Interfacial coupling and its size dependence in PbTiO3 and PbMg1/3Nb2/3O3 multilayers

Multilayers of Pb(Mg1/3Nb2/3)O-3 (PMN)-PbTiO3 (PT) were deposited through pulsed laser ablation deposition with different periodicities (d=10, 20, 30, 40, 50, 60, and 70 nm) for a constant total thickness of the film. The presence of superlattice reflections in the x-ray diffraction pattern clearly showed the superlattice behavior of the fabricated structures over a periodicity range of 20-50 nm. Polarization hysteresis and the capacitance-voltage characteristics of these films show clear size dependent ferroelectric and antiferroelectric (AFE) characteristics. Presence of long-range coupling and strain in multilayers with lower periodicity (similar to 10 nm) exhibited a clear ferroelectric behavior similar to a solid solution of PMN and PT. Multilayers with higher periodicities (20-50 nm) exhibited antiferroelectric behavior, which could be understood from the energy arguments. On further increase of periodicity, they again exhibit ferroelectric behavior. The polarization studies were carried out beyond the Curie temperature T-c of PMN to understand the interlayer interaction. The interaction is changed to a ferroelectric-paraelectric interlayer and tends to lose its antiferroelectric behavior. The behavior of remnant polarization P-r and dP(r)/dT with temperature clearly proves that the AFE coupling of these superlattices is due to the extrinsic interfacial coupling and not an intrinsic interaction as in a homogeneous conventional AFE material. The evidence of an averaged behavior at a periodicity of similar to 10 nm, and the behavior of individual materials at larger periodicities were further confirmed through dielectric phase transition studies. The presence of AFE interfacial coupling was insignificant over the dielectric phase transition of the multilayers.

Triangular Ising antiferromagnet in a staggered field

We study the equilibrium properties of the nearest-neighbor Ising antiferromagnet on a triangular lattice in the presence of a staggered field conjugate to one of the degenerate ground states. Using a mapping of the ground states of the model without the staggered field to dimer coverings on the dual lattice, we classify the ground states into sectors specified by the number of "strings." We show that the effect of the staggered field is to generate long-range interactions between strings. In the limiting case of the antiferromagnetic coupling constant J becoming infinitely large, we prove the existence of a phase transition in this system and obtain a finite lower bound for the transition temperature. For finite J, we study the equilibrium properties of the system using Monte Carlo simulations with three different dynamics. We find that in all the three cases, equilibration times for low-field values increase rapidly with system size at low temperatures. Due to this difficulty in equilibrating sufficiently large systems at low temperatures, our finite-size scaling analysis of the numerical results does not permit a definite conclusion about the existence of st phase transition for finite values of J. A surprising feature in the system is the fact that unlike usual glassy systems; a zero-temperature quench almost always leads to the ground state, while a slow cooling does not.

Dynamics and local structure of colossal magnetoresistance manganites

We report Extended X-ray Absorption Fine Structure and anelastic spectroscopy measurements on on hole doped manganese oxides La1-xCaxMnO3 which present the colossal magnetoresistance effect. EXAFS measurements were realized both in the absence and presence of an applied magnetic field of 1.1 Tesla, in a wide temperature range (between 330 and 77 K) and at various dopings (x = 0.25 and x = 0.33). The magnetic field orders the magnetic moments so favouring the electron mobility and the reduction of Mn-O octahedra distortions. We observe the presence of four short and two long Mn-O distances (1.93 and 2.05 Angstrom respectively) above and also below the metal-insulator phase transition. The overall distortion decreases but does not completely disappear in the metallic phase suggesting the possible coexistence of metallic and insulating regions at low temperatures. The magnetic field reduces the lattice distortions showing evidence of a microscopic counterpart of the macroscopic colossal magnetoresistance. We also present preliminary anelastic relaxation spectra in a wide temperature range from 900 K to 1 K on a sample with x = 0.40, in order to study the structural phase transitions and the lattice dynamics. A double peak has been observed at the metal-insulator transition in the imaginary part of Young's modulus. This double peak indicates that the metal-insulator transition could be a more complex phenomenon than a simple second order phase transition. In particular the peak at lower temperatures can be connected with the possible presence of inhomogeneous phase structures. Another intense dissipation peak has been observed corresponding to the structural orthorhombic-trigonal transition around 750 K.

Characterization of barium titanate fine powders formed from hydrothermal crystallization

A detailed evaluation of size, shape and microstrains of BaTiO3 crystallites produced by hydrothermal crystallization at 90 – 180 °C and 0.1 – 1.2 MPa, from amorphous TiO2· xH2O (3 < × < 8) gel and aqueous Ba(OH)2 is presented, using X-ray line-broadening and TEM studies. Whereas the concentration of Ba(OH)2 and the acceptor impurities affect the crystallite shape, the stoichimetry with respect to Ba/Ti, donor as well as acceptor impurities, and the temperature of crystallization influence the microstrains. It is shown that strains in the crystallites are related to the point defects in the lattice. Compensation of the residually present hydroxyl ions in the oxygen sublattice by cation vacancies results in strains leading to metastable presence of the cubic phase at room temperature. Studies on the diffuse phase transition behaviour of these submicron powders show that the stable tetragonal phase is produced only on annealing at high temperatures where the mobility of cations vacancies are larger. Heat-treatment reduces anisotropy and strain in undoped samples, whereas annealing is less effective in doped materials. Comparison of the crystillite size by TEM showed better agreement with the Warren—Averbach method.

High-pressure NMR investigations of the protonic conductor (NH4)4Fe(CN)6.1.5H2O

The effect of high hydrostatic pressure up to 1.5 GPa on ionic motion in (NH4)4Fe(CN)6.1.5H2O has been studied by wide-line 1H NMR experiments performed in the temperature range from room temperature to 77 K. The experiments at room temperature have shown a large increase in the second moment at 0.45 GPa as a result of a pressure-induced phase transition. The temperature dependence study up to 0.425 GPa has shown a gradual increase in the values of activation energy and attempt frequency with increase in pressure. The activation volume for motion at 300 K has been estimated to be 6% of molar volume. Vacancy-assisted ionic jumps are concluded to be the mode of charge transport. Second moments estimated at 77 K show evidence for tunnelling reorientation of at least one of the two NH4+ groups in the compound.

Crystal chemistry of a new solid solution in the BaO-Bi2O3-Nb2O5 system: Ba-5x/2-Bi(1-x)5/3Nb5O15

A solid solution of the type Ba5x/2Bi(1-x)5/3Nb5O15 has been identified in the BaO-Bi2O3-Nb2O5 system for the first time. The limits of the solid solution are within the range 0.52 <= x <= 0.80. The compositions x = 0.52, 0.60, 0.72, 0.77, 0.78, and 0.80 were synthesized by the solid-state technique from the starting materials in stoichiometric quantities. The powder X-ray patterns of all the phases in the domain indicate a structural similarity to tetragonal tungsten bronzes (TTBs). The compositions below x = 0.52 and those above x = 0.80 exhibit barium niobate and bismuth niobate impurities, respectively. Single crystals of the composition x = 0.77 were obtained by the melt cooling technique. The crystal structure of Ba3.85/2Bi1.15/3Nb5O15 (x = 0.77) was solved in the tetragonal space group P4bm (No. 100) with a = 12.4938 (14) angstrom, c = 3.9519 (2) A, V = 616.87 (10) angstrom(3), and Z = 2 and was refined to an R index of 0.034. Dielectric measurements on all the phases indicate a typical relaxor behavior with a broad phase transition at T-m approximate to 300 K.

Carbon nanotube reinforced supramolecular gels with electrically conducting, viscoelastic and near-infrared sensitive properties

Pristine and long-chain functionalized single-walled carbon nanotubes (SWNTs) were incorporated successfully in supramolecular organogels formed by an all-trans tri(p-phenylenevinylene) bis-aldoxime to give rise to new nanocomposites with interesting mechanical, thermal and electrical properties. Variable-temperature UV-vis and fluorescence spectra reveal both pristine and functionalized SWNTs promote aggregation of the gelator molecules and result in quenching of the UV-vis and fluorescence intensity. Electron microscopy and confocal microscopy show the existence of a densely packed and directionally aligned fibrous network in the resulting nanocomposites. Differential scanning calorimetry (DSC) of the composites shows that incorporation of SWNTs increases the gel formation temperature. The DSC of the xerogels of 1-SWNT composites indicates formation of different thermotropic mesophases which is also evident from polarized optical microscopy. The reinforced aggregation of the gelators on SWNT doping was reflected in the mechanical properties of the composites. Rheology of the composites demonstrates the formation of a rigid and viscoelastic solid-like assembly on SWNT incorporation. The composites from gel-SWNTs were found to be semiconducting in nature and showed enhanced electrical conductivity compared to that of the native organogel. Upon irradiation with a near IR laser at 1064 nm for 5 min it was possible to selectively induce a gel-to-sol phase transition of the nanocomposites, while irradiation for even 30 min of the native organogel under identical conditions did not cause any gel-to-sol conversion.

Freezing of a colloidal liquid subject to shear flow

A nonequilibrium generalization of the density-functional theory of freezing is proposed to investigate the shear-induced first-order phase transition in colloidal suspensions. It is assumed that the main effect of a steady shear is to break the symmetry of the structure factor of the liquid and that for small shear rate, the phenomenon of a shear-induced order-disorder transition may be viewed as an equilibrium phase transition. The theory predicts that the effective density at which freezing takes place increases with shear rate. The solid (which is assumed to be a bcc lattice) formed upon freezing is distorted and specifically there is less order in one plane compared with the order in the other two perpendicular planes. It is shown that there exists a critical shear rate above which the colloidal liquid does not undergo a transition to an ordered (or partially ordered) state no matter how large the density is. Conversely, above the critical shear rate an initially formed bcc solid always melts into an amorphous or liquidlike state. Several of these predictions are in qualitative agreement with the light-scattering experiments of Ackerson and Clark. The limitations as well as possible extensions of the theory are also discussed.

Combustion of ammonium perchlorate-based composite propellants in presence of methylammonium perchlorates

The effect of tri- and tetramethylammonium perchlorates (MAP-3 and MAP-4) on the burning rate of ammonium perchlorate (AP) based propellants has been determined at various pressures. Both additives increase the burning rate; however, MAP-3 has a moderate effect, whereas MAP-4 has a rather large effect. To explain the results, the thermal decomposition and calorimetric values of the propellants having these additives have been examined. Compound MAP-3 affects the thermal decomposition rate considerably, whereas MAP-4 has virtually no effect on the decomposition rate. The contrasting effects of MAP-4 on decomposition and burning rate suggest that the enhancement of burning rate may be due to the catalysis of gas-phase reactions. Further, detailed differences between behaviour of MAP-3, and MAP-4 appear to be attributable to the melting and low-temperature exotherm of MAP-3 and nonmelting and high-temperature exotherm of MAP-4.

Transfer of F- in the reaction of SF6- with SOF4: Implications for SOF4 production in corona discharges

The temperature (T) and electric field-to-gas pressure (E/P) dependences of the rate coefficientk for the reaction SF 6 � +SOF4rarrSOF 5 � +SF5 have been measured. ForT<270>k approaches a constant of 2.1×10�9 cm3/s, and for 433>T>270 K,k decreases withT according tok (cm3/s)=0.124 exp [�3.3 lnT(K)]. ForE/Pk has a constant value of about 2.5×10�10 cm3/s, and for 130 V/cm·torr>E/P>60 V/cm·torr, the rate is approximately given byk (cm3/s)sim7.0×10�10 exp (�0.022E/P). The measured rate coefficient is used to estimate the influence of this reaction on SOF4 production from negative, point-plane, glow-type corona discharges in gas mixtures containing SF6 and at least trace amounts of O2 and H2O. A chemical kinetics model of the ion-drift region in the discharge gap is used to fit experimental data on SOF4 yields assuming that the SF 6 � +SOF4 reaction is the predominant SOF4 loss mechanism. It is found that the contribution of this reaction to SOF4 destruction falls considerably below the estimated maximum effect assuming that SF 6 � is the predominant charge carrier which reacts only with SOF4. The results of this analysis suggest that SF 6 � is efficiently deactivated by other reactions, and the influence of SF 6 � +SOF4 on SOF4 production is not necessarily more significant than that of other slower secondary processes such as gas-phase hydrolysis

Effect of particle size on the dielectric behaviour of double propionates

Introduction Dicalcium strontium propionate (DCSP) undergoes a ferroelectric phase transition at about 28 1.5 K, with the spontaneous polarization occurring along the tetragonal C-axis.1 Takashige et al.2,3 have recently reported ferroelectricity in annealed samples of dicalcium lead propionate (DCLP) in the range 191 K to 331 K. The removal of the inner biasing field by annealing has been known in the case of DCLP3 and DCSP.4 Because of the possible dependence of the inner biasing field on the particle size, a study of the temperature dependence of the dielectric behaviour of the powdered samples of these compounds was undertaken.

Effect of sintering on optical, structural and photoluminescence properties of ZnO thin films prepared by sol-gel process

Zinc oxide (ZnO) thin films have been deposited on glass substrates via sol-gel technique using zinc acetate dihydrate as precursor by spin coating of the sol at 2000 rpm. Effects of annealing temperature on optical, structural and photo luminescence properties of the deposited ZnO films have been investigated. The phase transition from amorphous to polycrystalline hexagonal wurtzite structure was observed at an annealing temperature of 400 degrees C. An average transmittance of 87% in the visible region has been obtained at room temperature. The optical transmittance has slightly increased with increase of annealing temperature. The band gap energy was estimated by Tauc's method and found to be 3.22 eV at room temperature. The optical band gap energy has decreased with increasing annealing temperature. The photoluminescence (PL) intensity increased with annealing temperature up to 200 degrees C and decreased at 300 degrees C. (c) 2010 Elsevier B.V. All rights reserved.

Dielectric properties of electron irradiated PbZrO3 thin films

The present paper deals with the study of the effects of electron (8 MeV) irradiation on the dielectric and ferroelectric properties of PbZrO3 thin films grown by sol-gel technique. The films were (0.62 mu m thick) subjected to electron irradiation using Microtron accelerator (delivered dose 80, 100, 120 kGy). The films were well crystallized prior to and after electron irradiation. However, local amorphization was observed after irradiation. There is an appreciable change in the dielectric constant after irradiation with different delivered doses. The dielectric loss showed significant frequency dispersion for both unirradiated and electron irradiated films. T (c) was found to shift towards higher temperature with increasing delivered dose. The effect of radiation induced increase of E >'(T) is related to an internal bias field, which is caused by radiation induced charges trapped at grain boundaries. The double butterfly loop is retained even after electron irradiation to the different delivered doses. The broader hysteresis loop seems to be related to radiation induced charges causing an enhanced space charge polarization. Radiation-induced oxygen vacancies do not change the general shape of the AFE hysteresis loop but they increase P (s) of the hysteresis at the electric field forced AFE to FE phase transition. We attribute the changes in the dielectric properties to the structural defects such as oxygen vacancies and radiation induced charges. The shift in T (C), increase in dielectric constant, broader hysteresis loop, and increase in P (r) can be related to radiation induced charges causing space charge polarization. Double butterfly and hysteresis loops were retained indicative of AFE nature of the films.

1-Anilino-8-naphthalene sulfonate (ANS) binding to proteins revisited: Investigation of dye binding to molten globule states by electrospray ionization mass spectrometry

The binding of 1-anilino-8-naphthalene-sulfonic acid to globular proteins at acidic pH has been investigated by electrospray ionization mass spectrometry (ESIMS). Mass spectra of apomyoglobin recorded in the pH range 2−7 establish that maximal ANS binding is observed at pH 4.0. As many as seven distinct species may be observed in the gas phase which correspond to protein molecules containing one to six molecules of bound ANS. At neutral pH only a single molecule of ANS is bound. In the case of cytochrome c, maximal binding is observed at pH 4.0, with five molecules being bound. Binding is suppressed at neutral pH. In both cases ESIMS demonstrates maximal ANS binding at pH values where the proteins have been reported to exist in molten globule states. ANS binding is not observed for lysozyme, which has a tightly folded structure over the entire pH range. Reduction of disulfide bonds in lysozyme leads to the detection of ANS-bound species at neutral pH. Binding is suppressed at low pH due to complete unfolding of the reduced protein. The results suggest that ESIMS may provide a convenient method of probing the stoichiometry and distribution of dye complexes with molten protein globules

Modulus Spectroscopy and Dielectric Dispersion Studies in Alkali Metal Perchlorates

Alkali metal perchlorates (KClO4, RbClO4, and CsClO4) undergo a structural phase transition from the orthorhombic to the cubic phase at elevated temperatures. A detailed dielectric study of these crystals across the phase transition is carried out at different frequencies. The crystals are found to exhibit pronounced dielectric dispersion in the kHz frequency range. The results support the view that these transitions are of order–disorder type. The dielectric behaviour at temperatures above Tc is discussed in terms of modulus spectroscopy. An estimate of conductivity relaxation times above the phase transition temperatures made from modulus spectroscopy data gives values of 3.1, 12.2 and 17.7 μs for KClO4, RbClO4, and CsClO4, respectively.