C. Michael Roland

Acoustic and dynamic mechanical properties of a polyurethane rubber

Acoustical and dynamic mechanical measurements were carried out on a commercial polyurethane rubber, DeSoto PR1547. The sound speed and attenuation were measured over the range from 12.5 to 75 kHz and 3.9 to 33.6 degrees C. Shear modulus was measured from 10(-4) to 2 Hz and -36 to 34 degrees C. The peak heights of the shear loss tangent varied with temperature, demonstrating thermorheological complexity. At higher temperatures, time-temperature superpositioning could be applied, with the shift factors following the Williams-Landel-Ferry equation. From the combined acoustical and mechanical measurements, values for the dynamic bulk modulus were determined. Moreover, superposition of the bulk modulus data was achieved using the shift factors determined from the dynamic mechanical shear measurements. Finally, this work illustrates the capability and the working rules of acoustical measurements in a small tank.

Dynamic crossover in supercooled liquids induced by high pressure

The physics underlying the dynamics of molecules near their glass temperature, T g , comprises one of the major unsolved problems in condensed matter. Of particular interest are the striking changes in relaxation properties observed at temperatures ∼1.2 times higher than T g . Herein, we describe experiments in which these changes in dynamics are induced by pressure variations. For several supercooled liquids, the relaxation time associated with the change in dynamics is found to be invariant to both temperature and pressure. That is, the time scale of the molecular motions determines the onset of strong intermolecular cooperativity and the accompanying dynamical changes. While thermodynamic variables such as temperature and pressure influence the crossover in dynamics, the governing variable is the time scale.

Dielectric α-relaxation and ionic conductivity in propylene glycol and its oligomers measured at elevated pressure

Structural dynamics and volume were measured as a function of both temperature and pressure for a propylene glycol and its oligomers (PPG), and the results compared with previous data on higher molecular weight polypropylene glycols. PPG is of special interest because the terminal groups form hydrogen bonds; thus, by studying different molecular weights, the manner in which hydrogen bonding influences the dynamics in the supercooled regime can be systematically investigated. The fragility (Tg-normalized temperature dependence) of the dimer and trimer of PPG increases with pressure, similar to results for other H-bonded liquids, but different from van der Waals glass formers. This behavior is believed to be due to the effect of pressure in decreasing the extent of hydrogen bonding. From the combined temperature and volume dependences of the relaxation times, the relative degree to which thermal energy and volume govern the dynamics was quantified. With decreasing molecular weight, the relative contribution...

The dynamics crossover region in phenol- and cresol-phthalein-dimethylethers under different conditions of pressure and temperature

Dielectric relaxation times over a broa dr a nge of temperature and pressure for the glass former phenolphthalein-dimethylether (PDE) reveal a change of dynamics at a characteristic relaxation time τB .T he value of τB was found to be largely insensitive to the particular combination of pressure and temperature of the measurement. Data for a second glass former, cresolphthalein-dimethylether, having a molecular structure very close to that of PDE, were also analysed. In this case, τB is much smaller, so the change of dynamics could not be observed in the elevated pressure experiments. The PDE data were in good agreement with the Adam–Gibbs model near Tg(τ > τB) ,w hile deviating for τ< τB .F ina lly, a possible connection between the observed TB and theoretical models is presented.

Volumetric study of n-octyloxy-cyanobiphenyl (8OCB)

Volumetric measurements were carried out on n-octyloxy-cyanobiphenyl (8OCB) over temperatures from ambient to 150°C at pressures up to 200 MPa, encompassing the liquid, nematic and smectic liquid crystalline, and crystal states. From the step changes in volume at the transitions, the phase boundaries and the associated activation enthalpies and energies were determined. The results are consistent with prior studies that were limited to a narrower range of thermodynamic conditions. The thermodynamic potential parameter, Γ, found for the isotropic–nematic transition, =3.15, is significantly smaller than the scaling exponent γ (=4.4) that superposes the longitudinal relaxation times in the nematic state. From this non-equivalence, we conclude that the order parameter must vary with pressure along the clearing line. By comparing the phase behaviour of the nematic state for isochoric and isobaric conditions, the relative contribution of volume was determined to be less that the effect of thermal energy on the thermodynamic stability.

The role of the isothermal bulk modulus in the molecular dynamics of super-cooled liquids

Elastic models imply that the energy expended for a flow event in ultra-viscous matter coincides with the elastic work required for deforming and re-arranging the environment of the moving entity. This is quite promising for explaining the strong non-Arrhenius behavior of dynamic quantities of fragile super-cooled liquids. We argue that the activation volume obtained from dielectric relaxation and light-scattering experiments for super-cooled liquids should scale with the Gibbs free energy of activation, with a proportionality constant determined by the isothermal bulk modulus and its pressure derivative, as described by an earlier thermodynamic elastic model. For certain super-cooled liquids the bulk compression transpiring in the local environment, as governed by the isothermal bulk modulus, play a significant role in the reorientational dynamics, with far-field density fluctuations and volume changes avoided by shear deformation.