Terminal stage of highly viscous flow.

The shear misfit model for highly viscous flow is based upon a theoretical prediction for its terminal stage in terms of irreversible Eshelby relaxations in five-dimensional shear space. The model is shown to predict a small δ-function (Debye peak) in the dielectric spectrum, in agreement with experimental evidence. It is extended to density fluctuations, and a relation between adiabatic and isothermal compressibility jumps at the glass transition is derived. The model is applied to high-precision measurements of the shear, dielectric, and bulk relaxation data in two vacuum pump oils and in squalane, a short chain polymer with a strong secondary relaxation peak. The terminal stage of aging data in squalane demonstrates that the adiabatic density fluctuations contribute a fast component to the thermal expansion, explaining why the thermal expansion seems to equilibrate a bit faster than the dynamic heat capacity.

Eshelby description of highly viscous flow-Half model, half theory.

A recent description of the highly viscous flow ascribes it to irreversible thermally activated Eshelby transitions, which transform a region of the undercooled liquid to a different structure with a different elastic misfit to the viscoelastic surroundings. The description is extended to include reversible Eshelby transitions, with the Kohlrausch exponent ß as a free parameter. The model answers several open questions in the field.

Structural relaxation and highly viscous flow.

The highly viscous flow is due to thermally activated Eshelby transitions which transform a region of the undercooled liquid to a different structure with a different elastic misfit to the viscoelastic surroundings. A self-consistent determination of the viscosity in this picture explains why the average structural relaxation time is a factor of eight longer than the Maxwell time. The physical reason for the short Maxwell time is the very large contribution of strongly strained inherent states to the fluidity (the inverse viscosity). At the Maxwell time, the viscous no-return processes coexist with the back-and-forth jumping retardation processes.

Pragmatical access to the viscous flow of undercooled liquids.

The paper derives a relation for the viscosity of undercooled liquids on the basis of the pragmatical model concept of Eshelby relaxations with a finite lifetime. From accurate shear relaxation data in the literature, one finds that slightly less than half of the internal stresses relax directly via single Eshelby relaxations; the larger part dissolves at the terminal lifetime, which is a combined effect of many Eshelby relaxations.

Modeling the nonlinear dielectric response of glass formers.

The recently developed pragmatical model of asymmetric double-well potentials with a finite lifetime is applied to nonlinear dielectric data in polar undercooled liquids. The viscous effects from the finite lifetime provide a crossover from the cooperative jumps of many molecules at short times to the motion of statistically independent molecules at long times. The model allows us to determine the size of cooperatively rearranging regions from nonlinear ω-data and throws new light on a known inconsistency between nonlinear ω and 3ω-signals for glycerol and propylene carbonate.

Retardation and flow at the glass transition.

The crossover from back-and-forth jumps between structural minima to the no-return jumps of the viscous flow is modeled in terms of an ensemble of double-well potentials with a finite decay probability. The ensemble is characterized by the Kohlrausch-exponent ß of the time dependence t(ß) of the response at short times. The model is applied to shear and dielectric data from the literature.

Probing cooperative liquid dynamics with the mean square displacement.

Literature data for picosecond mean square displacements show that the anharmonicity explains only about half of the fragility (with different fractions for different glass formers). The other half must be ascribed to the Adam-Gibbs mechanism of a growing cooperatively rearranging region. One can measure both influences separately by a simultaneous measurement of liquid and crystal in the coexistence region.

Evaluation of x-ray Brillouin scattering data.

Making use of the classical second-moment sum rule, it is possible to convert a series of constant-Q x-ray Brillouin scattering scans (Q momentum transfer) into a series of constant frequency scans over the measured Q range. The method is applied to literature results for the longitudinal phonon dispersion in several glass formers. The constant frequency scans are well fitted in terms of a Q-independent phonon damping depending exclusively on the frequency, in agreement with two recent theories of the boson peak. The method allows us to link the x-ray Brillouin scattering to the diffuse Umklapp scattering from the boson peak vibrations at higher momentum transfer on an absolute intensity scale.

Bulk and shear relaxation in glasses and highly viscous liquids.

The ratio δB/δG between the couplings of a relaxational process to compression and shear, respectively, is calculated in the Eshelby picture of structural rearrangements within a surrounding elastic matrix, assuming a constant density of stable structures in distortion space. The result is compared to experimental data for the low-temperature tunneling states in glasses and to Prigogine-Defay data at the glass transition, both from the literature.

On the mechanism of the highly viscous flow.

The asymmetry model for the highly viscous flow postulates thermally activated jumps from a practically undistorted ground state to strongly distorted, but stable structures, with a pronounced Eshelby backstress from the distorted surroundings. The viscosity is ascribed to those stable distorted structures which do not jump back, but relax by the relaxation of the surrounding viscoelastic matrix. It is shown that this mechanism implies a description in terms of the shear compliance, with a viscosity which can be calculated from the cutoff of the retardation spectrum. Consistency requires that this cutoff lies close to the Maxwell time. The improved asymmetry model compares well with experiment.

Scaling the temperature-dependent boson peak of vitreous silica with the high-frequency bulk modulus derived from Brillouin scattering data.

The position and strength of the boson peak in silica glass vary considerably with temperature T. Such variations cannot be explained solely with changes in the Debye energy. New Brillouin-scattering measurements are presented which allow determining the T dependence of unrelaxed acoustic velocities. Using a velocity based on the bulk modulus, scaling exponents are found which agree with the soft-potential model. The unrelaxed bulk modulus thus appears to be a good measure for the structural evolution of silica with T and to set the energy scale for the soft potentials.

Vibrational dynamics of permanently densified GeO2 glasses: densification-induced changes in the boson peak.

Vitreous GeO(2), one of the main prototypes of strong glasses, was densified at several pressures up to 6 GPa, achieving more than 20% of densification. The density dependence of the vibrational density of states and of the low temperature properties of these glasses was investigated by means of inelastic neutron scattering and calorimetric measurements. With increasing density, both the boson peak and the bump in c(p)/T(3) versus T plot exhibit variations which are stronger than the elastic medium expectation. If one reduces the measured spectra to a common master curve, one finds that this is only possible for the densified samples; the first densification step has an additional effect, similar to other cases in the literature. Nevertheless, the existence of a master curve for the three densified samples proves that the total number of excess modes remains constant on further densification. The experimental data are discussed in the framework of different theoretical models.

An asymmetry model for the highly viscous flow.

The shear flow is modeled in terms of local structural rearrangements. Most of these rearrangements are strongly asymmetric, because the embedding matrix tends to be elastically adapted to the initial state and to have a marked elastic misfit with regard to the final state. As one approaches the Maxwell time, the asymmetry becomes time dependent, thus enabling the system to leave the initial state. The model explains the Kohlrausch behavior at the main peak in terms of the interaction between different local structural rearrangements.

Neutron scattering study of the vibrations in vitreous silica and germania.

The incoherent approximation for the determination of the vibrational density of states of glasses from inelastic neutron or x-ray scattering data is extended to treat the coherent scattering. The method is applied to new room temperature measurements of vitreous silica and germania on the thermal time-of-flight spectrometer IN4 at the High Flux Reactor in Grenoble. The inelastic dynamic structure factor at the boson peak turns out to agree reasonably well with simulation results, but the long-wavelength fraction exceeds the expectation of the Debye model, in particular, in germania.

A new interpretation of dielectric data in molecular glass formers.

Literature dielectric data of glycerol, propylene carbonate, and ortho-terphenyl show that the measured dielectric relaxation is a decade faster than the Debye expectation but still a decade slower than the breakdown of the shear modulus. From a comparison of time scales, the dielectric relaxation seems to be due to a process which relaxes not only the molecular orientation but also the entropy, the short range order, and the density. On the basis of this finding, we propose an alternative to the Gemant-DiMarzio-Bishop extension of the Debye picture.

Intermediate length scale dynamics of polyisobutylene.

We report on a neutron spin echo investigation of the intermediate scale dynamics of polyisobutylene studying both the self-motion and the collective motion. The momentum transfer (Q) dependences of the self-correlation times are found to follow a Q(-2/beta) law in agreement with the picture of Gaussian dynamics. In the full Q range of observation, their temperature dependence is weaker than the rheological shift factor. The same is true for the stress relaxation time as seen in sound wave absorption. The collective times show both temperature dependences; at the structure factor peak, they follow the temperature dependence of the viscosity, but below the peak, one finds the stress relaxation behavior.

Brillouin and Umklapp scattering in polybutadiene: comparison of neutron and x-ray scattering.

We report a comparison of high resolution inelastic x-ray Brillouin scattering to coherent inelastic neutron scattering for amorphous deuterated polybutadiene, done for one temperature in the glass phase and another one in the melt. The x-ray scattering proves to be by far the better technique for such a polymer within its present resolution bounds. The neutron scattering allows one to extend these measurements to a much better resolution, showing an additional quasielastic signal in the melt. The results suggest x-ray measurements at higher momentum transfer, to see whether they are complementary to neutrons.