D. Fioretto

Two crossover regions in the dynamics of glass forming epoxy resins

Broadband dielectric spectroscopy, heat capacity spectroscopy (3ω method), and viscosimetry have been used to study the dynamic glass transition of two glass-forming epoxy resins, poly [(phenyl glycidyl ether)-co-formaldehyde] and diglycidyl ether of bisphenol-A. In spite of their rather simple molecular structure, the dynamics of these systems is characterized by two well-separated crossover regions where the relaxation times of main transition and the two secondary relaxations β and γ approach each other. The main transition has three parts: The a process at high temperature, the a′ process between the two crossover regions, and the α process at low temperatures. Both the γ-crossover region [around a temperature Tc(γ)∼(1.4–1.5)Tg and a relaxation time τc(γ)≈10−10 s] and the β-crossover region [around Tc(β)∼(1.1–1.2)Tg and τc(β)≈10−6 s] could be studied within the experimentally accessible frequency–temperature window. Different typical crossover properties are observed in the two regions. The γ-crossove...

Broadband Depolarized Light Scattering Study of Diluted Protein Aqueous Solutions

A broadband depolarized light scattering (DLS) study is performed on diluted lysozyme aqueous solutions as a function of temperature and concentration. The dynamical susceptibility, obtained in a wide spectral range (0.6-36000 GHz) through the coupled use of interferometric and dispersive devices, is interpreted and compared with neutron scattering and Raman-induced optical Kerr-effect literature data, thus giving a general picture of relaxation phenomena. We show that the proposed approach represents a suitable tool for investigating the hydration dynamics of protein-water solutions. A detailed analysis of the quasi-elastic scattering region evidences the existence of two distinct relaxational processes at picosecond time scales. The fast process (fractions of picosecond) is attributed to bulk water dynamics, while the slow one (few picoseconds) is attributed to dynamical rearrangements of water molecules strongly influenced by the protein (hydration water). The retardation effect here estimated of about 6-7 can be regarded as a direct measure of the increased protein-water and water-water hydrogen bond stability of the water molecules within the protein hydration shell. Interestingly, a similar effect was previously observed on small hydrophilic sugar molecules. Moreover, backbone and side chains torsional motions of the protein in the 600-5300 GHz frequency range are found to be insensitive to thermal variations and to eventual changes occurring in the premelting zone.

Light Scattering Spectra of Water in Trehalose Aqueous Solutions: Evidence for Two Different Solvent Relaxation Processes

Light scattering spectra on aqueous solutions of trehalose were recorded in a wide frequency range combining the use of a double monochromator and a multipass Fabry-Perot interferometer. Experimental results indicate the presence of a slow relaxation mode related to the solute dynamics, which is clearly separated from the solvent one. The spectral analysis reveals the existence of two separate solvent relaxation processes assigned to hydrating and bulk water molecules. The picosecond dynamics of water molecules directly interacting with the solute (proximal water) is consistently delayed with the corresponding relaxation time increase is about 5-6 times compared to the bulk. The slowing down induced by the sugar on the water dynamics mainly involves a restricted hydration layer constituted of 16-18 water molecules. These results improve our knowledge about the influence of carbohydrates on the fast rearrangement dynamics of water and may serve as a model to gain important insight on basic solvation properties of other biorelevant systems in aqueous media.

More Is Different: Experimental Results on the Effect of Biomolecules on the Dynamics of Hydration Water.

Biological interfaces characterized by a complex mixture of hydrophobic, hydrophilic, or charged moieties interfere with the cooperative rearrangement of the hydrogen-bond network of water. In the present study, this solute-induced dynamical perturbation is investigated by extended frequency range depolarized light scattering experiments on an aqueous solution of a variety of systems of different nature and complexity such as small hydrophobic and hydrophilic molecules, amino acids, dipeptides, and proteins. Our results suggest that a reductionist approach is not adequate to describe the rearrangement of hydration water because a significant increase of the dynamical retardation and extension of the perturbation occurs when increasing the chemical complexity of the solute.

Bond-controlled configurational entropy reduction in chemical vitrification

Glass formation is usually viewed in terms of physical vitrification: a liquid in a metastable state is cooled or compressed so as to avoid crystallization. However, glasses may also be formed by chemical vitrification, a process involving progressive polymerization of the constituent molecules via the formation of irreversible chemical bonds. The formation of most of the materials used in engineering plastics and the hardening of natural and synthetic resins are based on chemical vitrification. Despite the differences in the molecular processes involved in chemical and physical vitrification, surprising similarities are observed in the slowing down of the dynamics and in the thermodynamical properties of the resulting glasses. Explaining such similarities would improve general understanding of the glass transition and may disclose its universal nature. Here we report dielectric and photon-correlation measurements that reveal the origin of the similarity in the dynamical behaviour of physical and chemical glass formers. We find that the evolution of their configurational restrictions proceeds in a similar manner. In particular, we make a connection between the reduction in configurational entropy and the number of chemical bonds, a quantity that can be controlled in experiments.

CHANGES IN THE DYNAMICS OF SUPERCOOLED SYSTEMS REVEALED BY DIELECTRIC SPECTROSCOPY

The dynamics of monoepoxy, diepoxy, and triepoxy glass-formers from below to above the glass transition temperature, Tg, has been investigated through the temperature behavior of relaxation times, strengths, and conductivity, determined in a wide frequency range (102–2×1010 Hz). In all systems the main and secondary relaxations define a splitting temperature TS∼1.3×Tg; moreover, a crossover temperature TB∼TS is recognized, marking the separation between two different Vogel–Fulcher regimes for the structural dynamics. The strengths behavior reflects the distribution of the overall energy between the relaxation processes and no peculiar behavior is revealed at TS. A strong increase characterizes the strength of the secondary relaxation on crossing the glass transition from the lower temperatures. Conductivity data have been analyzed to test the dynamics in terms of the Debye–Stokes–Einstein (DSE) diffusion law. The prediction of the DSE model is well verified for mono- and diepoxide up to the high viscosity...

Brillouin scattering determination of the whole set of elastic constants of a single transparent film of hexagonal symmetry

In this work it is shown that the Brillouin light scattering technique can be successfully applied for determining the five effective elastic constants of a single transparent film of hexagonal symmetry, in the micron range of thicknesses. Measurements have been performed on a polycrystalline ZnO film, about 1.3 mu m thick, supported by a Si substrate. A major result of this work is that the elastic constant c66 is selectively determined for the first time from detection of the shear horizontal mode travelling parallel to the film surface. Similarly, a selective determination of c11 is attained from observation of the longitudinal mode guided by the film. The three remaining elastic constants, namely c13, c33, and c44, can be then obtained from detection of the Rayleigh surface mode and of the longitudinal bulk wave propagating at different angles from the surface normal.

Brillouin scattering by surface acoustic modes for elastic characterization of ZnO films

Brillouin scattering from surface phonons was used for determining the dispersion curves of guided acoustic modes propagating along piezoelectric ZnO films. Measurements were performed on films of different thicknesses in the range between 20 and 320 nm, deposited by RF magnetron sputtering on Si and SiO/sub 2/ substrates. Brillouin spectra from Rayleigh acoustic modes are taken in the backscattering geometry at different incidence angles between 30 degrees and 70 degrees . The experimental data for the ZnO/Si films fit the expected theoretical dispersion curves fairly well for film thicknesses greater than 150 nm, while they appreciably depart from the same curves for smaller thicknesses. This behavior is interpreted in terms of a reduction of the effective elastic constants of the film in a layer near the interface, due to the lattice misfit between the film and the substrate. This effect was not observed in the case of ZnO films deposited on fused quartz substrates.<<ETX>>

Hydration and Aggregation in Mono- and Disaccharide Aqueous Solutions by Gigahertz-to-Terahertz Light Scattering and Molecular Dynamics Simulations

The relaxation properties of hydration water around fructose, glucose, sucrose, and trehalose molecules have been studied by means of extended frequency range depolarized light scattering and molecular dynamics simulations. Evidence is given of hydration dynamics retarded by a factor ξ = 5-6 for all the analyzed solutes. A dynamical hydration shell is defined based on the solute-induced slowing down of water mobility at picosecond time scales. The number of dynamically perturbed water molecules N(h) and its concentration dependence have been determined in glucose and trehalose aqueous solutions up to high solute weight fractions (ca. 45%). For highly dilute solutions, about 3.3 water molecules per sugar hydroxyl group are found to be part of the hydration shell of mono- and disaccharide. For increasing concentrations, a noticeable solute-dependent reduction of hydration number occurs, which has been attributed, in addition to simple statistical shells overlapping, to aggregation of solute molecules. A scaling law based on the number of hydroxyl groups collapses the N(h) concentration dependence of glucose and trehalose into a single master plot, suggesting hydration and aggregation properties independent of the size of the sugar. As a whole, the present results point to the concentration of hydroxyl groups as the parameter guiding both sugar-water and sugar-sugar interactions, without appreciable difference between mono- and disaccharides.

Density fluctuations in the intermediate glass-former glycerol: A Brillouin light scattering study

Brillouin scattering has been used to measure the dynamic structure factor of glycerol as a function of temperature from the high temperature liquid to the glassy state. Our investigation aims at understanding the number and the nature of the relaxation processes active in this prototype glass forming system in the high frequency region. The associated character of glycerol is reflected by a rather simple relaxation pattern, while the contributions coming from intramolecular channels are negligible in the GHz frequency region. The temperature behavior of the characteristic frequency and lifetime of the longitudinal acoustic modes is analyzed, suggesting that a phenomenological model which only includes the structural (α) process and the unrelaxed viscosity is able to catch the leading contributions to the dynamics of the density fluctuations. This ansatz is also supported by a combined analysis of light and inelastic x-ray scattering spectra. The temperature dependence of the characteristic time of the α-...