Effect of Molecular Weight on Glass Transition by Differential Scanning Calorimetry

1974 ◽  
Vol 52 (18) ◽  
pp. 3170-3175 ◽  
Author(s):  
Louis-Philippe Blanchard ◽  
Jean Hesse ◽  
Shadi Lal Malhotra

The influence of molecular weight (900 to 1.8 × 106) on the glass transition temperature of low polydispersity polystyrene (anionically prepared) has been studied by differential scanning calorimetry at heating rates of 5 to 80 °C min−1. Over the range of molecular_weight studied, and at an extrapolated heating rate of 1 °C min−1,[Formula: see text] A thermally prepared polystyrene sample ([Formula: see text]and Pd = 3.2) showed a Tge value of 93 °C, some 10° below the value predicted by the above equation. Low molecular weight species in the highly polydisperse sample are believed to be responsible for the discrepancy. The changes in heat capacity brought about by the glass transitions are accompanied in all cases on heating by an endothermic peak and this regardless of the heating rate (even extrapolated to 1 °C min−1) or the molecular weight of the sample, suggesting that the glass transition phenomenon encountered with polystyrene is a process involving a positive heat effect.

1982 ◽  
Vol 55 (1) ◽  
pp. 245-252 ◽  
Author(s):  
C. Kow ◽  
M. Morton ◽  
L. J. Fetters ◽  
N. Hadjichristidis

Abstract The glass transition temperatures for a series of high-1,4 linear and star-branched polyisoprenes have been measured by differential scanning calorimetry. The Fox-Flory relation for the linear polyisoprenes was found to be Tg=Tg∞−1.76×104Mn−1. The influence of hydroxyl groups on Tg was also examined for low molecular weight (<2.2×104) polyisoprenes.


Polymers ◽  
2019 ◽  
Vol 12 (1) ◽  
pp. 5 ◽  
Author(s):  
César Leyva-Porras ◽  
Pedro Cruz-Alcantar ◽  
Vicente Espinosa-Solís ◽  
Eduardo Martínez-Guerra ◽  
Claudia I. Piñón-Balderrama ◽  
...  

Phase transition issues in the field of foods and drugs have significantly influenced these industries and consequently attracted the attention of scientists and engineers. The study of thermodynamic parameters such as the glass transition temperature (Tg), melting temperature (Tm), crystallization temperature (Tc), enthalpy (H), and heat capacity (Cp) may provide important information that can be used in the development of new products and improvement of those already in the market. The techniques most commonly employed for characterizing phase transitions are thermogravimetric analysis (TGA), dynamic mechanical analysis (DMA), thermomechanical analysis (TMA), and differential scanning calorimetry (DSC). Among these techniques, DSC is preferred because it allows the detection of transitions in a wide range of temperatures (−90 to 550 °C) and ease in the quantitative and qualitative analysis of the transitions. However, the standard DSC still presents some limitations that may reduce the accuracy and precision of measurements. The modulated differential scanning calorimetry (MDSC) has overcome some of these issues by employing sinusoidally modulated heating rates, which are used to determine the heat capacity. Another variant of the MDSC is the supercooling MDSC (SMDSC). SMDSC allows the detection of more complex thermal events such as solid–solid (Ts-s) transitions, liquid–liquid (Tl-l) transitions, and vitrification and devitrification temperatures (Tv and Tdv, respectively), which are typically found at the supercooling temperatures (Tco). The main advantage of MDSC relies on the accurate detection of complex transitions and the possibility of distinguishing reversible events (dependent on the heat capacity) from non-reversible events (dependent on kinetics).


2015 ◽  
Vol 59 (1) ◽  
pp. 109-118 ◽  
Author(s):  
Jolanta Tomaszewska-Gras ◽  
Sławomir Bakier ◽  
Kamila Goderska ◽  
Krzysztof Mansfeld

Abstract Thermodynamic properties of selected honeys: glass transition temperature (Tg), the change in specifi c heat capacity (ΔCp), and enthalpy (ΔH) were analysed using differential scanning calorimetry (DSC) in relation to the composition i.e. water and sugar content. Glass transition temperatures (Tg) of various types of honey differed significantly (p<0.05) and ranged from -49.7°C (polyfloral) to -34.8°C (sunflower). There was a strong correlation between the Tg values and the moisture content in honey (r = -0.94). The degree of crystallisation of the honey also influenced the Tg values. It has been shown that the presence or absence of sugar crystals influenced the glass transition temperature. For the decrystallised honeys, the Tg values were 6 to 11°C lower than for the crystallised honeys. The more crystallised a honey was, the greater the temperature difference was between the decrystallised and crystallized honey. In conclusion, to obtain reliable DSC results, it is crucial to measure the glass transition after the complete liquefaction of honey.


2006 ◽  
Vol 116-117 ◽  
pp. 54-57 ◽  
Author(s):  
Jacqueline Lecomte-Beckers ◽  
Ahmed Rassili ◽  
Marc Robelet ◽  
Claude Poncin ◽  
R. Koeune

This paper focuses on the liquid fraction curves of several steels and the correlation between liquid fraction, temperature and heating rate. The work has been performed along two main axes. First, the solid fraction versus temperature has been obtained experimentally by differential scanning calorimetry (DSC), limited to low heating rates. Then, a shift of the liquid fraction curves has been noticed at high industrial heating rates. The quantification of this effect could not be carried out by DSC and required the elaboration of another experimental device.


2011 ◽  
Vol 295-297 ◽  
pp. 929-933 ◽  
Author(s):  
E.H. Agung ◽  
S.M. Sapuan ◽  
M.M.H. Megat Ahmad ◽  
H.M.D.K. Zaman ◽  
U. Mustofa

Differential scanning calorimetry (DSC) was used to study the thermal behaviour of abaca fibre reinforced high impact polystyrene (HIPS) composites. Thermal analysis is based upon the detection of changes in the heat content (enthalpy) and the glass transition temperature (Tg) of optimum condition of abaca fibre reinforced HIPS composites. In this research, glass transitions temperature (Tg) of neat HIPS occurred below the Tg of optimum condition of composites as the temperature of an amorphous state. The endothermic peak of composites was in to range 430-435°C including neat HIPS and it observed that enthalpy of abaca fibre reinforced HIPS composites yielded below the neat HIPS 748.79 J/g.


2009 ◽  
Vol 81 (10) ◽  
pp. 1931-1952 ◽  
Author(s):  
Bernhard Wunderlich

With standard differential scanning calorimetry (DSC), it is possible to derive calorimetric data for equilibrium or metastable samples. The introduction of temperature-modulated DSC (TMDSC) permits in its quasi-isothermal (non-scanning) mode (TMDC), long-time apparent heat capacity measurements of high precision (±1 %). For flexible molecules, heat capacity measurements from the various calorimetric methods could be combined in the ATHAS Data Bank, which now contains experimental data for over 200 materials. These data were linked to the vibrational and large-amplitude motion of the constituent atoms and molecules, to provide a base for the judgement of the thermal analyses, extending outside the range of equilibrium or metastability with an error of only 2-5 %. The TMDC together with DSC is now able to quantitatively assess the reversibility of thermal processes. A sufficient number of systems have been analyzed in this fashion to develop better understanding of macro-, micro-, and nanophases of flexible macromolecules. The new concepts discussed are: (1) multiple glass transitions due to possible rigid-amorphous fractions (RAFs) and glass transitions within crystals, both observed in semicrystalline macromolecules, and (2) locally reversibly melting on the surface of chain-folded crystals. The locally reversible melting decreases with crystal perfection and also disappears when the chains become rigid.


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