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Abstract  

The nucleating efficiency and selectivity of different β-nucleating agents was characterised and compared by differential scanning calorimetry, (DSC) and temperature-modulated DSC (TMDSC). The nucleating agents were the calcium salts of pimelic and suberic acid (Ca-pim and Ca-sub), linear trans-γ-quinacridone (LTQ), a commercial nucleator NJ Star (NJS) and an experimental product (CGX-220). The efficiency and the selectivity of Ca-sub and Ca-pim are extremely high. NJS is efficient above a critical concentration, which is connected with its partial dissolution in polypropylene melt. LTQ and CGX-220 possess strong overall nucleating ability and moderate selectivity. Using TMDSC, we found that three consecutive processes take place during the heating of β-nucleated samples cooled down to room temperature: reversible partial melting of the β-form, irreversible βα-recrystallisation, and the melting of the α-modification formed during βα-recrystallisation or being present in samples prepared with non-selective β-nucleators. Melting of the α-phase contains both reversible and irreversible components.

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TOPEM, a new temperature modulated DSC technique

Application to the glass transition of polymers

Journal of Thermal Analysis and Calorimetry
Authors:
Iria Fraga
,
S. Montserrat
, and
J. Hutchinson

Abstract  

TOPEM is a new temperature modulated DSC technique, introduced by Mettler-Toledo in late 2005, in which stochastic temperature modulations are superimposed on the underlying rate of a conventional DSC scan. These modulations consist of temperature pulses, of fixed magnitude and alternating sign, with random durations within limits specified by the user. The resulting heat flow signal is analysed by a parameter estimation method which yields a so-called ‘quasi-static’ specific heat capacity and a ‘dynamic’ specific heat capacity over a range of frequencies. In a single scan it is thus possible to distinguish frequency-dependent phenomena from frequency-independent phenomena. Its application to the glass transition is examined here.

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Abstract  

A new method is presented to analyze the irreversible melting kinetics of polymer crystals with a temperature modulated differential scanning calorimetry (TMDSC). The method is based on an expression of the apparent heat capacity,
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $$\Delta \tilde C{e}^{---{i\alpha }} = mc_p + i(1/{\omega }F'_{T}$$ \end{document}
, with the true heat capacity, mcp, and the response of the kinetics,
\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $$F'_{\text{T}}$$ \end{document}
. The present paper experimentally examines the irreversible melting of nylon 6 crystals on heating. The real and imaginary parts of the apparent heat capacity showed a strong dependence on frequency and heating rate during the melting process. The dependence and the Cole-Cole plot could be fitted by the frequency response function of Debye's type with a characteristic time depending on heating rate. The characteristic time represents the time required for the melting of small crystallites which form the aggregates of polymer crystals. The heating rate dependence of the characteristic time differentiates the superheating dependence of the melting rate. Taking account of the relatively insensitive nature of crystallization to temperature modulation, it is argued that the ‘reversing’ heat flow extrapolated to ω → 0 is related to the endothermic heat flow of melting and the corresponding ‘non-reversing’ heat flow represents the exothermic heat flow of re-crystallization and re-organization. The extrapolated ‘reversing’ and ‘non-reversing’ heat flow indicates the melting and re-crystallization and/or re-organization of nylon 6 crystals at much lower temperature than the melting peak seen in the total heat flow.
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Abstract  

One of the benefits of temperature-modulated DSC (TMDSC) is its ability to measure thermal conductivity and thermal diffusivity without DSC cell modifications or additional accessories. Thermal conductivity of solid materials from 0.1 to about 1 W m-1 K-1 measured. Applications of this approach have been discussed in the literature but no description is yet available concerning the derivation of the working equations. This presentation provides a detailed derivation of the working equations used to obtain thermal conductivity and thermal diffusivity from TMDSC data.

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Journal of Thermal Analysis and Calorimetry
Authors:
A. Boller
,
I. Okazaki
,
K. Ishikiriyama
,
G. Zhang
, and
B. Wunderlich

Abstract  

The quality of measurement of heat capacity by differential scanning calorimetry (DSC) is based on the symmetry of the twin calorimeters. This symmetry is of particular importance for the temperature-modulated DSC (TMDSC) since positive and negative deviations from symmetry cannot be distinguished in the most popular analysis methods. Three different DSC instruments capable of modulation have been calibrated for asymmetry using standard non-modulated measurements and a simple method is described that avoids potentially large errors when using the reversing heat capacity as the measured quantity. It consists of overcompensating the temperature-dependent asymmetry by increasing the mass of the sample pan.

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Abstract  

Temperature modulated DSC (TMDSC) at low temperatures requires attention to the selection of experimental parameters that are within the capability of the instrumentation as well as special care in calibration of heat capacity measurement when high precision is required. Data are presented to facilitate selection of appropriate modulation periods and amplitudes at low temperature when using a mechanical cooling accessory. The standard error of the mean heat capacity measurement for a sapphire standard increased with decreasing temperature, decreasing period, and increasing pan mass. For ice in hermetically sealed pans, the standard error of the mean heat capacity measurement was larger than for sapphire and did not follow a predictable trend with changes in temperature and period of modulation. This was attributed to changes in sample geometry between successive measurements due to melting and resolidification. A simple one-point temperature calibration by TMDSC may be unsuitable for precise measurement of heat capacity because of the random error caused by sample placement and the systematic error caused by cell asymmetry, temperature dependence of the calibration constant, and different sample thermal conductivities. An alternative calibration procedure using standard DSC and either a linear or second order fit of the calibration constant over the temperature range of interest is proposed.

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Abstract  

Temperature-modulated DSC (TMDSC) was used to enhance the perfection of crystals of different poly(p-phenylene sulfide) samples formed during slow cooling from the melt. The sample preparation was made with modulated cooling using a cool-heat mode. Re-heating the samples prepared by slow conventional and modulated coolings indicated that the melting point of the samples prepared by modulated cooling is considerably higher than the melting point of the samples crystallized with conventional cooling. Thus, the perfection of crystallites can be improved if the outer layers just deposited on their surface are re-melted and re-crystallized immediately.

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Abstract  

The frequency dependences of the complex-specific heat of the sodium borate glasses, xNa2O·(100 − x)B2O3, where x denotes molar concentration of Na2O, have been investigated by temperature-modulated DSC. The temperature dependences of α-relaxation time have been analyzed in Angell plot, and the fragility index has been determined. The composition dependence of the fragility index has been discussed on the basis of the variations of the structural units of the borate network. The origin of the fragility of the borate system relates to the distribution of the coordination number of boron atom.

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Abstract  

The curing reaction of a thermosetting system is investigated by DSC and temperature modulated DSC (TMDSC). When the material vitrifies during curing, the reaction becomes diffusion controlled. The phase shift signal measured by TMDSC includes direct information on the reaction kinetics. For long periods the phase shift is approximately proportional to the partial temperature derivative of the reaction rate. This signal is very sensitive for changes in the reaction kinetics. In the present paper an approach to determine the diffusion control influence on the reaction kinetics from the measured phase shift is developed. The results are compared with experimental data. Further applications of this method for other reactions are proposed.

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Abstract  

The application of non-linear heating program to a heat-flux DSC apparatus has attracted much attention. From thermodynamics viewpoint, it is shown that the variation of enthalpy of a sample changing with temperature change is due, to both the true heat capacity of the sample and the enthalpy of some transformations occurring in the sample, characterized by its degree of advance. Using the simple assumption that the rate of the transformation is proportional to the distance from the thermodynamic equilibrium, an electrical model of the thermal event is given. Using the coupled cell model of the DSC apparatus, we show how to obtain the rate of transformation of the sample and heat capacity, which is directly related to the base line of the experiment.

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