Metastable phases in HxLi1-xTaO3 waveguide layers and pure LiTaO3

The formation of high-temperature phases in low-doped H:LiTaO₃ waveguide layers in Z-cut LiTaO₃ has been observed both by refractive-index and IR-spectra measurements. This permits us to correlate the index jumps to the changes of the OH bonds in the crystal lattice. Reversible phase transitions were detected in the temperature interval T=50–200 °C over a wide range of hydrogen content including as-grown LiTaO₃. The high-temperature phases are metastable close to room temperature. This was demonstrated by tracing the time evolution of the refractive-index change. It was shown that the high-temperature phases are responsible for the long-term refractive-index instabilities in both H:LiTaO₃ waveguides and virgin LiTaO₃. Received: 7 May 2001 / Revised version: 10 August 2001 / Published online: 30 October 2001     

Second-order optical non-linearity of proton exchanged lithium tantalate waveguides

A detailed correlation between the fabrication conditions, crystallographic phase state of H_xLi_1-xTaO₃ waveguides and second-order optical non-linearity has been investigated by using reflected SHG measurements from the polished waveguide end face. The non-linearity, strongly reduced after the initial proton exchange, is found to be restored and even increased after annealing. However, this apparent increase in the non-linearity is accompanied by a strong degradation of the quality of the SHG reflected beam in the region of the initial as-exchanged waveguide due to beam scattering. The high temperature proton exchange technique has been shown to produce high-quality α-phase waveguides with essentially undegraded non-linear optical properties. There is no phase transition when the α-phase waveguides are fabricated by direct exchange. This phase presents the same crystalline structure as that of LiTaO₃ and maintains the excellent non-linear properties of the bulk material. The results obtained are important for the design, fabrication and optimization of guided-wave non-linear optical devices in LiTaO₃. Received: 21 May 2001 / Published online: 23 October 2001     

Effect of stresses on the OH libration bands in proton-exchanged LiNbO3 optical waveguides

i -H_xLi_1-xNbO₃ phases generated on x-cut LiNbO₃ the new anisotropic libration mode at 890–940 cm^-1 is observed in addition to the known isotropic mode at 960–970 cm^-1, whereas the same phases on z-cut exhibit only latter isotropic libration mode. The observed phenomena are explained as a result of anisotropic stresses generated in the x-cut waveguides, whereas the stresses in the structures on z-cut are isotropic. The OH-bond librations are clearly anisotropic in the α, κ₁, and κ₂ phases generated on both z- and x-cuts, which indicates a fundamental difference of the local symmetry of the proton’s position in the β_i phases compared to the α, κ₁, and κ₂ H_xLi_1-xNbO₃ phases. Received: 4 May 1998/Revised version: 26 June 1998     

Pressure-induced amorphization of Gd2(MoO4)3: A high pressure Raman investigation

High pressure Raman spectroscopic studies on Gd₂(MoO₄)₃(GMO) have been carried out at ambient temperature in the diamond cell to 10 GPa hydrostatic pressure. These experiments have revealed pressure-induced phase transitions in GMO near 2 GPa and 6.0 GPa. The first transition is from Pba2(β′) phase to another undetermined crystalline phase, designated as phase II, and the second transition is to an amorphized state. On releasing pressure there is a partial reversion to the crystalline state. The Raman data indicate that the amorphization is due to disordering of the MoO₄ tetrahedral units. Further, it is inferred from the nature of the Raman bands in the amorphized material that the Mo-O bond lengths and bond angles have a range of values, instead of a few set values. The results of the present study as well as previous high pressure-high temperature quenching experiments strongly support that pressure-induced amorphization in GMO is a consequence of the kinetically impededβ toα phase transition. The system in frustration becomes disordered. The rare earth trimolybdates crystallizing in theβ′ structure are all expected to undergo similar pressure-induced amorphization.     

Phase control of iron silicides using femtosecond laser irradiation

Phase control of Fe–Si amorphous thin film in micro area is demonstrated using femtosecond laser irradiation. A femtosecond laser beam with a high repetition rate over 200 kHz and tightly focused through an objective lens promotes both crystallization and phase transformation from an amorphous phase into crystalline β-FeSi₂, α-FeSi₂, or ε-FeSi phases. Formation of each crystalline phase is possible by changing the pulse energy or the scanning speed of the incident laser beam.     

Effect of the ceramic grain size and concentration on?the?dynamical mechanical and dielectric behavior of?poly(vinilidene fluoride) Pb(Zr0.53Ti0.47)O3 composites

In this work, poly(vinilidene fluoride)/Pb(Zr_0.53Ti_0.47)O₃([PVDF]_1−x /[PZT] _x ) composites of volumetric fractions x and (0–3) type connectivity were prepared in the form of thin films. PZT powder of crystallite size of 0.84, 1.68, and 2.35 μm in different amounts of PZT (10, 20, 30, and 40%) was mixed with the polymeric matrix. The crystalline phase of the polymeric matrix was the nonpolar α-phase and the polar β-phase. Dielectric and dynamic mechanical (DMA) measurements were performed to these composites in order to evaluate the influence of particle size and the amount of PZT filler with respect to the PVDF matrix. The inclusion of ceramic particles in the PVDF polymer matrix increases the complex dielectric constant and dynamical mechanical response of the composites. A similar behavior is observed for the α- or β-phase of the polymeric matrix indicating that the PVDF polymer matrix is not particularly relevant for the composite behavior. On the other hand, ceramic size and especially content play the major role in the increase of the dielectric response and the room temperature storage modulus. In particular, the storage modulus increases with increasing PZT concentration, but this increase is more pronounced, in terms of maximum value, for the sample with 2.35 μm particle size; DMA reveals two main relaxations in the analyzed samples. A low-temperature process maximum at ca. −40°C, usually labeled by β or α _a associated to the T _g of the polymer and the α-relaxation at temperatures above 30°C. The β-relaxation is also observed in the dielectric measurements. The models used to asses the dielectric behavior of the samples with increasing PZT concentration indicate that the particle–matrix interaction plays a relevant role, as well as the particle asymmetry and relative orientation, being the Yamada model the most appropriate to describe the composite behavior. An erratum to this article can be found at     

First-principles study of high pressure phase transformations in Li<Subscript>3</Subscript>N

The lattice dynamics of lithium nitride (Li₃N) under high pressure are extensively investigated to probe its phase transformations by using the pseudopotential plane-wave method within the density functional theory. A new second order α↦α^′-Li₃N phase transition is identified for the first time. The newly proposed α^′-phase possesses a hexagonal symmetry with four ions in the unit cell having a space group of P-3m1. Further enthalpy and phonon calculations support the existence of this phase, which stabilizes in a narrow pressure range of 2.8 – 3.6 GPa at zero temperature. Upon further compression, transitions to denser packed phases of β-and γ-Li₃N are typical first order. The analysis of the electronic densities of states suggests that all the high pressure modifications of Li₃N are insulators and, interestingly, the typical behavior of compression is to broaden the band gap.     

The decay of the neutron–rich nucleus 216Bi

The decay of the neutron–rich isotope ²¹⁶Bi, produced by proton–induced spallation at the PS Booster–ISOLDE facility, was investigated by β-γγ, αγ coincidence and spectrum-multiscaling measurements. A new method for reducing isobaric contamination enabled to cover the unknown region “east” of ²⁰⁸Pb for the isobaric chain A=216. The half-life of the β decay of ²¹⁶Bi was found as T_1/2= 135 ± 5 s. Its decay scheme was extended and the possible shell model configurations are proposed. Received: 13 July 1999 / Revised version: 22 September 1999     

Dislocation structure of α<Subscript>2</Subscript>/β two-phase Ti-21.4Al-5.6Nb alloy

An electron microscopic analysis of the dislocation structure of two-phase α₂/β Ti-21.4 at % Al-5.6 at % Nb alloy deformed at ambient temperature was performed. It was established that after deformation, the microstructure of the α₂ phase consists of mobile a-superdislocations in the basal and prism planes and of 2c + a-superdislocations in the pyramidal planes. Some dislocations with the Burgers vector [0001] in the prism planes were also observed. Deformation transfer from the α₂ to the β phase occurs only due to a-super-dislocations with a Burgers vector corresponding to the Burgers orientation relations between these phases. The reasons for the increase in plasticity in two-phase Ti₃Al with Nb alloys are discussed.     

Thermodynamic parameters of diffuse phase transitions in Ag2Te

A differential thermal analysis in vacuum and studies of the coefficients of electrical conductivity and thermal conductivity, and of the thermal emf are made in Ag₂Te in the neighborhood of the structural phase transition. It is shown that these data can be used to calculate the switching factor L(T), determine the region in which the phases coexist within the transition, and calculate the thermodynamic parameters. Prior to and after the main phase transition, additional displacement transitions are observed. It is found that the phase transition takes place roughly according to the scheme α _{385 K}→α′_{405 K}→β′_{420 K}→β _{440 K}. The specific heat C _p, changes in entropy ΔS and transition enthalpy ΔH, as well as the minimum phase fluctuation volume V, and the heat Q of the phase transition are determined. It is shown that excesses of Te and Ag have almost no effect on the transition temperatures T ₀, but have a substantial effect on the thermodynamic parameters. Fiz. Tverd. Tela (St. Petersburg) 40, 1693–1697 (September 1998)     

Phonon Spectrum and Structural Transformations at High Pressures in Vanadyl IV Phthalocyanine Crystals

The Raman scattering spectra and crystalline structure of vanadyl IV phthalocyanine (VOPc) at normal and high pressures has been studied. According to the X-ray diffraction data, the initial microcrystalline powder represented a mixture of the triclinic α phase (79%) and the monoclinic β phase (21%) possessing P$$\bar {1}$$ and P21/c symmetry, respectively. Raman spectra of the two phases are similar, but the phonon modes of the β phase are shifted toward higher frequencies (energies). The pressure dependence of the spectra of the α phase has been determined and it is established that the interval of 2.3–3.4 GPa reveals reversible pressure-dependent variations: above 3 GPa, some phonon modes exhibit splitting and the coefficients of pressure-induced (baric) shift for almost all modes show a decrease. A high-pressure feature observed in the Raman spectra can be related to changes in intermolecular interactions in crystalline structure of the α phase. The pressure dependence of the α phase unit cell volume measured at pressures increasing up to 4 GPa is a smooth monotonic function that can be well described by the Murnaghan equation of state. The obtained data were used to calculate the Grüneisen parameters of VOPc phonon modes.     

Comparison of the electro-optic coefficient r33 in well-defined phases of proton exchanged LiNbO3 waveguides

The electro-optic coefficient, r₃₃, of proton exchanged LiNbO₃ waveguides has been measured in well-defined phases of the exchanged layer. Namely, in two low index-jump α-phases, i.e. unannealed soft-exchanged (SPE) and annealed (APE) guides, and in two high index-jump phases, i.e. β₁ guides and, for comparison, ordinary proton exchanged (PE) guides (having a mixture of phases). The following values have been obtained (in pm/V): 22.1±0.6 for SPE; 20.9±0.7 for APE; 0.33±0.01 for β₁; and 0.76±0.04 for PE. Differences between these values are discussed in terms of the structure of the phase involved. Received: 18 May 2001 / Revised version: 22 August 2001 / Published online: 30 October 2001     

Raman characteristics of carbon nitride synthesized by nitrogen-ion-beam-assisted pulsed laser deposition

Raman characteristics of carbon nitride films synthesized by nitrogen-ion-beam-assisted pulsed laser deposition were investigated. In addition to the D (disorder) band and G (graphitic) band commonly observed in carbon nitride films, two Raman bands located at 1080–1100 and 1465–1480 cm^-1 were found from our carbon nitride films. These two bands were well matched with the predicted Raman frequencies for βC₃N₄ and the observed Raman bands reported for carbon nitride films, indicating their relation to carbon-nitrogen stretching vibrations. Furthermore, the relative intensity ratio of the two Raman bands to the D and G bands increased linearly with increasing nitrogen content of the carbon nitride films. Received: 30 October 2000 / Accepted: 5 February 2001 / Published online: 2 October 2001     

Recent Result of Muon Catalyzed t–t Fusion at RIKEN-RAL

We have measured X-rays and neutrons associated with the muon catalyzed t–t fusion process at the RIKEN-RAL Muon facility. In the X-ray measurement, we observed K_α and K_β X-rays originating from the muon sticking process in muon catalyzed t–t fusion, and obtained the K_α X-ray yield and the K_β/K_α intensity ratio. An average recoil energy of the (μ⁻α) atoms in a solid T₂ medium was determined from the observed Doppler broadening width of the K_α X-ray line. The obtained t–t fusion neutron has shown an exponential time spectrum with a single component and a continuous energy spectrum with a maximum energy of 9 MeV. We have determined the t–t fusion neutron yield, the t–t fusion cycling rate and the muon sticking probability from the neutron data. The obtained maximum neutron energy is a very peculiar value from the view point of the reaction Q value (11.33 MeV) with the three-particle decay mode at the exit channel: t + t → α + n + n + Q. The obtained neutron energy distribution was analyzed by a simple model with two neutron energy components; reasonable agreement has been obtained, suggesting a strong (n–α) correlation in the exit channel of the t–t muon catalyzed fusion reaction. This revised version was published online in August 2006 with corrections to the Cover Date.     

The structure of 99Ru from (α,3n) reaction

The results of in-beam investigations of excited states of ⁹⁹Ru using the ⁹⁸Mo(α,3n) reaction are presented. Angular distributions of γ–rays and γ–γ coincidences have been measured. Excited states have been identified up to an energy of E = 5603 keV and spin of I^π= 31/2⁻. Mean lifetimes τ have been determined using the DSA method for eleven levels. Aligned angular momenta are discussed and the probable (νh _11/2) origin of a backbending at frequency about 0.5 MeV was confirmed. The possible role of (νd _5/2) alignment at frequencies above 0.5 MeV was pointed out. Received: 13 January 1999 / Revised version: 26 March 1999     

Anode materials for lithium ion batteries in the Li-Zn-P system

This paper presents an exhaustive study of the Li-Zn-P system through the synthesis and electrochemical characterisation of several binary and ternary phases: Li₉ZnP₄, LiZnP, Zn₃P₂ (α and β), ZnP₂ (α and β), LiZn, and LiZn₄. Three synthetic routes have been used to prepare these materials: ceramic synthesis and ball milling without and with annealing. Li-Zn-P system phases have been evaluated through X-ray diffraction and electrochemical reactivity towards lithium. Exhibiting high specific capacities at potentials close to 0.7 V vs. Li⁺/Li, some of these materials are promising as negative electrode materials for lithium ion battery. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

LiFAP-based PVdF–HFP microporous membranes by phase-inversion technique with Li/LiFePO<Subscript>4</Subscript> cell

Polyvinylidenefluoride–hexafluoropropylene-based (PVdF–HFP-based) gel and composite microporous membranes (GPMs and CPMs) were prepared by phase-inversion technique in the presence 10 wt% of AlO(OH) _n nanoparticles. The prepared membranes were gelled with 0.5-M LiPF₃(CF₂CF₃)₃ (lithium fluoroalkylphosphate, LiFAP) in EC:DEC (1:1 v/v) and subjected to various characterizations; the AC impedance study shows that CPMs exhibit higher conductivity than GPMs. Mechanical stability measurements on these systems reveal that CPMs exhibit Young’s modulus higher than that of bare and GPMs and addition of nanoparticles drastically improves the elongation break was also noted. Transition of the host from α to β phase after the loading of nanosized filler was confirmed by XRD and Raman studies. Physico-chemical properties, like liquid uptake, porosity, surface area, and activation energy, of the membranes were calculated and results are summarized. Cycling performance of Li/CPM/LiFePO₄ coin cell was fabricated and evaluated at C/10 rate and delivered a discharge capacity of 157 and 148 mAh g⁻¹ respectively for first and tenth cycles.     

On bound state computations in three- and four-electron atomic systems

A variational approach is developed for bound state calculations in three- and four-electron atomic systems. This approach can be applied to determine, in principle, an arbitrary bound state in three- and four-electron ions and atoms. Our variational wave functions are constructed from four- and five-body Gaussoids that respectively depend on six (r ₁₂, r ₁₃, r ₁₄, r ₂₃, r ₂₄, r ₃₄) and ten (r ₁₂, r ₁₃, r ₁₄, r ₁₅, r ₂₃, r ₂₄, r ₂₅, r ₃₄, r ₃₅ and r ₄₅) relative coordinates. The approach allows operating with the more than one electron spin functions. In particular, the trial wave functions for the ¹ S states in four-electron atomic systems include the two independent spin functions χ₁ = αβαβ + βαβα − βααβ − αββα and χ₂ = 2ααββ + 2ββαα − βααβ − αββα − βαβα − αβαβ. We also discuss the construction of variational wave functions for the excited 2³ S states in four- electron atomic systems.     

Time-resolved,stress-induced,and anisotropic phase transformation of a piezoelectric polymer

We investigate the time-dependent and anisotropic phase transformation of poly (vinylidene difluoride) (PVDF) under bending. Using combined techniques of an atomic force microscope and a Fourier transform infrared spectroscope, observation of surface morphology and phase transformation in time was made. Results showed that bending stress induces the transformation of amorphous, α,β, and γ crystalline phases. Specifically, the amorphous phase was transformed into the β phase when the bending force was applied. In addition, the transformation observed was time and direction dependent. The anisotropic behavior observed brings insights into the origin of the piezoelectricity of PVDF.     

Enhancement of ionic conductivity in the composite solid electrolyte system: TlI–Al2O3

This paper reports the heterogeneously doped alumina (Al₂O₃) on the ionic conductivity of thallium iodide. Composite materials of formula (1 − x) TlI–xAl₂O₃, x = 0–0.7 have been prepared and studied by X-ray diffraction, differential scanning calorimetry, and electrical conductivity. X-ray diffraction and differential scanning calorimetry proved the formation of composite in this binary system. The maximum enhancement observed is about three orders of magnitude with respect to the host material. The enhancement of electrical conductivity in comparison with pure thallium iodide can be interpreted with the space charge layer model. Moreover, the increased content of alumina in the system leads to the disappearance of phase transition β–α thallium iodide, which is usually observed in the pure compound. This behavior was explained by stabilizing effect of β-phase at high temperatures and suppression of α-phase at higher contents of alumina.