Dynamic mechanical analysis transition temperatures

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. 

Thermal Properties. Spider dragline silk was thermally stable to about 230°C based on thermal gravimetric analysis (tga) (33). Two thermal transitions were observed by dynamic mechanical analysis (dma), one at —75° C, presumed to represent localized mobiUty in the noncrystalline regions of the silk fiber, and the other at 210°C, indicative of a partial melt or a glass transition. Data from thermal studies on B. mori silkworm cocoon silk indicate a glass-transition temperature, T, of 175°C and stability to around 250°C (37). The T for wild silkworm cocoon silks were slightly higher, from 160 to 210°C. 

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. 

Glass transition temperature (Tg), measured by means of dynamic mechanical analysis (DMA) of E-plastomers has been measured in binary blends of iPP and E-plastomer. These studies indicate some depression in the Tg in the binary, but incompatible, blends compared to the Tg of the corresponding neat E-plastomer. This is attributed to thermally induced internal stress resulting from differential volume contraction of the two phases during cooling from the melt. The temperature dependence of the specific volume of the blend components was determined by PVT measurement of temperatures between 30°C and 270°C and extrapolated to the elastomer Tg at —50°C. 

A reversible succession of order-order and order-disorder transition was observed for a poly(ethylene-a/f-propylene)- -poly(ethylene-co-butylene)-b-polystyrene terpolymer, which shows at room temperature non-hexagonally packed PS cylinders. Upon heating, this system reorganizes to a hexagonally packed one, and at higher temperatures dynamic-mechanical analysis indicates the transition to the disordered state [73],... 

ASTM E 1640-99, ASTM Book of Standards 2002. Standard Test Method for Assignment of the Glass Transition Temperature by Dynamic Mechanical Analysis . ASTM International, Conshohocken, PA. 

Electron irradiation causes chain scission and crosslinking in polymers. Both of these phenomena directly affect the glass transition temperature (Tg) of the materials. Thermomechanical (TMA) and dynamic-mechanical analysis (DMA) provide information about the Tg region and its changes due to radiation damage. Therefore, DMA and TMA were performed on all irradiated materials. 

Fig. 5 4. Glass transition temperature, Tg, measured by dynamic mechanical analysis as a function of wt% epoxy-compatible PPG size. After Drown et al. (1991).

The glass transition temperature can be measured in a variety of ways (DSC, dynamic mechanical analysis, thermal mechanical analysis), not all of which yield the same value [3,8,9,24,29], This results from the kinetic, rather than thermodynamic, nature of the transition [40,41], Tg depends on the heating rate of the experiment and the thermal history of the specimen [3,8,9], Also, any molecular parameter affecting chain mobility effects the T% [3,8], Table 16.2 provides a summary of molecular parameters that influence the T. From the point of view of DSC measurements, an increase in heat capacity occurs at Tg due to the onset of these additional molecular motions, which shows up as an endothermic response with a shift in the baseline [9,24]. 

The y transition observed from dynamic mechanical analysis at 1 Hz, is centred around - 150 °C. However, the temperature range available experimentally does not permit observation of the whole y relaxation. The temperature position is independent of the chemical composition of the xTy -y copolyamides. 

The dynamic mechanical analysis unambiguously shows that the antiplasticiser acts mainly on the cooperative motions involved in the high-temperature side of the j3 transition peak, implying several units. No effect is detected on the low-temperature side of the j3 peak. 

The ft transition of a series of MGIMx copolymers has been investigated by dynamic mechanical analysis [80]. The temperature dependence of the loss modulus, E"y at 1 Hz is shown in Fig. 138. In the region of the a transition, when increasing the MGI content, a shift towards a higher temperature is observed. 

T A a — glass transition temperature determined using dynamic mechanical analysis, K... 

Reaction of kenaf with succinic anhydride were done in xylene at 120°C and WPGs up to 80% were achieved [32]. Dynamic mechanical analysis was done on acetone-extracted esterified fibers in the WPG range of 30-80. The data showed that there was a reduced transition temperature from about 170°C down to about 135°C and that there was no change in this first transition temperature as the WPG increases. The data showed that complete modification of that melting species had taken place at a WPG of m35. This thermal behavior is similar to reported trends observed for water-plasticized lignin in wood. 

A convenient method for determining transition times and transition temperatures of polymeric materials is dynamic mechanical analysis. One type of instrument which is particularly suitable for polymeric solids is the freely oscillating torsion pendulum (TP). Advantages of the TP include its simplicity, sensitivity, relatively low frequency ( 1 Hz) which permits direct correlation of transition temperatures with static nonmechanical methods (e.g., dilatometry and calorimetry), and its high resolution of transitions A major disadvantage of the conventional TP is that test temperatures are limited by the inability of materials to support their own weight near load-limiting transition temperatures. 

---