endotherms were observed during the heating to melting temperature of soft and hard segments. Attributed to the simultaneous recrystallization and melting processes during heating, these features have been confirmed via MDSC, where an endotherm and an exotherm were noted in reversing and non-reversing components of the heat flow. Separating the non-reversing components from the reversing curves, the dependencies of polyurethane morphology on the length of the soft segment could be clarified using MDSC analysis. Soft segment lengthening significantly influences the morphology of soft segment domains in FPUs. The phase separation and crystallinity of the soft segment increased with its length. However, soft segment length exerted a minor influence on the dissociation temperature of the short-range ordered hard segment domain and on the melting temperature of hard segment crystals. Examination of the heats of melting based on the quasi-isothermal MDSC experiments indicated that the crystallinity of hard segment domains declined with increasing soft segment length.     

Melting and glass transitions in paraffinic and naphthenic oils

Naphthenic and paraffinic oils were analyzed by modulated differential scanning calorimetry (MDSC). The results showed several improvements in the analysis of thermal properties when compared with standard DSC. The glass transition temperature (T_g), the enthalpy relaxation at T_g, and the melting endotherms could be deconvoluted, and reversible melting could be identified. This allowed for an easier interpretation of the thermal properties of the oils. With MDSC, the T_gs in mineral oils were found to coincide with endothermic enthalpy relaxation, which is generally regarded as a melting endotherm with standard DSC. A decrease in heat capacity after T_g was attributed to the existence of rigid amorphous material. From Δc_p at T_g and the oil molecular weight, the number of repeat units in the oil chains was estimated at less than 20. The T_g of a hypothetical pure aromatic oil was found to be similar to that for petroleum asphaltenes, and that for a naphthenic oil of infinite molecular weight to be similar to that of petroleum resins.     

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).     

A modulated dsc study on the in situ polymerization of cyclic butylene terephthalate oligomers

The polymerization of a cyclic butylene terephthalate (CBT) oligomer was studied as a function of temperature (T=200 and 260°C, respectively) by modulated DSC (MDSC). The first heating was followed by cooling after various holding times (5, 15 and 30 min) prior to the second heating which ended always at T=260°C. This allowed us to study the crystallization and melting behavior of the resulting polybutylene terephthalate (PBT), as well. In contrary to the usual belief, the CBT polymerization is exothermic and the related process is superimposed to that of the CBT melting. The melting behavior of the PBT was affected by the polymerization mode (performed below or above the melting temperature of the PBT product) of the CBT. Annealing above the melting temperature of PBT yielded a product featuring double melting. This was attributed to the presence of crystallites with different degrees of perfection. The crystals perfection which occurred via recrystallization/remelting was manifested by a pronounced exothermic peak in the non-reversing trace.     

Calculation of smoothing factors for the comparison of DSC results

Complex mixtures of long chain organic compounds often show overlapping glass transition temperatures (T _gs) when analyzed by differential scanning calorimetry (DSC) or modulated DSC (MDSC). In such cases, subjective and inconsistent smoothing of data acquired under different conditions can lead to the misinterpretation of results. A quantitative method for the selection of smoothing factors for the analysis and comparison of (M)DSC results is presented. The method is most useful for the analysis of the derivative of the heat capacity, dC _p/dt or dC _p/dT, plots which best highlight overlapping T _gs. Four equations are shown to relate the heating rate and the smoothing factor. The equations allow a comparison of data acquired i) at different heating rates and plotted vs. temperature, ii) at a single heating rate and plotted vs. both time and temperature, i.e., dC _p/dt vs. dC _p/dT, iii) at different heating rates and plotted vs. both time and temperature, and iv) at different heating rates, and shown exclusively in the time domain. Examples of the use of the equations are provided for the analysis of bitumen, a complex mixture of natural origin.