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The glass transition temperature of a copolymer depends not only on chemical composition but also on its comonomer sequences. This experimental fact is explained by Barton's and Johnston's equations. Their equations, though complicated, become simple, if a suitable parameter is used to describe the comonomer sequences. It is shown that with these new expressions, their equations can be used to understand glass transition temperatures of two additional types of copolymers, compatible multiblock copolymers and homopolymers with various tacticities treated as steric copolymers.

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Abstract  

The thermomechanical properties of opaque and transparent polymer films of a solution of poly(4-methyl-1-pentene) (PMP) in cyclohexane and carbon tetrachloride obtained by casting on teflon and glass plates were investigated. The dynamic mechanical thermal analysis was applied in a frequency range from 0.01 to 100 Hz. The curves of loss tangent vs. temperature varied depending on the sample thermal history. The first part of these curves could relate to the backbone α relaxation into the unperturbed amorphous phase while the next relaxation could result from the backbone α relaxation into amorphous phase perturbed by the presence of the crystal domains. The Arrhenius plots of the first relaxation show a stronger curvature found in each of the transparent samples indicating strong dependency on specific volume. The second one in the case of transparent films and the first one for opaque samples might be approximate to straight lines.

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Abstract  

A discussion on the influence of grafted polar groups (succinic anhydride and succinil-fluorescein) in glass transition behaviour of atactic polypropylene is shown in this work, on the basis of the reaction conditions used to obtain the modified polymers, kind and amount of grafted groups, and the degradation processes which may take place. The Box-Wilson experimental design methodology for two independent variables (reactant concentration to obtain the modified polymer) has been used to follow variations in glass transition temperatures. The existence of undesired degradation processes is considered as independent of the grafting reactions, and the model predictions seem to agree with this latter.

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Abstract  

The heat capacity or the specific heat is for any crystalline, partially amorphous or completely amorphous substance or material a significant thermodynamic property. The glass transition may be regarded as the melting point of amorphous substances and materials, a transition property of an outstanding technical importance. A crucial point is the fact that the presence of a glass transition is an unequivocal proof of an amorphous content of a material. Furthermore, the change of the specific heat at the glass transition temperature enables the quantitative determination of the amorphicity on a relative or absolute level of any substance or material. The absolute determination of the amorphicity affords a calibration with a reference corresponding to the material under investigation. The crystallinity for this reference substance must be known from the preparation and or by any independent analytical method. The literature data for the specific heat and the glass transition of polystyrene were collected and evaluated. Data were found for the specific heat in literature from 10 to 470 K. The data were unified for each of the reported temperature in a mean value and the corresponding standard deviation was determined. An excellent conformity was found in the glassy state of polystyrene with standard deviations lower than 0.7%. The standard deviations above the glass transition were considerably higher. All these literature data were transferred for each of the literature sets separately into linear specific heat functions in the vicinity of the glass transition. One set of our measurements performed with the DSC 204 and with polystyrene SRM 705a as sample material was additionally integrated in the mean of these functions for the glassy state and the liquid amorphous state respectively. The addition of our results gave practically no change of the mean coefficients and only a decrease of the standard deviations. In such a way, the data with the best statistical base for the specific heat of polystyrene are listed in this paper ( ‘Conclusions’). The glass transition as a transition in and out of a non-equilibrium state, the glassy state, is sensitive to all kind of influences such as thermal and mechanical treatments as well as to the selected experimental conditions. Therefore, certain standardized conditions procedures must be fulfilled to get reproducible data. The literature data for the glass transition temperature were also used to get a mean value. However, two values were omitted for the formation of the mean, because the authors reported values, which were too low on the base of impurities present. The mean value of the glass transition for polystyrene is according to the literature 3692 K. A mean value of 3702 K was extrapolated for an infinite molecular mass. The DSC and TMDSC measurements for the three thermodynamic properties reported in this paper, namely the specific heat, the glass transition temperature and the corresponding change of the specific heat gave results without significant differences compared with the literature values. Atactic polystyrene is a rather ideal polymer together with sapphire as calibration substance to elucidate and validate the DSC and TMDSC procedures for the determination of the specific heat and the glass transition.

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The glass transition of an irradiated, ultra-high molecular weight, linear polyethylene was investigated by means of the Perkin-Elmer DSC-2 differential scanning calorimeter. The experimental specific heat data were compared with those of the nonirradiated sample, obtained by DSC and adiabatic calorimetry.

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Journal of Thermal Analysis and Calorimetry
Authors:
Marek Liška
,
Zdenek Černošek
,
Mária Chromčíková
,
Jana Holubová
,
Eva Černošková
, and
Libor Vozár

Abstract  

The results of StepScan DSC obtained for various oxides, chalcogenides, and organic glasses are discussed in connection with the commonly accepted theory of the glass transition. The new experimental features supporting the apparent idea of a reversible equilibrium being a part of the glass transition that is commonly interpreted as purely kinetic-relaxation phenomenon are discussed. Two alternative methods of the description of the reversible part of StepScan DSC record are compared:the empirical one using the exponential-power function [1 − exp(T/T g) n ], and the second one based on the van’t Hoff’s equation describing the temperature dependence of equilibrium constant in terms of reaction enthalpy, ΔH. The adequacy of the empirical description is rationalized in the framework of the Tool–Narayanaswamy–Moynihan’s relaxation theory.

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Thermal analysis of the influence of water content on glass transitions

Heat capacities of starches from different origins

Journal of Thermal Analysis and Calorimetry
Authors:
W. Louaer
,
A. Meniai
, and
J. Grolier

Abstract  

Starch is an important natural substance in which the water content has a significant influence on its structure and properties. In the present study, the effect of the water content on glass transition temperatures T g and heat capacities C p of wheat, maize and potato starches were investigated by high-sensitivity differential scanning calorimetry (temperature modulated TMDSC and conventional DSC). Thermal analysis measurements were performed on starch samples with different water contents. The exact water mass percentage of each sample was determined using the Karl-Fischer method. The obtained results show that the water content does influence the starch thermal properties in a systematic and measurable trend, the higher the water% the lower the glass transition temperature, and the higher the heat capacity jump during gelatinisation. At this stage possible interpretations of the results are just put forward and should be confirmed through complementary measurements.

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Abstract  

The activation energy associated with the glass transition relaxation of an epoxy system has been determined by using the three-point bending clamp provided in the recently introduced TA Instruments DMA 2980 dynamic mechanical analyzer. A mathematical expression showing the dependency of modulus measurements on the sample properties and test conditions has also been derived. The experimental results showed that the evaluation of activation energy is affected by the heating rate and test frequency, as well as the criterion by which the glass transition temperature (T g) is established. It has been found that the activation energy based on the loss tangent (tanδ) peak is more reliable than on the loss modulus (E 2) peak, as long as the dynamic test conditions do not cause excessive thermal lags.

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Abstract  

Relaxation times of bisphenol A polycarbonate around the glass transition temperature are estimated using the combination of differential scanning calorimetry (DSC) and thermostimulated depolarization currents (TSDC). These measurements are performed using samples with different thermal histories below and above the vitrification transformation. This protocol enables the extension of the range of equilibrium relaxation times measured by dielectric spectroscopy. By this mean we may recalculate the values of the Kauzmann temperature and fragility index.

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