Brillouin scattering and optical Kerr effect study of dimethacrylates: temperature effects

In this paper we report a temperature study of Brillouin scattering and optical Kerr effect in the ethane-1,2-diol dimethacrylate, pentane-1,5-diol dimethacrylate and hexane-1,6-diol dimethacrylate belonging to the series of dimethacrylate homologues. Using these methods we have studied the temperature behaviour of the hypersonic velocity, adiabatic compressibility and optical Kerr constant in the temperature range from 283 to 323 K.

The obtained results are compared to those obtained earlier from Brillouin scattering and optical Kerr effect experiments for butane-1,4-diol dimethacrylate and 2,2′-thiodiethyl dimethacrylate (a sulfur-containing monomer). The results are also discussed in terms of changes in the intermolecular interactions and arrangement in the liquid compounds under study.     

Evidences of nonideal mixing in poly(ethylene glycol)/organic solvent mixtures by Brillouin scattering

The concentration dependence of the hypersonic properties of solutions of poly(ethylene glycol) of mean molecular mass 600 g/mol (PEG600) in benzene and toluene has been investigated by Brillouin scattering. The two solvents are very similar in structure and chemical properties, but while benzene is nonpolar, toluene possess a modest dipole. In both solvents a high-frequency relaxation process has been observed at high concentrations which has been assigned to conformational rearrangements of the polymeric chains, triggered by reorientation of the side groups. In both cases, the concentration dependence of the adiabatic compressibility deviates significantly from linearity, indicating the existence of nonideal mixing phenomena driven by aggregation processes taking place in the systems. However, there is no temperature dependence for solutions of PEG600 in benzene; on the contrary, the results obtained for solutions of PEG600 in toluene are noticeably dependent on the temperature. The comparison of the experimental data with the results of previous experiments on similar systems allows a general picture for weakly interacting mixtures of hydrogen-bonded systems and organic solvents to be developed. In particular, in the presence of a nonpolar solvent molecule the local structure of the mixture is dominated by solute self-association processes and any resulting solute-solvent correlation is barely induced by excluded volume effects. At high enough dilution the self-aggregation of solute molecules produces a variety of new local topologies that cannot be observed in bulk solute, and as a consequence, the concentration evolution of the system is too rich to be described in terms of a linear combination of a few components over the whole concentration range. The situation seems to be simpler for the polar toluene solvent molecules, where a three-component model seems able to fit the experimental concentration dependence of the hypersonic velocity. This result is interpreted to imply that the interaction between the solvent dipoles and the active sites of the solute produces a relatively stable heterocoordination, while the relevance of self-association is partially reduced.     

Structural relaxation processes in polyethylene glycol/CCl4 solutions by Brillouin scattering

We present results of a Brillouin scattering experiment on solutions of poly(ethylene glycol) of mean molecular mass 600 g/mol (PEG600) in CCl4. The relaxation process detected has been assigned to conformational rearrangements of the polymeric chains, triggered by reorientation of the side groups. The concentration dependencies of the hypersound velocity and normalized absorption are compared against the indications from several models proposed in the literature. The concentration evolution of the system is described in terms of two distinct regimes. At high polymer content, the system is dominated by the structure of the dense polymer, where polymer-polymer interactions, together with excluded volume effects, induce the existence of a preferred local arrangement resulting in a narrow distribution of the relaxation times, with the average value of the relaxation time following a simple Arrhenius temperature dependence. As the concentration decreases, the original structure of the hydrogen bonded polymer network is destroyed, and a number of different local configuration coexist, giving rise to a wider distribution of relaxation times or to a multiple relaxation. At low concentrations, the experimental data are well fitted assuming a Vogel-Fulker-Tammon behavior for the average relaxation time. In addition, the observed deviation from the ideal behavior for the refractive index and the density suggests that CCl4 does not behave as an inert solvent, and due to polarization effects, it can develop local hetero-associated structures via electrostatic interaction with the O-H end groups of the polymeric chains. The hypothesis has been successfully tested by fitting the concentration behavior of the hypersonic velocity to a recent three-component model, suitable to describe the concentration dependence of sound velocity in moderately interacting fluids. The indication of the model furnishes a very high value for the association constant of the PEG600, confirming the literature indication that, in polymeric systems capable of developing long liner aggregates via hydrogen bonding interaction, the Brillouin probe is insensitive to the true length of the polymeric chains. The Brillouin scattering experiment just sees an effective hydrogen bonded aggregate that is huge relative to the length of the single polymeric chain and becomes sensitive only to the density fluctuations of the local segmental motions.     

High-Frequency Dynamical Behavior of Poly(ethylene glycol)+H2O Mixtures by Brillouin Spectroscopy

Brillouin spectroscopy has been used to examine high-frequency dynamical behavior of aqueous solutions of poly(ethylene glycol) (Mw ≈ 400g/mol) at 298K in the entire concentration region. It was found that a relaxation process takes place in the experimental frequency window that significantly affects the shape of experimentally recorded spectrum of the density fluctuations (dynamical structure factor). The process detected was attributed to segmental motion of the flexible polymeric chain. The full spectrum analysis of Brillouin spectra has been performed taking advantage of the relaxation function previously used in describing a single relaxation process in dielectric examination of water solutions of PEG 400. The proposed data processing procedure permits a qualitative reproduction of concentration dependencies of the hypersonic wave velocity and absorption measured. The shapes of the concentration dependencies of the relaxation times obtained from the Brillouin and the dielectric spectroscopies are in good agreement over a very broad concentration range, although their absolute values are scaled by the factor of 3. This result indicate that the two processes revealed independently by dielectric and Brillouin spectroscopies, apparently separated in time-scale, are just the same relaxation process.     

Emission characteristics of an LiF: F2 colour centre laser in the visible

Energetic and spectral characteristics of an LiF : F₂ colour centre laser operating in the visible (λ ≈ 685 nm) are de-described. Optical gain coefficient of the crystal amounts to about 15 cm^-1 at an F₂-centres concentration of 5 × 10¹⁷ cm^-3.     

Temperature study of Brillouin light scattering in selected dimethacrylates

Selected dimethacrylates forming multifunctional monomers have been studied using Brillouin spectroscopy. The hypersound wave propagation velocity and adiabatic compressibility of the compounds studied have been determined. It has been revealed that these quantities depend on both temperature and the structure of the molecule chain of the monomer. Some characteristic features obtained from the Brillouin study have been discussed in terms of molecular interactions.