A. Patkowski

Depolarized dynamic light scattering studies of ortho‐terphenyl dynamics above Tg

Depolarized Rayleigh spectra of ortho‐terphenyl (OTP) were measured in the temperature range from Tg to Tg+190 K. Two samples prepared with and without ‘‘clusters’’ were used for the measurement. Four different Fabry–Perot interferometers covering the time range from about 0.5 ps to 100 ns were employed. Two relaxation modes were observed: a slow mode with all its characteristics of the α process, and a fast mode with a constant, temperature independent relaxation time of about 3 ps. The fast mode has not been reported heretofore. The intensity of the fast mode vanishes at about the Vogel–Fulcher–Tamman temperature T0. The relaxation times of these two processes are found to be identical for both OTP with and without clusters. The temperature dependence of the relaxation time of the α process is Arrhenius at high temperatures, but shows a Williams–Landel–Ferry (WLF) behavior in the range from Tg to Tg+80 K for both samples with and without the long‐range density fluctuations (i.e., cluster).

The relative contributions of temperature and volume to structural relaxation of van der Waals molecular liquids

Pressure-volume-temperature measurements were carried out on two van der Waals liquids, 1,1′-bis(p-methoxyphenyl)cyclohexane (BMPC) and 1,1′-di(4-methoxy-5methylphenyl)cyclohexane (BMMPC). In combination with dielectric spectroscopy results, the relative contribution of temperature and density to the structural relaxation times were quantified. We find that the ratio of the isobaric expansion coefficient [−ρ−1 (∂ρ/∂T)P, where ρ is mass density and T is temperature, evaluated at P=0.1 MPa] to the coefficient of isochronal expansivity [−ρ−1 (∂ρ/∂T)τ, evaluated at τ=1 s] equals 0.58 and 0.72 for BMPC and BMMPC, respectively. This indicates that density exerts more influence on the structural relaxation times than does thermal energy. Corroborating this finding, the ratio of the isochoric activation energy to the activation energy at constant pressure is determined to be ca. 0.4 at ambient pressure for both glass formers. The prevalence of density over thermal energy is contrary to prevailing ideas concerning...

Spectrum of fast dynamics in glass forming liquids: Does the "knee＇＇ exist?

A knee-shaped feature observed earlier in light scattering spectra of Ca0.4K0.3(NO3)1.4 (CKN) below Tc is used as a strong argument in favor of mode-coupling theory of the glass transition (MCT). Our careful measurements reveal no “knee” in the spectra of two glass forming liquids, CKN and ortho-terphenyl. Instead of the knee the spectra show nontrivial broadening and an increase of the intensity with a temperature increase. Both variations are confirmed by neutron scattering measurements on CKN and are neither expected in the asymptotic MCT predictions nor in any other model.

Diffusion and microstructural properties of solutions of charged nanosized proteins: Experiment versus theory

We have reanalyzed our former static small-angle x-ray scattering and photon correlation spectroscopy results on dense solutions of charged spherical apoferritin proteins using theories recently developed for studies of colloids. The static structure factors S(q), and the small-wave-number collective diffusion coefficient D(c) determined from those experiments are interpreted now in terms of a theoretical scheme based on a Derjaguin-Landau-Verwey-Overbeek-type continuum model of charged colloidal spheres. This scheme accounts, in an approximate way, for many-body hydrodynamic interactions. Stokesian dynamics computer simulations of the hydrodynamic function have been performed for the first time for dense charge-stabilized dispersions to assess the accuracy of the theoretical scheme. We show that the continuum model allows for a consistent description of all experimental results, and that the effective particle charge is dependent upon the protein concentration relative to the added salt concentration. In addition, we discuss the consequences of small ions dynamics for the collective protein diffusion within the framework of the coupled-mode theory.

Does fragility depend on pressure? A dynamic light scattering study of a fragile glass-former

Relaxation times of the α-process in the fragile glass-forming liquid diglycidyl ether of bisphenol-A (EPON 828) were measured in a broad pressure (1–1500 bar) and temperature (264–293 K) ranges by means of the depolarized dynamic light scattering—photon correlation spectroscopy. Based on this experimental data the fragility of the supercooled liquid was calculated in two ways: as a steepness index m of the “Angell plot” and as the DT-parameter from the Vogel–Fulcher–Tammann Law, and was studied as a function of pressure. It was found, that while the steepness index depends on pressure, the DT parameter is pressure independent. The pressure dependence of the glass transition temperature Tg in EPON 828 was found to be nonlinear. Additionally, we established a relationship between the steepness index mT, the activation volume ΔV#, and the coefficient ∂Tg/∂Pg. In this pressure dependent study we found that also for EPON 828 the nonexponentiality of the correlation function of the α-process correlates well wi...

Pressure and temperature dependence of structural relaxation in diglycidylether of bisphenol A

The structural (α-) relaxation in diglycidylether of bisphenol A (DGEBA) has been examined using three spectroscopic methods: dielectric spectroscopy (DS), dynamic light scattering–photon correlation spectroscopy (LS), and mechanical spectroscopy. The DS and LS measurements were carried out as a function of both temperature and pressure. Moreover, pressure-volumetemperature measurements were obtained for the DGEBA. These data allow an assessment of the relative contributions of thermal energy and free volume to structural relaxation in DGEBA. The results clearly show a substantial role for both thermal and free volume fluctuations in the dramatic slowing down of the dynamics. The combined temperature- and pressure-dependences of the dielectric and light scattering relaxation times were analyzed using the Avramov equation, implying that the fragility (normalized temperature dependence) is pressure independent over the studied range of pressures. The pressure dependence was the same as measured by the diffe...

Density fluctuations around the glass-transition of low molecular weight glass-forming liquids

Abstract The Rayleigh-Brillouin spectra of ortho-terphenyl (OTP) samples with and without ‘clusters’ were measured in the temperature range from Tg to Tg + 200 K. The values of the Landau-Placzek ratio for cluster-free OTP were low, in agreement with the theoretical predictions, while for OTP with clusters much higher values were obtained. The isotropic part of the Rayleigh intensity for OTP with clusters contained an additional angular-dependent component that could be reversibly reduced after annealing the samples at temperatures > Tm. Rotational relaxation times of OTP samples with and without clusters were measured by means of depolarized Rayleigh spectroscopy. In addition to the usual rotational relaxation time, an additional fast component was found. The relaxation time of the fast process was practically constant in the entire temperature range amounting to 3 ps and the intensity decreased to zero around TO. The temperature dependence of the rotational relaxation time cannot be described by the Wohlrausch-Landel-Ferry formula over the entire relaxation time range from 4 × 10−11 to 10 s, but only down to 10−10 s.

Structure and short-time dynamics in suspensions of charged silica spheres in the entire fluid regime.

We present an experimental study of short-time diffusion properties in fluidlike suspensions of monodisperse charge-stabilized silica spheres suspended in dimethylformamide. The static structure factor S(q), the short-time diffusion function D(q), and the hydrodynamic function H(q) have been probed by combining x-ray photon correlation spectroscopy experiments with static small-angle x-ray scattering. Our experiments cover the full liquid-state part of the phase diagram, including de-ionized systems right at the liquid-solid phase boundary. We show that the dynamic data can be consistently described by the renormalized density fluctuation expansion theory of Beenakker and Mazur over a wide range of concentrations and ionic strengths. In accordance with this theory and Stokesian dynamics computer simulations, the measured short-time properties cross over monotonically, with increasing salt content, from the bounding values of salt-free suspensions to those of neutral hard spheres. Moreover, we discuss an upper bound for the hydrodynamic function peak height of fluid systems based on the Hansen-Verlet freezing criterion.

Diffusion of spheres in crowded suspensions of rods

Translational tracer diffusion of spherical macromolecules in crowded suspensions of rodlike colloids is investigated. Experiments are done using several kinds of spherical tracers in fd-virus suspensions. A wide range of size ratios L/2a of the length L of the rods and the diameter 2a of the tracer sphere is covered by combining several experimental methods: fluorescence correlation spectroscopy for small tracer spheres, dynamic light scattering for intermediate sized spheres, and video microscopy for large spheres. Fluorescence correlation spectroscopy is shown to measure long-time diffusion only for relatively small tracer spheres. Scaling of diffusion coefficients with a/xi, predicted for static networks, is not found for our dynamical network of rods (with xi the mesh size of the network). Self-diffusion of tracer spheres in the dynamical network of freely suspended rods is thus fundamentally different as compared to cross-linked networks. A theory is developed for the rod-concentration dependence of the translational diffusion coefficient at low rod concentrations for freely suspended rods. The proposed theory is based on a variational solution of the appropriate Smoluchowski equation without hydrodynamic interactions. The theory can, in principle, be further developed to describe diffusion through dynamical networks at higher rod concentrations with the inclusion of hydrodynamic interactions. Quantitative agreement with the experiments is found for large tracer spheres, and qualitative agreement for smaller spheres. This is probably due to the increasing importance of hydrodynamic interactions as compared to direct interactions as the size of the tracer sphere decreases.

Diffusion of spheres in isotropic and nematic networks of rods: Electrostatic interactions and hydrodynamic screening

Translational diffusion of a small charged tracer sphere in isotropic and nematic suspensions of long and thin charged rods is investigated as a function of ionic strength and rod concentration. A theory for the diffusive properties of a small sphere is developed, where both (screened) hydrodynamic interactions and charge interactions between the tracer sphere and the rod network are analyzed. Hydrodynamic interactions are formulated in terms of the hydrodynamic screening length. As yet, there are no independent theoretical predictions for the hydrodynamic screening length for rod networks. Experimental tracer-diffusion data are presented for various ionic strengths as a function of the rod concentration, both in the isotropic and nematic states. Orientational order parameters are measured for the same ionic strengths as a function of the rod concentration. The hydrodynamic screening length is determined from these experimental data and scaling relations obtained from the above mentioned theory. For the isotropic networks, a master curve is found for the hydrodynamic screening length as a function of the rod concentration. For the nematic networks the screening length turns out to be a very sensitive function of the orientational order parameter.