Glass time dependence

Geva E and Skinner J L 1998 Optical line shapes of single molecules in glasses temperature and scan-time dependence J. Phys. Chem 109 4920-6... 

Whether or not a polymer is rubbery or glass-like depends on the relative values of t and v. If t is much less than v, the orientation time, then in the time available little deformation occurs and the rubber behaves like a solid. This is the case in tests normally carried out with a material such as polystyrene at room temperature where the orientation time has a large value, much greater than the usual time scale of an experiment. On the other hand if t is much greater than there will be time for deformation and the material will be rubbery, as is normally the case with tests carried out on natural rubber at room temperature. It is, however, vital to note the dependence on the time scale of the experiment. Thus a material which shows rubbery behaviour in normal tensile tests could appear to be quite stiff if it were subjected to very high frequency vibrational stresses. 

Figure 5.11 (Crisp Wilson, 1974b) shows the time-dependent variation of the concentration of soluble ions in setting and hardening cements. Note that the concentrations of aluminium, calcium and fluoride rise to maxima as they are released from the glass. After the maximum is reached the concentration of soluble ions decreases as they are precipitated. Note that this process is much more rapid for calcium than for aluminium and the sharp decline in soluble calcium corresponds to gelation. This indication is supported by information from infrared spectroscopy which showed that gelation (initial set) was caused by the precipitation of calcium polyacrylate. This finding was later confirmed by Nicholson et al. (1988b) who, using Fourier transform infrared spectroscopy (FTIR), found that calcium polyacrylate could be detected in the cement paste within one minute of mixing the cement. There was no evidence for the formation of any aluminium polyacrylate within nine minutes and substantial amounts are not formed for about one hour (Crisp et al, 1974).

Figure 5.11 The time-dependent variation, in setting and hardening cements, of the concentration of soluble ions Al ", Ca, F and PO (expressed as P Oj). These ions are released from the glass powder into the cement matrix (Crisp Wilson, 1974b).

Cement formation with fluoride glasses - - -)-tartaric acid The presence of (+)-tartaric acid in a cement formulation exerts a profound effect on the cement-forming reaction. The nature of the underlying chemical reaction is changed and this is reflected in time-dependent changes in viscosity. 

The time-dependent dispersion coefficients for water flowing in a bed of catalyst type C are compared with flow in a packing of 2 mm glass beads at different flow... 

Fig. 3.3.7 Time dependence of the axial dispersion coefficients D for water flow determined by NMR horizontal lines indicate the asymptotic values obtained from classical tracer measurements. (a) Water flow in packings of 2 mm glass beads at different flow rates and (b) water flow in catalyst.

Observed monomer concentrations are presented by Figure 2 as a function of cure time and temperature (see Equation 20). At high monomer conversions, the data appear to approach an asymptote. As the extent of network development within the resin advances, the rate of reaction diminishes. Molecular diffusion of macromolecules, initially, and of monomeric molecules, ultimately, becomes severely restricted, resulting in diffusion-controlled reactions (20). The material ultimately becomes a glass. Monomer concentration dynamics are no longer exponential decays. The rate constants become time dependent. For the cure at 60°C, monomer concentration can be described by an exponential function. 

The results for the glass crystallization of PET annealed at 80 °C as before are shown in Fig. 8. In the early stage of spinodal decomposition up to 20 min, the characteristic wavelength A remains constant at a value of 15 nm, which agrees with the theoretical expectation that only the amplitude of density fluctuations increases whilst keeping a constant characteristic wavelength. In the late stage from 20 to 100 min it increases up to 21 nm just before crystallization. Such a time dependence of A in nm can be represented by... 

---