Relaxation time displacements

Figure B2.5.4. Periodic displacement from equilibrium through a sound wave. The frill curve represents the temporal behaviour of pressure, temperature, and concentrations in die case of a very fast relaxation. The other lines illustrate various situations, with 03Xj according to table B2.5.1. 03 is the angular frequency of the sound wave and x is the chemical relaxation time. Adapted from [110].

FIG. 18 Mean-square displacements gi t) vs time for chains with 7 = 128 in a narrow non-adsorbing sUt (Z)= l,e = 0) at density cp = 1.5. Straight lines show effective exponents = 0.56, and = 0.84, respectively. Broken horizontal lines show (above) and (below), (b) Log-log plot of the relaxation time r 3 vs N for the case (D = 1, e = 0) and various densities (p as indicated. Straight lines show interpretations in terms of effective exponents Zgff (r oc [16]. 

If the equilibrium is suddenly displaced, the results obtained in Chapter 3 show that the re-equilibration process will follow first-order kinetics. It is customary in this field to refer to r, the relaxation time, which is defined as reciprocal of the first-order rate constant for re-equilibration. In this case, we have... 

Fig. 5.13. Relaxation time r3 plotted vs. temperature for the coarse-grained model of PE with N = 20, using the random hopping algorithm (upper set of data) or the slithering snake algorithm (lower set of data), respectively. The time r3 is of the same order as the Rouse relaxation time of the chains, and is defined in terms of a crossing criterion for the mean-square displacements [41], g3(t = r3) = g2(t = r3) [See Eqs. (5.2) and 5.3)]. From [32]...

The concept of a T2 cut-off that partitions the relaxation time distribution between the pores which can be displaced and those that cannot does not always apply. An exception is when there is significant diffusional coupling between the micropores that retain water at a high capillary pressure and the macropores in close proximity to the microporous system [26, 27]. A spectral BVI model or a forward model has been suggested to interpret these systems [30, 31, 53]. 

Droplet suspensions (gas-liquid, two-component system) Since the inertia of a liquid suspended in the gas phase is higher than the inertia of the gas, the time for the displacement of liquid under the pressure waves should be considered. Temkin (1966) proposed a model to account for the response of suspension with pressure and temperature changes by considering the suspensions to move with the pressure waves according to the Stokes s law. The oscillatory state equation is thereby approximated by a steady-state equation with the oscillatory terms neglected, which is valid if the ratio of the relaxation time to the wave period is small, or... 

The diode laser is scanned up and down in frequency by a triangle wave, so that the scan should be linear in time and have the same rate in both directions. In the thermal accommodation coefficient experiments, the external beam heats the microsphere to a few K above room temperature and is then turned off. The diode laser is kept at fairly low power ( 7 pW) so that it does not appreciably heat the microsphere. Displacement of a WGM s throughput dip from one scan trace to the next is analyzed to find the relaxation time constant as the microsphere returns to room temperature. Results from the two scan directions are averaged to reduce error due to residual scan nonlinearity. This is done over a wide range of pressures (about four orders of magnitude). The time constant provides the measured thermal conductivity of the surrounding air, and fitting the thermal conductivity vs. pressure curve determines the thermal accommodation coefficient, as described in Sect. 5.5.2. 

The wavelength of the torsion normal mode with relaxation time r = 1 ns is A >50 bp for a >3.8x10 12 dyn-cm [from Eq. (4.34)]. Thus, the shortest torsion normal modes resolved in the FPA have wavelengths extending over about five full turns of the helix. The rms angular displacement of a base pair around its helix axis is about 18° at t= 1 ns and increases without bound as t goes to infinity. 

Sikorsky and Romiszowski [172,173] have recently presented a dynamic MC study of a three-arm star chain on a simple cubic lattice. The quadratic displacement of single beads was analyzed in this investigation. It essentially agrees with the predictions of the Rouse theory [21], with an initial t scale, followed by a broad crossover and a subsequent t dependence. The center of masses displacement yields the self-diffusion coefficient, compatible with the Rouse behavior, Eqs. (27) and (36). The time-correlation function of the end-to-end vector follows the expected dependence with chain length in the EV regime without HI consistent with the simulation model, i.e., the relaxation time is proportional to l i+2v The same scaling law is obtained for the correlation of the angle formed by two arms. Therefore, the model seems to reproduce adequately the main features for the dynamics of star chains, as expected from the Rouse theory. A sim-... 

The observations above can be rapidly turned into a semi-quantitative theory for star-polymer stress-relaxation [24] which is amenable to more quantitative refinement [25]. The key observation is that the diffusion equation for stress-re-lease, which arises in linear polymers via the passage of free ends out of deformed tube segment, is now modified in star polymers by the potential of Eq. (16). Apart from small displacements of the end, the diffusion to any position s along the arm will now need to be activated and so is exponentially suppressed. Each position along the arm, s, will possess its own characteristic stress relaxation time T(s) given approximately by... 

Finally, the structural relaxation time for any diffusing species in the supercooled liquid is proportional to the probability of this species having access to a free volume over the minimum value Vf required for an elementary displacement. 

The viscosity relates to the longest relaxation time in a system. If we consider Rouse diffusion along the tube with a Rouse diffusion coefficient DJ l/ NQ) then an initial tube configuration is completely forgotten when the mean-square displacement along the tube fulfils (r (t))tube=(contour length ly. Thus, for the longest relaxation time, we obtain ... 

There are two types of charging currents and condenser charges, which may be described as rapidly forming or instantaneous polarizations and slowly forming or absorptive polarizations. The total polarizability of the dielectric is the sum of contributions due to several types of charge displacement in the materials caused by the applied field. The relaxation time is the time required for polarization to form or disappear. The magnitude of the polarizability, k, of a dielectric is related to the dielectric constant, s, as follows ... 

A further development is possible by noting that the high frequency shear modulus Goo is related to the mean square particle displacement (m ) of caged fluid particles (monomers) that are transiently localized on time scales ranging between an average molecular collision time and the structural relaxation time r. Specifically, if the viscoelasticity of a supercooled liquid is approximated below Ti by a simple Maxwell model in conjunction with a Langevin model for Brownian motion, then (m ) is given by [188]... 

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