Physical ageing transition temperature

The effect of physical aging on the crystallization state and water vapor sorption behavior of amorphous non-solvated trehalose was studied [91]. It was found that annealing the amorphous substance at temperatures below the glass transition temperature caused nucleation in the sample that served to decrease the onset temperature of crystallization upon subsequent heating. Physical aging caused a decrease in the rate and extent of water vapor adsorption at low relative humidities, but water sorption could serve to remove the effects of physical aging due to a volume expansion that took place in conjunction with the adsorption process. 

A unified approach to the glass transition, viscoelastic response and yield behavior of crosslinking systems is presented by extending our statistical mechanical theory of physical aging. We have (1) explained the transition of a WLF dependence to an Arrhenius temperature dependence of the relaxation time in the vicinity of Tg, (2) derived the empirical Nielson equation for Tg, and (3) determined the Chasset and Thirion exponent (m) as a function of cross-link density instead of as a constant reported by others. In addition, the effect of crosslinks on yield stress is analyzed and compared with other kinetic effects — physical aging and strain rate. 

The investigation of the ft transition of PMMA ([1], Sect. 8.1.3) has revealed that physical ageing has an influence on the dynamic mechanical response in the ft-a crossover temperature region. As a consequence, it is worth checking whether it leads to some changes in the plastic deformation behaviour [32]. 

The physical and chemical properties of both the solidified adhesive and the plastic substrate affect the quality of the bonded joint. Major elements of concern are the thermal expansion coefficient, modulus, and glass transition temperature of the substrate relative to the adhesive. Special consideration is also required of polymeric surfaces that can change during normal aging or on exposure to operating environments. 

The main consequence of this reduced mobility is an extension of the glass transition region towards the high temperature side it will show a lower and an upper value, viz. Tg(L) and Tg(U), the values of the undisturbed amorphous region and that of regions with reduced mobility. By means of this model, Struik could interpret his measurements on volume relaxation (physical ageing) and creep in semicrystalline materials. 

Struik also (1987-1989) showed that his concept of physical ageing and its affects on the mechanical behaviour can be extended to semi-crystalline polymers the only additional assumption needed is that in semi-crystalline polymers the glass transition is broadened and extended towards the high temperature side. Fig. 13.55 illustrates this. 

In the vicinity of glass transition, both Eqs. (47) and (48) become Eqs. (42) and (43), respectively. The calculated dependence of the physical aging rate on temperature for polystyrene (PS), poly(vinyl chloride) (PVC), and poly(vinyl acetate) (PVAc) is shown in Fig. 17. There are five parameters (e, p, f xr, 7 ) in Eqs. (23), (2), (15) and (19). We have chosen p = 1/2. ft = 1/30, and xr = 30 min for these linear polymers in our theoretical calculation. The other two parameters r. = h and Tr are listed in Table 1. The calculation reveals that the Struik exponent (p) increases from zero above 7 to a constant below Tg, and then decreases to zero at 200 K below Tg. The three polymers all show a similar type of temperature dependence of physical aging rate, which compares well with the reported observations (see Fig. 15 of Ref. 2). 

The master curves and shift factors of transient and dynamic linear viscoelastic responses are calculated for linear, semi-crystalline, and cross-linked polymers. The transition from a WLF dependence to an Arrhenius temperature dependence of the shift factor in the vicinity of Tg is predicted and is related to the temperature dependence of physical aging rate. 

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