Glass transition temperature molar mass

Interestingly, our own studies have revealed that both the shape of the macromolecule and the glass transition temperature, Tg, change with irradiation time. For example, the irradiation of a bimodal commercial sample of polyvinylcarbazole (PNVK) (Fig. 5.31a) in dichloromethane occurred with an initial increase in (the number average) molar mass (M ) and an apparent loss in the bimodal nature of the polymer (Tab. 5.16, Fig. 5.31b). A similar initial increase in has been observed by Price [39] during a sonically induced polymerisation. 

The polymers are easily soluble in polar solvents like TFIF, DMAc, and DMSO, indicating that the solubility is enhanced by the large number of polar end groups and the branched structure. It is fully amorphous with a glass transition temperature between 90 and 110 C,depending on molar mass. 

Figure 10. LCT configurational entropy ScT as a function of the reduced temperature 5T = (T — To)/To for low and high molar mass F-F and F-S polymer fluids at constant pressure of P = 1 atm (0.101325 MPa). The product ScT is normalized by the thermal energy k To at the ideal glass transition temperature To- (Used with permission from J. Dudowicz, K. F. Freed, and J. F. Douglas, Journal of Physical Chemistry B 109, 21350 (2005). Copyright 2005 American Chemical Society.)...

Figure 17. Specific volume Vt and isothermal compressibility (at the glass transition temperature Tg) calculated from the LCT as a function of the inverse number l/M of united atom groups in single chains for constant pressure (P = I atm 0.101325 MPa) F-F and F-S polymer fluids. Both quantities are normahzed by the corresponding high molar mass limits (i.e., by...

Figure 22. The configurational entropy Sc per lattice site as calculated from the LCT for a constant pressure, high molar mass (M = 40001) F-S polymer melt as a function of the reduced temperature ST = (T — To)/Tq, defined relative to the ideal glass transition temperature To at which Sc extrapolates to zero. The specific entropy is normalized by its maximum value i = Sc T = Ta), as in Fig. 6. Solid and dashed curves refer to pressures of F = 1 atm (0.101325 MPa) and P = 240 atm (24.3 MPa), respectively. The characteristic temperatures of glass formation, the ideal glass transition temperature To, the glass transition temperature Tg, the crossover temperature Tj, and the Arrhenius temperature Ta are indicated in the figure. The inset presents the LCT estimates for the size z = 1/of the CRR in the same system as a function of the reduced temperature 5Ta = T — TaI/Ta. Solid and dashed curves in the inset correspond to pressures of P = 1 atm (0.101325 MPa) and F = 240 atm (24.3 MPa), respectively. (Used with permission from J. Dudowicz, K. F. Freed, and J. F. Douglas, Journal of Physical Chemistry B 109, 21350 (2005). Copyright 2005, American Chemical Society.)...

The linkage of conventional low molar mass Lc s to a linear polymer main chain via a flexible spacer provides a method to realize systematically the liquid crystalline state in linear polymers. Above the glass transition temperature Tg the polymer main chain can be assumed to exhibit, at least in the nematic state, an almost free motion of the chain segments, causing a tendency towards a statistical chain conformation. Due to their mobility, the polymer main chains are able to diffuse past each other, which is a condition to obtain the liquid state. Therefore such polymers can be classified as liquids of high viscosity10O). 

Polyurethane Networks. Andrady and Sefcik (1983) have applied the same relationship as Rietsch et al. (1976), to the glass transition temperature of networks based on poly(propylene oxide) diols with a controlled molar mass distribution, crosslinked by aromatic triisocyanates. They obtained a Kr value of 25 K kg mol-1, about twice that for PS networks. They showed that the length distribution of elastically active chain lengths, directly related to the molar mass distribution of the starting poly(propylene oxide), has practically no effect on Tg. 

Klc = critical stress intensity factor in mode I, MPam1/2 Km = stress concentration factor Me = average molar mass between crosslinks, kg mol 1 Mn = number-average molar mass, kg mol 1 p = hydrostatic pressure, Pa Tg = glass transition temperature, K... 

For miscible blend phases, these parameters need to be described as a function of the blend composition. In a first approach to describe the behavior of the present PPE/PS and SAN/PMMA phases, these phases will be regarded as ideal, homogeneously mixed blends. It appears reasonable to assume that the heat capacity, the molar mass of the repeat unit, as well as the weight content of carbon dioxide scale linearly with the weight content of the respective blend phase. Moreover, a constant value of the lattice coordination number for PPE/PS and for SAN/PMMA can be anticipated. Thus, the glass transition temperature of the gas-saturated PPE/SAN/SBM blend can be predicted as a function of the blend composition (Fig. 17). Obviously, both the compatibilization by SBM triblock terpolymers and the plasticizing effect of the absorbed carbon dioxide help to reduce the difference in glass transition temperature between PPE and SAN. 

As is well known, the glass-rubber transition is of considerable importance technologically. The glass transition temperature (Tg) determines the lower use limit of a rubber and the upper use limit of an amorphous thermoplastic material. With increasing molar mass the ease of "forming" (shaping) diminishes. 

Table 5.4 Molecular structure and glass transition temperature (°C) of the low-molar-mass, non-emissive HTL materials (12-16)...

Table 8.3 Molar mass dependence of the glass transition temperature [see Eq. (8.136)] and WLF coefficients of high molar mass polymers [see Eq. (8.134) with To — Tg]...

Assuming that the chain ends have more free volume than monomers in the middle of the chain, derive the molar mass dependence of the glass transition temperature of polymer melts [Eq. (8.135)]. 

Demonstrate that the glass transition temperature of ring polymers decreases with increasing molar mass. 

T g glass transition temperature of high molar mass... 

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