Differential scanning calorimetry polymer degradation

Stoliarov, S. I. and Walters R. N. (2008) Determination of the heats of gasification of polymers using differential scanning calorimetry, Polymer Degradation and Stability 93(2)422-427. 

Vasanthan, N., Ly, O., 2009. Effect of microstructure on hydrolytic degradation studies of poly(L-lactic acid) by FTIR spectroscopy and differential scanning calorimetry. Polym. Degrad. Stabil. 94, 1364-1372. 

Induction time and later degradation of outdoor exposed poiypropylene cast film studied by differential scanning calorimetry. Polymer Degradation and Stability, 85 (1997), p. 199-207... 

The progress of polymer degradation may be followed by a wide variety of techniques, some of them being mentioned at the right column in the Bolland-Gee scheme (Scheme 2). There are techniques that directly monitor some of the elementary reaction steps such as, for example, oxygen absorption (reaction 2), differential scanning calorimetry (DSC) (reaction 3), chemiluminescence (reaction 11) analytical and/or spectral methods of determination of hydroperoxides, etc. 

Brack, H.-P, Ruegg, D., Biihrer, H., Slaski, M., Alkan, S. and Scherer, G. G. 2004. Differential scanning calorimetry and thermogravimetric analysis investigation of the thermal properties and degradation of some radiation-grafted films and membranes. Journal of Polymer Science Part B Polymer Physics 42 2612-2624. 

TGA analysis shows that polymer degradation starts at about 235°C which corresponds to the temperature of decomposition of the cellobiose monomer (m.p. 239°C with decom.). Torsion Braid analysis and differential scanning calorimetry measurements show that this polymer is very rigid and does not exhibit any transition in the range of -100 to +250 C, e.g. the polymer decomposition occurs below any transition temperature. This result is expected since both of the monomers, cellobiose and MDI, have rigid molecules and because cellobiose units of the polymer form intermolecular hydrogen bondings. Cellobiose polyurethanes based on aliphatic diisocyanates, e.g. HMDI, are expected to be more flexible. 

Thermal analysis is a group of techniques in which a physical property of a substance is measured as a function of temperature when the sample is subjected to a controlled temperature program. Single techniques, such as thermogravimetry (TG), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), dielectric thermal analysis, etc., provide important information on the thermal behaviour of materials. However, for polymer characterisation, for instance in case of degradation, further analysis is required, particularly because all of the techniques listed above mainly describe materials only from a physical point of view. A hyphenated thermal analyser is a powerful tool to yield the much-needed additional chemical information. In this paper we will concentrate on simultaneous thermogravimetric techniques. 

Comparison of several techniques (namely Fourier transform infrared spectroscopy (FTIR), simultaneous thermogravimetric analysis-differential scanning calorimetry (TGA-DSC) and ultrasonic spectroscopy) for assessing the residual physical and mechanical characteristics of polymer matrix composites (PMCs) exposed to excessive thermal loads showed the measured power spectra of ultrasonic energy to correlate with performance of graphite fibre epoxy matrix composites exposed to thermal degradation, and also that analyses with the three techniques all pointed to the same critical temperature at which thermally induced damage increased sharply [58],... 

The mercaptide thermolysis may behave differently in the presence or absence of polymers [Conte et al., 2007]. However, in most cases, the inorganic phase generated by the thermal degradation of mercaptide molecules dissolved in polymer corresponds exactly to that resulting from the thermal degradation of pure mercaptide. Consequently, a preliminary study of neat mercaptide thermolysis by thermal analysis approaches [differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA)] is usually performed before nanocomposite preparation and characterization. 

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