Glass transition temperature scanning calorimetry

Glass-transition temperatures are commonly determined by differential scanning calorimetry or dynamic mechanical analysis. Many reported values have been measured by dilatometric methods however, methods based on the torsional pendulum, strain gauge, and refractivity also give results which are ia good agreement. Vicat temperature and britde poiat yield only approximate transition temperature values but are useful because of the simplicity of measurement. The reported T values for a large number of polymers may be found ia References 5, 6, 12, and 13. 

The thermal glass-transition temperatures of poly(vinyl acetal)s can be determined by dynamic mechanical analysis, differential scanning calorimetry, and nmr techniques (31). The thermal glass-transition temperature of poly(vinyl acetal) resins prepared from aliphatic aldehydes can be estimated from empirical relationships such as equation 1 where OH and OAc are the weight percent of vinyl alcohol and vinyl acetate units and C is the number of carbons in the chain derived from the aldehyde. The symbols with subscripts are the corresponding values for a standard (s) resin with known parameters (32). The formula accurately predicts that resin T increases as vinyl alcohol content increases, and decreases as vinyl acetate content and aldehyde carbon chain length increases. 

Differential scanning calorimetry (DSC) is fast, sensitive, simple, and only needs a small amount of a sample, therefore it is widely used to analyze the system. For example, a polyester-based TPU, 892024TPU, made in our lab, was blended with a commercial PVC resin in different ratios. The glass transition temperature (Tg) values of these systems were determined by DSC and the results are shown in Table 1. 

The modified NBR samples were characterized by differential scanning calorimetry [11,78-80,98]. The glass-transition temperature (T ) decreased with the level of hydrogenation. In the case of HFNBR, Tg increased with an increase in the addition of aldehyde groups to the polymer chain. Thermogravimetric analysis of the modified polymers have also been carried out [15]. 

Strict control of the fusion process is imperative. In addition to thickness, hardness, continuity and adhesion checks, correct cure may be assessed by differential scanning calorimetry techniques, which are designed to measure any difference in the glass transition temperature of a laboratory-cured powder and the cured coating taken from the factory-coated pipe. 

Figure 10.7 The phase diagram (a) and the glass transition temperatures (b) of a PSC/PVME mixture obtained, respectively, by light scattering and differential scanning calorimetry (DSC). Irradiation experiments were performed in the miscible region at 127 C indicated by (X) in the figure of trans-cinnamic acid-labeled polystyrene/poly(vinyl methyl ether) blends.

Brittle colorless films of PBPP may be cast from tetrahydrofuran solution. The insoluble portion of PBPP is swelled by the tetrahydrofuran and gives rise to free-standing films on solvent evaporation. Differential scanning calorimetry experiments on PBPP show a glass transition temperature at 40 °C, and some indication of a melting transition at 170° C. 

ASTM E 1356-98, ASTM Book of Standards 2002. Standard Test Method for Assignment of the Glass Transition Temperature by Differential Scanning Calorimetry or Differential Thermal Analysis . ASTM International, Conshohocken, PA. 

Richardson, S.J. 1989. Contribution of proton exchange to the oxygen-17 nuclear magnetic resonance transverse relaxation rate in water and starch-water systems. Cereal Chem. 66, 244-246. Richardson, M.J. and Saville, N.G. 1975. Derivation of accurate glass transition temperatures by differential scanning calorimetry. Polymer 16, 753-757. 

Differential scanning calorimetry (DSC) and thermomechanical analysis (TMA) were used to measure the glass transition temperatures (Tgs) of the uncured and cured AT-resins respectively (Figure 6). 

Thermal Properties. Each of the polyimide film samples was evaluated by differential scanning calorimetry to determine the glass transition temperature (Table I). The general observation is that the BTDA-ODA polyimide films have a higher glass transition temperature than the BDSDA-ODA polyimide films whether they are nonmodifled or are modified with cobalt chloride. This is in agreement with the work of Frye ( ) in which the dianhydride moiety, not the dieunine, was found to control the polyimide glass transition temperature. 

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