Modulated temperature DSC measurements relating to the cold crystallization process of poly(ethylene terephtalate)

The modulated temperature differential scanning calorimetric method (MT-DSC) yields three temperature dependent signals, an underlying heat capacity curve from the underlying heat flow rate (corresponding to the conventional DSC signal), and a complex heat capacity curve with a real part (storage heat capacity) and an imaginary part (loss heat capacity). These curves have been measured in the cold crystallization region for poly(ethylene terephtalate) with a modified Perkin-Elmer DSC-7. The underlying curve shows the well known large exothermic crystallization peak. The storage heat capacity shows a step change which reproduces the change in heat capacity during crystallization. This curve may be used as baseline, to separate the crystallization heat flow rate from the underlying heat flow rate curve. The loss heat capacity curve exhibits a small exothermic peak at the temperature of the step change of the storage curve. It could be caused by changes of the molecular mobility during crystallization.Dedicated to Professor Wunderlich on the occasion of his 65th birthday     

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 Theoretical Approach to Temperature Modulated Power Compensation DSC

The steady state of temperature modulated power compensation DSC has been theoretically investigated for measurements of complex heat capacity, taking accounts of heat capacities of heat paths, heat loss to the environment, and mutual heat exchange between the sample and the reference material. Thermal contact between the sample cell and the cell holder is also taken into accounts. Rigorous and general solutions are obtained. From these solutions application of the technique to heat capacity measurements is discussed. 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).     

Miscibility of polymer blends studied by a simplified method of data analysis using light heating modulated temperature DSC

A simple method of application of light heating modulated temperature DSC to a study of miscibility of polymer blends has been developed. In this method only the sample was measured and the standard materials were not used. The total heat flow, the complex heat capacity, the reversing and non-reversing heat flows were obtained as values measured from those quantities in hypothetical glassy state at T>T_g. The values of the hypothetical glassy state were calculated by extrapolation from T<T_g. The present method gives relative values but useful information can be obtained from the results. Some results from miscible and immiscible polymer blends are shown. This revised version was published online in July 2006 with corrections to the Cover Date.     

Modulated differential scanning calorimetry

Modulated-temperature differential scanning calorimetry was used to measure the glass transition temperature,T _g, the heat capacity relaxation in the glassy state and the increment of heat capacity, C_p, in the glass transition region for several polymers. The differential of heat capacity with respect to temperature was used to analyseT _g and C_p simply and accurately. These measurements are not affected by complex thermal histories.     

Modulated‐temperature differential scanning calorimetry study of temperature‐induced mixing and demixing in poly(vinylmethylether)/water

The heat capacity or reversing heat flow signal from modulated‐temperature differential scanning calorimetry can be used to measure the onset of phase separation in a poly(vinylmethylether)/water mixture, clearly showing the special type III lower critical solution temperature demixing behavior. Characteristic of this demixing behavior is a three‐phase region, which is detected in the nonreversing heat flow signal. Stepwise quasi‐isothermal measurements through the phase transition show large excess contributions in the (apparent) heat capacity signal, caused by demixing/remixing heat effects on the timescale of the modulation (fast process). These excess contributions and their time‐dependent evolutions (slow process) are useful in understanding the kinetics of phase separation and the morphology (interphase) development. Care has to be taken, however, in interpreting the heat capacity signal derived from the amplitude of the modulated heat flow because nonlinear effects lead to the occurrence of higher harmonics. Therefore, the raw heat flow signal for quasi‐isothermal demixing and remixing measurements is also examined in the time domain. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1824–1836, 2003     

General Theory of Steady State of tm-DSC and its Application to Complex Heat Capacity Measurements

For complex heat capacity measurements, steady state of various types of temperature modulated DSC is theoretically investigated by a set of common comprehensive fundamental equations of heat balance. Heat capacities of heat paths, heat loss to the environment and mutual heat exchange between the sample and the reference material are taken into accounts together with thermal contact effect between the cell and its holder plate. Rigorous and general solutions have been obtained, and useful relations for complex heat capacity measurements have been derived for each type of DSC. They are compared with each other to elucidate unique features of each type of DSC.This revised version was published online in November 2005 with corrections to the Cover Date.     

Temperature modulated differential scanning calorimetry (TMDSC) in the region of phase transitions. Part 1: theoretical considerations

For temperature modulated differential scanning calorimetry (TMDSC) a simple model, the low pass filter, is presented which allows to see and calculate the influence of heat transfer into the sample on magnitude and phase shift of the modulated part of the measured heat flow rate and the heat capacity determined from it. A formula is given which enables to correct the measured magnitude of the periodic heat flow rate function and the calculated heat capacity in dependence on the thermal resistance and heat capacity of the sample. The correction becomes very important in regions where the heat capacity changes considerably as in the melting region. The approach is successfully tested with model substances with well-known excess heat capacity in the transition region.     

Temperature and Heat Flow Calibration of A DSC-instrument in the Temperature Range Between −100 and 160°C

Thermoanalytical instruments are extensively used in R&D as well as in industrial quality control. A quantitative analysis of the data of a thermoanalytical measurement requires a careful calibration of the instrument. In differential scanning calorimetry (DSC) the quantities that have to be calibrated are the temperature and the heat flow. These two quantities are usually calibrated by evaluating melting or solid-solid transitions of some reference materials with well known transition enthalpies and temperatures. In this contribution we investigate temperature and heat flow calibration in the temperature range between −100 and 160°C. We included 9 different samples for the analysis and established some general rules for the calibration process. As a result we found that with a well calibrated instrument the heat flow can be measured with 90% confidence to about ± 3% accuracy in this temperature range. With respect to temperature calibration we find that accuracies of ±0.8°C (90% confidence) may be expected. These values represent general accuracy limitations of DSC’s due to varying heat transfer conditions within the samples. This revised version was published online in July 2006 with corrections to the Cover Date.     

Heat Transfer in a Disc-Type DSC Apparatus IV. Applicability of the coupled cells model to periodic temperature modulation

The application of non-linear heating programs to a heat-flux DSC apparatus has attracted much attention. On the basis of thermodynamics, the change in enthalpy of a sample during a temperature change ΔT is due, on the one hand to the true heat capacity of the sample ΔT C_pξ and on the other, to the enthalpy of some transformation occurring in the sample Δ_rH Δξ. These contributions can be separated on the basis of the kinetics of the transformation. The coupled cells model of a disc type, heat flux DSC apparatus has been tested, using true heat capacities and a sine modulation of the temperature of the furnace around a constant temperature. In the range from 2 to 60 mHz, the amplitude and phase shift of the calorimetric signal were measured at several frequencies. Theoretical equations, based on the model, and using the thermal Ohm's law explains the results with a reasonable accuracy. A non-linear DSC experiment affords two ways of determination of the heat capacity of a sample making possible a distinction between the enthalpic effect and heat capacity. This revised version was published online in July 2006 with corrections to the Cover Date.     

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.     

Temperature modulated differential scanning calorimetry (TMDSC) in the region of phase transitions. Part 2: some specific results from polymers

By means of four different examples (pressure crystallised, gel crystallised, nascent and highly stretched polyethylenes (PEs)) it is shown that temperature modulated DSC offers advantages against common DSC. It is possible to see dynamic processes inside the sample during melting. This way we found (i) that during melting of high pressure crystallised PE the so-called ₂-process (known from DMA) takes place, (ii) the lamellae doubling in gel crystallised UHMWPE can be seen in TMDSC signals, though no balance heat flow rate is visible in the common DSC, (iii) the same is true for the recrystallisation in nascent and highly stretched PE many degrees before the melting peak appears. To separate these results from the measured curves the knowledge of the heat transport into and within the sample is needed. A simple low pass filter model has proved its worth for this purpose.     

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.     

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.     

Quasi-isothermal measurement of frequency dependent heat capacity of semicrystalline polyethylene at the melting temperature using light heating modulated temperature DSC

Frequency dependence of the heat capacity of semicrystalline polyethylene was measured using light heating modulated temperature DSC (LMDSC). The quasi-isothermal measurement was carried out in the melting temperature range of the crystal. Two decades of the frequency, from 0.01 to 1 Hz, was covered by the LMDSC instrument constructed in the author's laboratory. It was found that in the melting temperature range polyethylene exhibited Debye relaxation with the relaxation time of 14 s and had excess heat capacity independent of the kinetics. The excess heat capacity and the relaxation strength could be attributed to the disordered crystals generated during rapid cooling from the molten state and/or its surrounding amorphous region instead of the stable crystals reorganized during the quasi-isothermal measurement.     

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.     

DSC法测定PS玻璃化温度的再研究

对Fevotte提出的由DSC曲线构建玻璃化温度谱图的方法进行了改进,将橡胶态含量为0.5时的温度定义为聚合物的Tghr.采用改进Fevotte方法重新研究了PS的玻璃-橡胶态转变,PS的Tghr值比半比热外推法结果Tghc高约4K,当考察热处理时间和降温速率对聚合物玻璃-橡胶态转变的影响规律时,改进方法得到的结果与理论分析更为一致.聚合物的Tghr受热历史影响,随热处理条件改变,通过对不同降温速率冷却后样品滞后焓数据的拟合,推测PS样品的Tghr在377.5～390.9K范围内变化.     

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。     

Modulated Differential Scanning Calorimetry Observation of Physical Ageing in Polymers

Modulated-temperature differential scanning calorimetry (M-TDSC) is becoming a useful tool in the characterisation of thermal behaviour of polymers. In this paper, we discuss whether the non-reversing M-TDSC signal can be used, quantitatively and directly, to study the process of physical ageing in polymers. Difference exists between the values of relaxation enthalpy determined by using average heat capacity, <C _p>, signal as for conventional DSC and non-reversing heat capacity, C ⁿ _p, signal. When the signal of reversing heat capacity of unaged sample is considered as baseline for <C _p> and C ⁿ _p signals, the difference disappears. It is concluded that non-reversing M-TDSC signal can be used to observe the process of physical ageing semi-qualitatively and directly. With increasing annealing time, the peak of the imaginary part, C″_p, of the complex heat capacity becomes narrow, but peak area changes little. This indicated that C″_p is not correlated with relaxation enthalpy. It may be related to entropy change during the modulation. However, the entropy change is quite small. This revised version was published online in August 2006 with corrections to the Cover Date.