Brillouin light scattering study of polymeric glassy sulfur

We present here a study of the acoustic dynamics of polymeric glassy sulfur. The data have been collected in the GHz frequency range by means of Brillouin light scattering for different scattering geometries. The choice of the experimental setup allows us to obtain information on the refractive index, n, that comes out to be close to that corresponding to the high temperature polymeric liquid phase. The longitudinal acoustic excitations have been investigated as a function of temperature from deep into the glassy state up to the glass transition temperature. The temperature dependence of the sound velocity is compared to the one measured in the liquid phase. We find that the sound velocity of the glass can be linearly extrapolated from that of the polymeric liquid measured in the THz frequency range with inelastic X-ray scattering.     

Influence of pressure on fast dynamics in polyisobutylene

Influence of pressure on fast dynamics and elastic properties in polyisobutylene is studied using Raman, Brillouin and neutron scattering spectroscopy. Analysis of the results shows that the boson peak frequency increases with pressure stronger than the longitudinal sound velocity measured by Brillouin scattering. Moreover, the boson peak intensity decreases under pressure stronger in Raman scattering than in neutron scattering suggesting a decrease in the light-to-vibrations coupling coefficient C(ν). The strong decrease of the microscopic peak intensity under pressure in Raman spectra supports this suggestion. We argue that variations in C(ν) might be related to amplitude of structural fluctuations. We speculate that change in disorder and/or overall density under pressure is the main cause for the observed variations.     

Mechanical relaxation near glass transition studied by various methods

Viscosity in pure shear deformation mode was measured for various glasses. The temperature dependence of viscosity was of hydrodynamic (Vogel-Tammann-Fulcher) type and of the hopping (Arrhenius) type above and below the glass transition temperature. Double Arrhenius dependence was seen in glasses containing molecular chains. Internal friction was measured near and above the glass transition for metallic and polymer glasses. The viscoelastic relaxation was observed and the result was analyzed by adopting the Maxwell model and the Maxwell relation. In the relaxation a correlation between the pre-exponential factor and the activation energy (compensation effect) was seen. Ultrasound and Brillouin scattering experiments were performed for a polymer glass. Relaxation was seen near the glass transition in the sound velocity and sound attenuation. The activation energy values for the relaxation obtained by various experiments were compared by adopting the idea of potential energy landscape.     

Effect of polymerization on the boson peak, from liquid to glass

Reactive epoxy-amine mixtures during isothermal polymerization have been characterized by Raman scattering measurements in order to follow the modification of the vibrational density of states. In the initially liquid solutions an increasing number of Van der Waals bonds are replaced by stiffer covalent bonds. During the chemical reaction, the molecular diffusion slows down and ultimately the systems are frozen in a glassy structure. The transformation from reactive liquids to chemical glasses is accompanied by microscopic structural changes driven by the bonding process. During the reaction the samples density and the sound velocity increase, both of them contribute to significantly change the Debye level. By combining Raman with Brillouin inelastic X-ray scattering measurements, we compare the relative variations of the boson peak with that of the Debye level. We find that the shift and intensity variation of the boson peak are fully explained by the modification of the elastic properties of the medium and a boson peak master curve is obtained.     

Study of the dynamic structure factor of strong glasses

The dynamic structure factors (DSFs) of several strong glasses (SF6, SF10, BK7, SUPRASIL) measured by Brillouin light scattering spectroscopy are reported. Spectra have been collected, at and above room temperature, at two scattering angles, θ=90° and θ=180° corresponding to exchanged wavevector q values ranging from 0.0256 to 0.0448 nm⁻¹. In particular we find that the isotropic spectral lineshapes are in all cases well described by the simple hydrodynamic theory of an amorphous solid. The width of the Brillouin peaks are found to be consistent with the predicted q² dependence at both investigated temperatures. This damping is however found to account only partially for the strong asymmetry of the Brillouin line clearly visible on a logarithmic intensity scale. As a matter of fact there is an excess intensity in the very low frequency plateau underlying the central component. The height of this plateau and hence the entire lineshape is well reproduced if a relaxation process is taken into account in the hydrodynamic equations. Owing to the intense elastic scattering we are able to determine unambiguously only the ratio between amplitude and characteristic time of this process which quantifies the sound dispersion to be of the order of a few percent in all samples. The temperature dependence of the parameters indicates that this relaxation cannot be attributed to thermally activated relaxation phenomena. These general findings favorably compare with molecular dynamics simulation results on similar systems.     

Pressure dependence of elastic properties of low-silica calcium alumino-silicate glasses

The hydrostatic and uni-axial pressure dependence of elastic properties of a low-silica calcium alumino-silicate glass (LSCAS) is determined by ultrasonic pulse-echo techniques at room temperature. The experimental results are used to obtain the third-order elastic constants (TOECs) of these glasses. The pressure dependence of fractal bond connectivity of these glasses is discussed. The normal behavior of positive pressure dependence of ultrasonic velocities was observed for the glass. The pressure dependence of both shear modulus and bulk modulus are positive for these glasses.     

Polar optical phonon scattering and negative Krömer–Esaki–Tsu differential conductivity in bulk GaN

GaN is being considered as a viable alternative semiconductor for high-power solid-state electronics. This creates a demand for the characterization of the main scattering channel at high electric fields. The dominant scattering mechanism for carriers reaching high energies under the influence of very high electric fields is the polar optical phonon (POP) emission. To highlight the directional variations, we compute POP emission rates along high-symmetry directions for the zinc-blende and wurtzite crystal phases of GaN. Our treatment relies on the empirical pseudopotential energies and wave functions. The scattering rates are efficiently computed using the Lehmann–Taut Brillouin zone integration technique. For both crystal phases, we also consider the negative differential conductivity possibilities associated with the negative effective mass part of the band structure.     

Origin of Rayleigh scattering and anomaly of elastic properties in vitreous and molten GeO2

Vitreous (v) and molten (m) GeO₂ were studied by Rayleigh and Mandel’shtam–Brillouin scattering spectroscopy and high-temperature acoustics. Original measurement apparatus and procedure were used that included Bayseian deconvolution of light scattering spectra of vGeO₂ and a specially designed high-temperature (up to 1500 °C) acoustic interferometer to measure temperature and frequency dependence of ultrasonic (US) velocity and attenuation in mGeO₂. Landau–Placzek ratios for vGeO₂ were found optically (from the light scattering spectrum) and acoustically (through the Schroeder’s formalism). Dispersion of optical and other physical parameters of vGeO₂ found by many authors is explained by the existence of small amount of GeO in the samples. It means that properties of vGeO₂ are under the influence of redox synthesis conditions controlling the GeO₂ ↔ GeO and coordination [GeO₄] ↔ [GeO₆] equilibrium in vGeO₂. Measurements of temperature dependencies of longitudinal ultrasonic velocities in mGeO₂ and in the PbO–GeO₂ glass melts as a function of PbO concentration shows existence of ‘water-like anomaly’ in mGeO₂ and in liquid germanates with the rich content of GeO₂ where equilibrium sound velocity increases with the temperature.     

Thermal and mechanical properties of rare earth aluminate and low-silica aluminosilicate optical glasses

Aluminate glasses containing 45–71.5 mol% alumina, 10–40 mol% rare earth oxide, and 0–30 mol% silica were synthesized from precursor oxides. The glass transition and crystallization temperatures were determined by differential scanning calorimetry; the structural and mechanical properties were investigated by Raman and Brillouin spectroscopy. The range of the supercooled liquid region varies from ∼40 °C to 200 °C, providing a useful working range for compositions with 5–30 mol% silica. Raman scattering showed the presence of isolated SiO₄ species that strengthen the network-forming structure, enhance glass formation, and stabilize the glass even when they are present at fairly low concentrations. Sound velocities were measured by Brillouin scattering. From these and other values, various elastic moduli were calculated. The moduli increased with both aluminum and rare earth content, as did the hardness of the glasses. Young’s modulus was in the range 118–169 GPa, 60–130% larger than that for pure silica glass.     

Ultrasonic measurement technique to study thermometric effects in glass

Ultrasonic measurements of shear wave propagation in alkali containing glasses reveal temporal instabilities and thermal after-effects which parallel thermometric effects, the secular rise and zero point depression in the ice point of glass thermometers. The ultrasonic method of observing these effects has advantages over the thermometric technique. Sound velocity is a dynamic quantity proportional to the elastic moduli and density which can be measured on an absolute basis and over a frequency range if desired. Thus in measuring instabilities in the elastic properties of glass the ultrasonic method provides additional information over the use of the thermometric technique whose measured changes relate only to density changes in the glass and only on a relative basis. In addition sound velocity can be measured over as wide a temperature range as desired extending from cryogenic to above glass transition range temperatures. Also no fixed reference points are required as with thermometers. Sample preparation is relatively simple and the availability of ‘packaged’ ultrasonic measurement facilities makes this method of measuring very small changes (ppm) in elastic properties very attractive.Data as a function of time and temperature are presented for a series of alkali-lead-silicates incorporating separately Li, Na, K, Rb, Cs, and for a lead silicate containing the alkaline earth Ba. The results indicate the reversible nature of the instabilities and after-effects and express their magnitudes and sensitivities to the temperature and temperature interval of measurement. They are also related to the thermal history of the glass, and the concentration and species of the incorporated alkali.     

Na2CaSi2O6–P2O5 based bioactive glasses. Part 1: Elasticity and structure

The glass structure and elastic properties of two bioglasses having bulk compositions near Na₂CaSi₂O₆ (45S5.2) and Na₂CaSi₃O₈ (55S4.1) were studied using both Raman and Brillouin scattering techniques. The annealed 45S5.2 glass has more Q² and Q⁰ but less Q³ species than 55S4.1 glass due to lower (Si⁴⁺ + P⁵⁺)/(Na⁺ + Ca²⁺) ratio. Brillouin scattering measurements of the as-annealed glasses indicated that 45S5.2 glass is ca. 2% and 9% higher in Young’s and bulk moduli than 55S4.1 glass due to more modifiers in the 45S5.2 glass. Nearly full crystallization of 45S5.2 glass was observed after treating it at 715 °C for ca. 30 min. Devitrification of the 45S5.2 glass caused an increase in the elastic moduli up to ca. 30% (fully crystallized) but a negligible change in density. This 45S5.2-derived crystalline phase displayed at least 17 Raman bands, and has the average elastic moduli of 72.4 (bulk), 41.6 (shear), and 104.7 (Young’s) GPa. The comparable elastic moduli with hydroxyapatite and the ability for developing a HCA layer in simulated body fluid indicate that the 45S5.2-derived phase may be better for using as a substitute of bone than its parent glass.     

Kinetics of crystallization of potassium chloride from aqueous solutions at 30 °C

The aim of this work is to use a diffusion layer model for the determination of individual rate constants of reaction and diffusion step of KCl at 30 °C. Crystal growth rate was measured by travelling microscope technique. From the measured values of the mean linear growth rate the resulting individual rate constants and the effectiveness factors (GARSIDE) are evaluated as a function of the driving force and of the flow velocity of solution. The significance of diffusional and surface reaction resistances against mass transfer is discussed in relation to the experimental conditions used.     

Study of transport properties co – evaporated lead telluride (PbTe) thin films

Thin films of lead telluride (PbTe) of thicknesses ranging from 1000 Å to 2500 Å have been prepared by co‐evaporation (three temperature) technique, onto precleaned amorphous glass substrates at various temperatures. The deposited samples were annealed and annealed samples were used for characterization. Resistivity of these samples was measured by four‐probe technique as a function of thickness and temperature. Activation energy for charge transport have been evaluated and found in the range of 0.09 to 0.106 eV. Thermoelectric power has been measured and found to be positive indicating that the samples are p‐type semiconducting material. Mobility variation with temperature has been estimated (evaluated) and correlated with scattering mechanism in the entire range of temperature studied. The X‐ray diffraction analysis confirmed that films are polycrystalline having cubic structure cell and lattice parameters are reported.     

Compositional design of high modulus glasses for disk substrates

Modified equations have been derived on the basis of Makishima–Machenzie (M–M) theory for direct determination of the elastic modulus of glasses from composition. This modified calculation model gives an excellent agreement between the measured and estimated values of elastic modulus for over 50 different glasses. Using this model we developed a glass in the Li₂O–MgO–Al₂O₃–Y₂O₃–TiO₂–SiO₂ system with elastic modulus value greater than 130 GPa and bending strength higher than 50 kg f/mm². This high modulus glass substrate is expected to provide a solution to the vibration problem of rapid rotation magnetic disk and allow higher track density per inch to be achieved for high performance hard-disk drives (HDDs).     

Brillouin scattering measurements of attenuation and velocity of hypersounds in SiO2B2O3 glasses

Measurements of hypersound wave velocity and attenuation (20–30 GHz) were made at room temperature by Brillouin scattering in SiO₂O₂O₃ glasses. The attenuation shows a maximum with composition. An explanation of this maximum is given in relation to the glass structure. It is thought that this maximum may be due to a coupling effect of hypersounds with structural relaxational process involving SiSi and SiOB bonds.     

Diffraction Elastic Constants for Textured Materials — Different Methods of Calculation

A systematic review of different types of traditional averages for diffraction elastic constants in textured materials is given. In addition a new type of average, which recently was suggested, is presented. These averages are of vital importance for a correct interpretation of internal (e.g. residual) stress measurements. The theoretically predicted diffraction elastic constants are compared with the experimental ones for rolled steel samples; there exists good agreement between theory and experiment.     

Static heterogeneity in metallic glasses and its correlation to physical properties

Glasses exhibit intriguing physical and mechanical properties resulting from their structure. We have investigated metal-glass dynamics using inelastic X-ray scattering and ultrasonic techniques for several Pd-, Pt-, and Zr-based glasses with varying fragility. In some cases we have observed a faster phase velocity at short wavelengths than long wavelengths, or positive dispersion. Here we apply elastic wave scattering theory to suggest that the behavior of acoustic phonons can be understood by considering the presence of intrinsic nanoscale elastic inhomogeneity with a certain correlation length, i.e., “static heterogeneity”. Furthermore, we suggest that such an elastic inhomogeneity could be the origin of many of the interesting physical and mechanical properties of metallic glasses.     

Elastic properties of zinc tris(thiourea) sulphate in a wide temperature range studied by Brillouin spectroscopy

The elastic properties of the zinc tris (thiourea) sulphate crystal were studied by Brillouin spectroscopy in the range 80 – 300 K. The measurements were made on single crystals obtained by the isothermal method. The temperature dependences of the Brillouin shift were determined for the crystal in the principal directions and in a few mixed directions on a tandem type spectrometer. The results revealed anomalies in the bulk wave propagation rate and in a few elastic constants at about 138 K. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Studies of nanostructuring in cesium magnesium tungsten phosphate glass

Cs₂O–MgO–WO₃–P₂O₅ glass was examined in a broad temperature range using heat capacity, Raman and Brillouin scattering methods. The main aim was to study the elastic properties of the as-prepared glass, the mechanism of nanostructuring in this material and the influence of nanostructuring on its elastic properties. It was shown that this glass exhibits prominent nanocrystallization during thermal treatment, giving Cs(Mg_0.25W_1.75)O₆ nanocrystals with the size of 4–10 nm. The crystallization process was hindered when crystallinity reached about 14 ± 0.6 wt%. The origin of this behavior was discussed. It was also demonstrated that the elastic properties are largely improved by nanocrystallization.     

X-ray study of the structure of multicomponent glasses based on mining-industry waste

The short-range order and microinhomogeneity structure of laboratory samples of glasses belonging to the diopside-orthoclase-apatite system with different percentages of components were investigated by X-ray diffraction and small-angle scattering. A correlation between a change in the chemical composition of a glass, causing its segregation, and the short-range order parameters was ascertained: an increase in the apatite content leads to a change in the short-range order parameters. The use of the X-ray small-angle scattering technique made it possible to reveal inhomogeneities of electron density in the glasses under study and the dependence of the sizes of inhomogeneities on the glass composition.