Experimental characterization of hexatic smectic phases through electro-optic studies and dielectric relaxation spectroscopy

The electro-optic and complex dielectric behaviour of an antiferroelectric liquid crystal 4-(1-methylheptyloxycarbonyl)phenyl 4'-(n-butanoyloxyprop-1-oxy)biphenyl-4-carboxylate, having chiral SmC_A* and hexatic smectic phases, have been investigated. Complex dielectric permittivities were measured as a function of frequency, d.c. bias field and temperature. Spontaneous polarization was measured by the current reversal technique; tilt angle was measured under a polarizing microscope using a low frequency electric field. The electro-optic properties and dielectric behaviour of the material are compared with results obtained by DSC and polarizing optical microscopy. Dielectric relaxation processes in SmC_A* and hexatic smectic phases were determined. The dielectric strength at the SmC_A* to hexatic smectic phase transition is discussed in terms of coupling between the long range bond orientational order and smectic C director. It seems from the results of spontaneous polarization and dielectric relaxation spectroscopy that the material might possess an additional phase between the SmC_A* and hexatic smectic I* phases.     

Dielectric spectroscopy of a smectic liquid crystal

Complex dielectric spectroscopy (frequency range 5 Hz-13 MHz) has been used to analyse the frequency, temperature and bias-field dependences of the molecular dynamics of a very high-spontaneous-polarization ferroelectric liquid crystalline material exhibiting SmA, SmC* and unknown SmX smectic phases. Different smectic phase transition temperatures have been observed from the study of the temperature dependence of the dielectric strength and the relaxation frequency. The phase transition temperatures (crystalline to isotropic phases) have also been described very accurately from the temperature-dependent symmetric and asymmetric shape parameters of the relaxation function and also the dc conductivity. In a planar aligned cell, two symmetric modes (Goldstone mode and domain mode) have been observed in both the SmX and SmC* phases. One asymmetric mode (X-mode) observed in the SmC* and SmA phases could be related to the interaction of dipoles of the ferroelectric liquid crystals being affected by the surface of the cell. The soft mode, which usually appears very close to the SmC*-SmA phase transition was not observed until the bias field was applied. The second order nature of the SmC*-SmA phase transition was revealed.     

Free energies of transfer of alkali halides from water to urea-water mixtures at 25°C from EMF measurements

The standard potentials_s E ^o of M/M⁺ (M=Li, Na, K, Rb, and Cs) electrodes in aqueous urea solutions containing 12, 20, 30 and 37% by weight of urea have been determined at 25°C from emf measurements on the cell M(Hg)/MCl (m), solvent/AgCl–Ag, from the activities of metals in amalgams by use of a similar type of cell in water, and from the values of_s E ^o of the Ag/AgCl electrode determined earlier. The standard free energies of transfer of MCl, G _t ^o (MCl), from water to the mixed solvents, computed by use of these values and those for the Ag–AgCl electrode, rise sharply from Li⁺ to Na⁺ but fall from Na⁺ to K⁺ and rather sharply from K⁺ to Cs⁺ with a maximum at Na⁺ in all the solvent compositions. This has been attributed to the superimposition of soft-soft interactions on the electrostatic interactions between the ions and the negative charge centers of the possible hydrogen-bonded solvent complexes in the mixed solvents. Comparison of G _t ^o (i) values for individual ions, obtained by a simultaneous extrapolation procedure, with those in aqueous mixtures of methanol,t-butanol, and dimethyl sulfoxide leads to the conclusion that the solvation of these ions in all these solvents is chiefly dictated by the acid-base type of ion-solvent interactions.     

Electrochemical and chemical polymerization of acrylamide

The electrochemical and chemical polymerization of acrylamide (AA) has been studied. The electrolysis of the monomer in N,N-dimethylformamide (DMF) containing (C₄H₉)₄NClO₄ as the supporting electrolyte leads to polymer formation in both anode and cathode compartments. The cathodic polymer dissolves in the reaction mixture and the anodic polymer precipitates during the course of polymerization. A plausible mechanism for the anodic and cathodic initiation reaction has been given. The chemical polymerization of acrylamide that has been initiated by HClO₄ is analogous to its anodic polymerization. The polymer yield increases with an increase in concentration of the monomer and HClO₄. Raising the reaction temperature also enhances the polymerization rate. The overall apparent activation energy of the polymerization was determined to be ca. 19 kcal/mole. The copolymerization of acrylamide was carried out with methyl methacrylate (MMA) in a solution of HClO₄ in DMF. The reactivity ratios are r₁ (AA) = 0.25 and r₂ = 2.50. The polymerization with HClO₄ appears to be by a free radical mechanism. When the polymerization of acrylamide is carried out with HClO₄ in H₂O, a crosslinked water-insoluble gel formation takes place.     

Dynamical parameters for dilute Mössbauer impurities

A simple theoretical analysis is presented for Mössbauer parameters and frequency moments of dilute⁵⁷Fe impurities in different metallic hosts. These parameters have been evaluated for a general harmonic solid using Green's function method. Our results suggest that the contribution due to force constant change term is significant for the mean square displacement whereas that due to mass disordering term is predominating in the evaluations of mean square velocity. The variation of frequency moments for the impurity with host Debye-temperatures modified by the host to impurity mass ratios are shown for a number of solids.     

ESR studies on calcite encrustation on Fili neotectonic fault, Greece

Electron spin resonance (ESR) study was done on calcite encrustation on Fili neotectonic fault surface, Greece. Normally such calcite encrustations on fault surfaces are not observed. Significantly, the ESR study has detected the presence of nitrate NO₃²⁻ radical in this calcite encrustation, havingg _⊥=2.0063±0.0001 and hyperfine coupling constantA _⊥=3.44 mT, the second such detection of nitrate NO₃²⁻ radical following a sample from Scott Glacier, Antarctica. From isochronal thermal annealing measurement the NO₃²⁻ radical was found to be quite stable, only fully annealed at 475°C. This study also shows that the ESR, as a tool, can be suitably applied to date the age of formation of the calcite encrustation with SO₃⁻ as an ESR dating signal by additive γ-ray irradiation. A preliminary estimation indicates the age of formation of calcite precipitation at Fili fault, Greece to be about 5600 years.     

Influence of Tb doping on the luminescence characteristics of ZnO nanoparticles

Structural and optical properties of the Tb-doped ZnO nanoparticles with average diameter ≈4 nm have been systematically investigated. Our X-ray diffraction studies show a contraction of the ZnO lattice with the increase of the Tb mole-fraction x for x ≤ 0.02 and an expansion beyond x ≈ 0.02. The photoluminescence spectra are found to be comprised of a near band edge ultra violet luminescence (UVL) and a broad green luminescence (GL) band. Under the atmospheric condition, the intensity of the GL band is found to increase with the Tb mole-fraction over the entire doping range. On the other hand, under the vacuum condition, it has been observed that the GL intensity decreases with the increase of x up to x ≈ 0.02 but further increase of x leads to a gradual revival of the GL emission. Our study suggests that for x ≤ 0.02, GL results due to the physisorption of certain groups on the surface of the nanoparticles (GL-groups). It is also found that in this Tb mole-fraction regime, Tb incorporates mostly on the surface of the nanoparticles and affects the UVL to GL intensity ratio by influencing the attachment of the GL-groups. However, for x > 0.02, GL originates not only from the GL-groups but also from certain point defects, which are likely to be generated due to the incorporation of Tb in the core of the nanoparticles. A simple rate equation model is introduced to get a quantitative understanding about the variation of the density of the centers responsible for the GL emission as a function of x under the atmospheric and the vacuum conditions.     

Acoustic source localization

In this article different techniques for localizing acoustic sources are described and the advantages/disadvantages of these techniques are discussed. Some source localization techniques are restricted to isotropic structures while other methods can be applied to anisotropic structures as well. Some techniques require precise knowledge of the direction dependent velocity profiles in the anisotropic body while other techniques do not require that knowledge. Some methods require accurate values of the time of arrival of the acoustic waves at the receivers while other techniques can function without that information. Published papers introducing various techniques emphasize the advantages of the introduced techniques while ignoring and often not mentioning the limitations and weaknesses of the new techniques. What is lacking in the literature is a comprehensive review and comparison of the available techniques; this article attempts to do that. After reviewing various techniques the paper concludes which source localization technique should be most effective for what type of structure and what the current research needs are.