Relaxation time glass transition

Concentration of locally favoured structures Structural relaxation time Glass transition temperature Two Order Parameters (Model)... 

An attempt has been made to describe the particular stress-optical behaviour observed close to Tg. The idea was to associate the entropic part of the stress with relaxation times corresponding roughly to the rubbery plateau and the terminal zone (see Fig. 12), whereas the non-entropic part is assumed to be related to shorter time relaxation phenomena (glass transition and glassy state). This approach is similar to that proposed by Inoue et al. [34] who considered two contributions to the stress with different associated stress-optical coefficients. 

The solidity of gel electrolytes results from chain entanglements. At high temperatures they flow like liquids, but on cooling they show a small increase in the shear modulus at temperatures well above T. This is the liquid-to-rubber transition. The values of shear modulus and viscosity for rubbery solids are considerably lower than those for glass forming liquids at an equivalent structural relaxation time. The local or microscopic viscosity relaxation time of the rubbery material, which is reflected in the 7], obeys a VTF equation with a pre-exponential factor equivalent to that for small-molecule liquids. Above the liquid-to-rubber transition, the VTF equation is also obeyed but the pre-exponential term for viscosity is much larger than is typical for small-molecule liquids and is dependent on the polymer molecular weight. 

Fig. 19. Experimental spin alignment decay curves of chain deuterated PS-d3 at temperatures above and below the glass transition for various evolution times t,. Note the different timescales of t2 at the different temperatures. The straight lines indicate the decays of the plateau values on the timescale of the spin-lattice relaxation time T,. Sample characterization Mw = 141000, Mw/Mn = 1.13, atactic...

The glass transition temperature can be chosen as the reference temperature, though this was not recommended by Williams, Landel, and Ferry, who preferred to use a temperature slightly above T. In order to determine relaxation times, and hence a, use can be made of dynamic mechanical, stress relaxation, or viscosity measurements. 

The WLF equation can be widely applied, and demonstrates the equivalence of time and temperature, the so-called time-temperature superposition principle, on the mechanical relaxations of an amorphous polymer. The equation holds up to about 100° above the glass transition temperature, but after that begins to break down. 

Since the glass transition corresponds to a constant value of the relaxation time [15], dTjdP is just the pressure coefficient of Tg. Comparing Equations 24.10 and 24.13, we see that the scaling exponent is related to quantities—thermal pressure coefficient, thermal expansion coefficient, Tg, and its pressure coefficient—that can all be determined from PVT measurements... 

In summary, the NFS investigation of FC/DBP reveals three temperature ranges in which the detector molecule FC exhibits different relaxation behavior. Up to 150 K, it follows harmonic Debye relaxation ( exp(—t/x) ). Such a distribution of relaxation times is characteristic of the glassy state. The broader the distribution of relaxation times x, the smaller will be. In the present case, takes values close to 0.5 [31] which is typical of polymers and many molecular glasses. Above the glass-to-liquid transition at = 202 K, the msd of iron becomes so large that the/factor drops practically to zero. 

Fig. 3. Schematic of Chambon-Winter gel spectrum. The longest relaxation time diverges to infinity. The relaxation time X0 marks the crossover to the short-time behavior, which depends on the material. The depicted case corresponds to a low-molecular-weight precursor (crossover to glass transition region)...

Fig. 11. Schematic of relaxation time spectrum of the critical gel of PBD 44 (Mw = 44 000). The entanglement and glass transition is governed by the precursor s BSW-spectrum, while the CW spectrum describes the longer modes due to the crosslinking [60]. denotes the longest relaxation time of PBD44 before crosslinking...

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