Phonons and fractons in sol-gel alumina: Raman study

We report Raman scattering from the boehmite, gamma-, delta- and alpha-phases of the alumina gel. Samples are characterized by transmission and scanning electron microscopy, X-ray diffraction and density measurements. The main Raman line in the boehmite phase is red-shifted as well as asymmetrically broadened with respect to that in the crystalline boehmite, signifying the nanocrystalline nature of the gel. Raman signatures are absent in the gamma- and delta-phases due to the disorder in cation vacancies. We also show that low frequency Raman scattering from the boehmite phase resembles that from a fractal network, characterized in terms of fraction dimension ($) over tilde d. Taking Hausdorff dimension D of the boehmite gel to be 2.5 (or 3.0), the value of ($) over tilde d is 1.33 +/- 0.02 (or 1.44 +/- 0.02), which is close to the theoretically predicted value of 4/3.

Structure of the Pyridine-Chloranil Complex in Solution: A Surprise from Depolarized Hyper-Rayleigh Scattering Measurements

In this article, we report the structure of a 1:1 charge transfer complex between pyridine (PYR) and chloranil (CHL) in solution (CHCl(3)) from the measurement of hyperpolarizability (beta(HRS)) and linear and circular depolarization ratios, D and D', respectively, by the hyper-Rayleigh scattering technique and state-of-the-art quantum chemical calculations. Using linearly (electric field vector along X) and circularly polarized incident light, respectively, we have measured two macroscopic depolarization ratios D = I(X,X)(2 omega)/I(X,Z)(2 omega) and D' = I(X,C)(2 omega)/I(Z,C)(2 omega) in the laboratory fixed XYZ frame by detecting the second harmonic (SH) scattered light in a polarization resolved fashion. The stabilization energy and the optical gap calculated through the MP2/cc-pVDZ method using Gaussian09 were not significantly different to distinguish between the cofacial and T-shape structures. Only when the experimentally obtained beta(HRS) and the depolarization ratios, D and D', were matched with the theoretically computed values from single and double configuration interaction (SDCI) calculations performed using the ZINDO-SCRF technique, we concluded that the room temperature equilibrium structure of the complex is cofacial. This is in sharp contrast to an earlier theoretical prediction of the T-shape structure of the complex.

Laser- induced optical properties change in Sb10S40Se50 chalcogenide thin films: An investigation through FTIR and XPS measurements

Chalcogenide glasses are interesting materials for their infrared transmitting properties and photo-induced effects. This paper reports the influence of light on the optical properties of Sb10S40Se50 thin films. The amorphous nature and chemical composition of the deposited film was studied by X-ray diffraction and energy dispersive X-ray analysis (EDAX). The optical constants, i.e., refractive index, extinction coefficient, and optical band gap as well as film thickness are determined from the measured transmission spectra using the Swanepoel method. The dispersion of the refractive index is discussed in terms of the single-oscillator Wemple-DiDomenico model. The dispersion energy parameter was found to be less for the laser-irradiated film, which indicates the laser-irradiated film is more microstructurally disordered as compared to the as-prepared film. It is observed that laser-irradiation of the films leads to decrease in optical band gap (photo-darkening) while increase in refractive index. The decrease in the optical band gap is explained on the basis of change in nature of films due to chemical disorderness and the increase in refractive index may be due to the densification of films with improved grain structure because of microstructural disorderness in the films. The optical changes are supported by X-ray photoelectron spectroscopy data. (C) 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Mono layer to Interdigitated Partial Bilayer Smectic C Transition in Thiophene-Based Spacer Mesogens: X-ray Diffraction and C-13 Nuclear Magnetic Resonance Studies

Mesophase organization of molecules built with thiophene at the center and linked via flexible spacers to rigid side arm core units and terminal alkoxy chains has been investigated. Thirty homologues realized by varying the span of the spacers as well as the length of the terminal chains have been studied. In addition to the enantiotropic nematic phase observed for all the mesogens, the increase of the spacer as well as the terminal chain lengths resulted in the smectic C phase. The molecular organization in the smectic phase as investigated by temperature dependent X-ray diffraction measurements revealed an interesting behavior that depended on the length of the spacer vis-a-vis the length of the terminal chain. Thus, a tilted interdigitated partial bilayer organization was observed for molecules with a shorter spacer length, while a tilted monolayer arrangement was observed for those with a longer spacer length. High-resolution solid state C-13 NMR studies carried out for representative mesogens indicated a U-shape for all the molecules, indicating that intermolecular interactions and molecular dynamics rather than molecular shape are responsible for the observed behavior. Models for the mesophase organization have been considered and the results understood in terms of segregation of incompatible parts of the mesogens combined with steric frustration leading to the observed lamellar order.

Characterization of alinite cements through X-ray diffraction and mas 29Si NMR studies

Alinite cements have been synthesized using mining and steel plant wastes and pulverized fuel ash (fly ash) as raw materials and a clinkering temperature of 1150°C. The cements possess hydration characteristics comparable to those of portland cements. X-ray diffraction studies on these samples confirm the presence of alinite as the predominant phase. MAS 29Si NMR spectra have been used to distinguish alinite and alite cements. While both show resonances characteristic of Q° type silicate species, the portland cements exhibit three distinct peaks corresponding to three inequivalent SiO4 units present, while alinite shows a single sharp peak corresponding to the unique Si position.

Hydration numbers of some metal acetates, monochloroacetates and trichloroacetates in solution from ultrasonic velocity and conpressibility measurements

Ultrasonic velocities in aqueous solutions of some metal acetates, monochloroacelates and trichloroacetates, and the respective acids have been measured at 1 MHz frequency using the pulse technique. The ultrsonic velocity, adiabatic compressibility and apperent molal compressibility were measured as a function of concentration. The apparent molal compressibility values at infinite dilution were calculated and used to determine the hydration numbers.

Cross-Layer Scheduling with Infrequent Channel and Queue Measurements

The downlink scheduling problem in multi-queue multi-server systems under channel uncertainty is considered. Two policies that make allocations based on predicted channel states are proposed. The first is an extension of the well-known dynamic backpressure policy to the uncertain channel case. The second is a variant that improves delay performance under light loads. The stability region of the system is characterised and the first policy is argued to be throughput optimal. A recently proposed policy of Kar et al [1] has lesser complexity, but is shown to be throughput suboptimal. Further, simulations demonstrate better delay and backlog properties for both our policies at light loads.

Mixed saturated-unsaturated alkyl-chain assemblies: Solid solutions of zinc stearate and zinc oleate

The linear saturated stearic acid and the bent mono-unsaturated oleic acid do not mix and form solid solutions. However, the zinc salts of these acids can. From X-ray diffraction and DSC measurements we show that the layered zinc stearate and zinc oleate salts form a homogeneous solid solution at all composition ratios. The solid solutions exhibit a single melting endotherm, with the melting temperature varying linearly with composition but with the enthalpy change showing a minimum. By monitoring features in the infrared spectra that are characteristic of the global conformation of the hydrocarbon chain, and hence can distinguish between stearate and oleate chains, it is shown that solid solution formation is realized by the introduction of gauche defects in a fraction of the stearate chains that are then no longer linear. This fraction increases with oleate concentration. It has also been possible from the spectroscopic measurements to establish a quantitative relation between molecular conformational order and the thermodynamic enthalpy of melting of the solid solutions.

Photoluminescence spectroscopy and lifetime measurements from self-assembled semiconductor-metal nanoparticle hybrid arrays

We present results of photoluminescence spectroscopy and lifetime measurements on thin film hybrid arrays of semiconductor quantum dots and metal nanoparticles embedded in a block copolymer template. The intensity of emission as well as the measured lifetime would be controlled by varying the volume fraction and location of gold nanoparticles in the matrix. We demonstrate the ability to both enhance and quench the luminescence in the hybrids as compared to the quantum dot array films while simultaneously engineering large reduction in luminescence lifetime with incorporation of gold nanoparticles. (C) 2010 American Institute of Physics. [doi:10.1063/1.3483162].

Ionic conductivity and dielectric measurements in single crystal β---AgI

Ionic conductivity measurements have been made on pure, copper-doped and cadmium-doped single crystals. Dielectric measurements in the frequency range 30Hz–100Hz showed that there was no anomalously to be (0.64 ± 0.02) eV and migration energies for silver ion intersitials and vacancies in the c direction to be (0.41 ± 0.02) eV and (0.50 ± 0.02) eV respectively. ESR measurements have shown that copper exists as Cu+ in these crystals. Dielectric measurements in the frequency range (OHz–100KHz showed that there was no anomalously high value for ε as reported earlier.

A furnace for in situ synchrotron Laue diffraction and its application to studies of solid-state phase transformations

The design of a new microfurnace for use for Laue diffraction studies of solid-state transformations is described. The furnace operates in the temperature range 298-573 K with a thermal stability of about ± 0.1 K. The potential of the synchrotron-radiation Laue diffraction technique for studies of structural phase transitions is demonstrated. Experimental data on phase transitions in caesium periodate, potassium tetrachlorozincate and pentaerythritol are presented.

Application of composition gradient solid electrolytes in sensors and thermodynamic measurements

New compos~tiong radient solid electrolytes are developed which have application in high temperature solid state galvanic sensors and provide a new tool for thermodynamic measurements. The electrolyte consists oi a solid solution between two ionic conductors with a common mobile ion and spatial variation in composition of otber coxup nents. Incorporation of the composite electrolyte in sensors permits the use oi dissimilar gas electrodes. It is demonsuated, both experimentall y and theoretically, that the composition gradient of the relativeiy immobile species does not give rise to a diffusion potential.The emi of a cell is determined by the activity of the mobile species at the two eiectrodes. The thermodynamic properties of solid solutions can be measured using the gradient solid electrolyte. The experimental stuay is based on model systems A?(COj)x(S04)l-x (A=Na,K),where S \.aria across the electrolyte. The functionally gradient solid electrolytes used for activity measurements consist of pure carbonate at one ena and the solid solution under stuav at the other. The identical vaiues of activity, obtained h m t hree different modes of operation of the ceil. indicate unit transport number for the ddi metal ion in the graciient electrolyte. Tlle activities in the solid solutions exhibit moderate positive deviations from Raoult 's law.