Raman spectroscopic study of phase transitions in undoped morphotropic PbZr1−xTixO3

Several PbZr_1−xTi_xO₃ (PZT) compositions in the proximity of the morphotropic phase boundary (MPB) were examined by means of Raman spectroscopy in the 15–800 K temperature range. Previous studies performed by other researchers using various techniques evidenced that, in the phase diagram of PZT, areas with rhombohedral/monoclinic and tetragonal/monoclinic phases coexist across the MPB. For these compositions, either long‐range or short‐range symmetry ordering of the monoclinic phase should be considered, so that no true rhombohedral–monoclinic–tetragonal phase boundary exists. In addition, the onset of antiferrodistortive phase transitions between high‐T and low‐T perovskite phases has been predicted by ab initio calculations and experimentally reported. In the present work, low‐T and high‐T Raman scattering spectra were collected on undoped PbZr_1−xTi_xO₃ with compositions x = 0.42, 0.45, 0.465, 0.48 and 0.53 in an attempt to clarify the current open issues on the phase diagram of PZT. Spectra clearly belonging to the respective phases were observed in the rhombohedral, monoclinic and tetragonal areas, thus confirming that monoclinic ordering is long‐range only for a narrow range of compositions. Raman measurements at cryogenic temperatures allowed detecting all predicted low‐T phases, including the tetragonal one. These results are in good agreement with both ab initio calculations and experimental results obtained by other authors on the same compositions. Copyright © 2010 John Wiley & Sons, Ltd.     

T-X Br phase diagram for the NH4Br x Cl1−x system

In this study using a mean field model we calculate the phase line equations for the β-δ, β-γ and γ-δ phase transitions in the NH₄Br_xCl_{1 x} system. We then fit our phase line equations to the experimentally observed T-X _Br phase diagram for this system. Our calculated phase diagram agrees well with the observed one for the NH₄Br_xCl_{1 x} system.     

Effect of the “negative chemical” pressure on the temperatures of phase transitions in the TlInS<Subscript>2</Subscript> layered crystal

The temperature dependences of the permittivity of TlInS_{2(1 −x)}Se_2x solid solutions have been experimentally investigated in the temperature range including the points of structural phase transitions in the solid solutions. It has been established that the isovalent substitution of selenium for sulfur in the anion sublattice of the TlInS_{2(1 − x)}Se_2x solid solutions shifts the phase transition temperatures T _i and T _c toward the low-temperature range with a simultaneous decrease in the temperature interval of the existence of the incommensurate phase. The T-x phase diagram is constructed for the solid solutions under study and the coordinates are determined for a critical point (of the Lifshitz type) at which the lines T _i (x) and T _c (x) converge in the phase diagram. The pattern of the T-x phase diagram for the TlInS_{2(1 − x)}Se_2x solid solutions has been analyzed within the phenomenological model of a virtual crystal.     

Investigation on FR(LT)–FR(HT) phase transition and pyroelectric properties of pulsed laser deposited Pb(Zr0.93Ti0.07)O3 thin films

The preparation process, crystallinity and electrical properties of pulse laser deposited Pb(Zr_xTi_1−x)O₃ (PZT) thin films were investigated in this paper. PZT (x = 0.93) thin film samples deposited at different substrate temperatures were prepared. Si (1 1 0) was the substrate; Ag and YBCO were the top electrode and the bottom electrode respectively. The bottom electrode YBCO was deposited on the Si substrate by pulsed laser deposition (PLD), and then PZT was epitaxially deposited on YBCO also by PLD. After annealing, the top electrode Ag was prepared on PZT by thermal evaporation, and then the Ag/PZT/YBCO/Si structured thin films were obtained. The XRD and the analysis of their electrical characters showed that, when the substrate temperature was elevated from 600 °C to 800 °C, the crystallinity and electrical properties of PZT thin films became better and better, and the F_R(LT)–F_R(HT) phase transition of PZT (x = 0.93) thin films occurred at 62 °C. The PZT film deposited at 800 °C had the best pyroelectric properties, and when the F_R(LT)–F_R(HT) phase transition of this film occurred, the peak value of pyroelectric coefficient (p) was obtained, with a value of 1.96 × 10⁻⁶ C/(cm² K). The PZT film deposited at 800 °C had the highest remnant polarization (P_r) and the lowest coercive field (E_c), with the values of 34.3 μC/cm² and 41.7 kV/cm respectively.     

Magnetization reversal in Co x (PZT)100 − x ferromagnet-ferroelectric nanogranulated composites

The process of magnetization reversal in Co _x (PZT)_{100 − x} composites is studied experimentally. At room temperature, the ferromagnetic state in as-prepared samples is found to arise only if the composite contains more than 60 at % of the metal phase. The concentration dependences of the coercive force and remanent magnetization derived from magnetic hysteresis loops are discussed in terms of the random anisotropy model.     

Electromagnetic properties of low-temperature co-fired xPZT+(1−x)NiCuZn-ferrite composites

To adjust the dielectric constant and the initial permeability of NiCuZn-ferrite materials for suppressing electromagnetic interference, Pb_0.95Sr_0.05(Zr_0.52Ti_0.48)O₃ (PZT) was introduced. The effects of PZT additive on the phase composition, densification, microstructures and electromagnetic properties of the ceramics with composition of xPZT+(1−x)NiCuZn-ferrite (where x=0-25 wt%) were investigated. The results show that these composites are mainly of spinel phase, exhibiting relatively high dielectric constant and initial permeability due to the mutual effects of magnetization of NiCuZn-ferrite phase and polarization of PZT phase. Meanwhile, relatively high-quality factor (Q) and excellent frequency stability were obtained for the samples with PZT additive. These materials are expected to be used as embedded inductors or embedded capacitors.     

First-principles study on the geometric and electronic structures and phase transition of PbZr1-xTixO3 solid solutions

With first-principles virtual-crystal approximation calculations, we systematically investigate the geometric and elec- tronic structures as well as the phase transition of lead zirconate titanate (PbZr1-xTixO3 or PZT) as a function of Ti content for the whole range of 0 ≤ x Ti ≤ 1. It can be found that, with the increase of the Ti content, the PbZr1-xTixO3 solid solu- tions undergo a rhombohedral-to-tetragonal phase transition, which is consistent with the experimental results. In addition, we also show the evolution in geometric and electronic structures of rhombohedral and tetragonal PbZr1-x TixO3 with the increasing content of Ti.     

Special points on the phase diagrams of langbeinites. The case of (x,T)-phase diagram of mixed K2xRb2(1−x)Cd2(SO4)3 crystals

We have studied special points that appear on the (x, T)-phase diagram of mixed K_2xRb_2(1?x)Cd₂(SO₄)₃ crystals. This phase diagram has been constructed issuing from the changes in domain structure occurring in the course of phase transitions. We have found that two triple points on the (x, T)-phase diagram of the above solid solutions are very close to each other in the phase space and can change their places or transform into a quadruple point. These special points are associated with disappearance of ferroelectric phases with the symmetries P1 and P2₁ taking place when Rb₂⁺ are substituted with K₂⁺ ions.     

Piezoelectric coefficients of multilayer Pb(Zr,Ti)O<Subscript>3</Subscript> thin films

Sol–gel techniques were used to prepare thin films of Pb(Zr _x ,Ti_1−x )O₃ (PZT) with three different Zr/Ti ratios and a graded PZT film with three different compositional layers. A Michelson interferometer was used to measure the thickness strains due to an applied ac electric field. Effective d ₃₃ piezoelectric strain coefficients were computed from the experimental data. Interfacial pinning caused these coefficients to differ from the true ones. They were corrected for the pinning using both an analytical model and finite-element analysis. The corrected coefficients of the PZT (52/48) sample were in excellent agreement with values of bulk materials. The coefficients of the multilayer sample were very low, probably due to insufficient poling or domain switching.     

Single crystal growth and superconductivity of Ca(Fe1−x Co x )2As2

We report the single crystal growth of Ca(Fe_1?x Co _x )₂As₂ (0?≤?x?≤?0.082) from Sn flux. The temperature–composition phase diagram is mapped out based on the magnetic susceptibility and electrical transport measurements. The phase diagram of Ca(Fe_1?x Co _x )₂As₂ is qualitatively different from those of Sr and Ba; this could be due to both the charge doping and structural tuning effects associated with Co substitution.     

Effect of shape anisotropy on the phase diagram of the Gay-Berne fluid

We have used the density functional theory to study the effect of molecular elongation on the isotropic-nematic, isotropic-smectic A and nematic-smectic A phase transitions of a fluid of molecules interacting via the Gay-Berne intermolecular potential. We have considered a range of length-to-width parameter 3.0 ⩽ x₀ ⩽ 4.0 in steps of 0.2 at different densities and temperatures. Pair correlation functions needed as input information in density functional theory are calculated using the Percus-Yevick integral equation theory. Within the small range of elongation, the phase diagram shows significant changes. The fluid at low temperature is found to freeze directly from isotropic to smectic A phase for all the values of x₀ considered by us on increasing the density while the nematic phase stabilizes in between isotropic and smectic A phases only at high temperatures and densities. Both isotropic-nematic and nematic-smectic A transition density and pressure are found to decrease as we increase x₀. The phase diagram obtained is compared with computer simulation result of the same model potential and is found to be in good qualitative agreement.     

Generic phase diagram of “electron-doped” T′ cuprates

We investigated the generic phase diagram of the electron doped superconductor, Nd_2−xCe_xCuO₄, using films prepared by metal organic decomposition. After careful oxygen reduction treatment to remove interstitial O_ap atoms, we found that the T_c increases monotonically from 24 K to 29 K with decreasing x from 0.15 to 0.00, demonstrating a quite different phase diagram from the previous bulk one. The implication of our results is discussed on the basis of tremendous influence of O_ap “impurities” on superconductivity and also magnetism in T′ cuprates. Then we conclude that our result represents the generic phase diagram for oxygen-stoichiometric Nd_2−xCe_xCuO₄.     

Magnetic and structural phase transitions in the shape-memory ferromagnetic alloys Ni2+x Mn1−x Ga

The results of an experimental investigation of the temperature dependences of the magnetic susceptibility and resistivity in the shape-memory ferromagnetic alloys Ni_2+x Mn_1−x Ga (x=0–0.20) are reported. A T−x phase diagram is constructed on the basis of these data. It is shown that partial substitution of Ni for Mn causes the temperatures of the structural (martensitic) T _M and magnetic T _C (Curie point) phase transitions to converge. In the region where T _C =T _M the transition temperature increases linearly with magnetic field in the range from 0 to 10 kOe. The kinetics of a magnetic-field-induced martensitic phase transition is investigated, and the velocities of the martensite-austenite interphase boundary during direct and reverse transitions are measured. A theoretical model is proposed and the T−x phase diagram is calculated. It is shown that there exist concentration ranges where the magnetic and martensitic transitions merge into a first-order phase transition. The theoretical results are in qualitative agreement with experiment. Zh. éksp. Teor. Fiz. 115, 1740–1755 (May 1999)     

A TEM study of crystal and domain structures of Nb-Doped 95/5 PZT ceramics

95/5 PZT ceramics with compositions of Pb(Zr_1–x Ti _x )₃+1 wt% Nb₂O₅ (x=0.025 and 0.04) are studied with TEM. The coexistence of both ferroelectric (F) and antiferroelectric (AF) phases in one ceramic grain at room temperature is confirmed for these two compositions. The AF phase is mainly tetragonal, while a pseudo-cubic arrangement of AF polarization is also possibly present. When the Ti⁴⁺ concentration is increased, the F phase becomes predominant. Direct interfaces between F and AF domains can be observed, the former expands at the expense of the latter when bombarded by 200 keV electrons.     

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     

Phase transitions in the ferromagnetic alloys Ni2+x Mn1−x Ga

The phase diagram of the cubic ferromagnetic shape-memory alloy Ni_2+x Mn_1−x Ga is constructed theoretically for the case when the Curie temperature is close to the structural transition temperature. This diagram agrees well with the experimental data obtained from resistance and magnetic susceptibility measurements. It is shown that the transition from the paramagnetic cubic phase to the ferromagnetic tetragonal phase can be second-order or first-order. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 3, 212–216 (10 February 1998)     

Relation between structure and magnetism of TixFe100−x alloys within the C14 Laves-phase stability range

We report about X-ray and magnetic investigations on polycrystalline alloys with hexagonal C14 (MgZn₂) structure of the system Ti_xFe_100−x in the concentration range 30.5x36.5 around the Laves-phase composition TiFe₂ (Ti_33.3Fe_66.6). Neighboring compositions Fe₅₀Ti₅₀ (with B2 structure) and Ti₁₅Fe₈₅ and Ti₂₀Fe₈₀ (with BCC structure) have also been investigated. From the data we establish a magnetic phase diagram for the C14 range of the system, showing a rather sharp transition from mainly ferromagnetic ordering in the range x<32 to a mainly antiferromagnetic ordering in the range x>32. The results can be made plausible microscopically by taking the site dependence of the moments into account. A revised structural equilibrium phase diagram is also given.     

Dynamical phase transition in two-dimensional fully frustrated Josephson junction arrays with resistively shunted junction dynamics

The dynamical phase transitions in two-dimensional fully frustrated Josephson junction arrays at zero temperature are investigated numerically with the resistively shunted junction model through the fluctuating twist boundary condition. The model is subjected to a driving current with nonzero orthogonal components i _x , i _y parallel to both axes of the square lattice. We find a roughly lattice size independent phase diagram with three dynamical phases: a pinned vortex lattice phase, a moving vortex lattice phase and a moving plastic phase. The phase diagram shows a direct transition from the pinned vortex to the moving vortex phase and the separation of the pinned vortex and the moving plastic phases. The time-dependent voltages v _x and v _y are periodic in the moving vortex lattice phase. But they are aperiodic in the moving plastic phase, resulting in non-monotonic characteristics and hysteresis in the current-voltage curves. It is found that the characteristic frequency is twice the time-averaged voltage in the moving vortex phase and around the time-averaged voltage in the plastic flow regime.Received: 29 May 2003, Published online: 2 October 2003PACS: 64.60.Ht Dynamic critical phenomena - 74.25.Sv Critical currents - 74.25.Fy Transport properties     

PbTiO3/PbZr0.3Ti0.7O3/PbTiO3夹心结构铁电薄膜子晶层的优化

用Sol-Gel法制备了Pb_(1+x)TiO₃/PbZr_03Ti_07O₃/Pb_(1+x)TiO₃(PT/PZT/PT)夹心结构及PZT铁电薄膜,为了获得高质量的PT/PZT/PT夹心结构铁电薄膜,使用不同过量Pb配比(x)的PbTiO₃ (PT)层进行制备,以获得优化的PT子晶层.X射线 关键词： PT/PZT/PT 夹心结构 子晶 铁电薄膜     

Interplay of metamagnetic and structural transitions in Ca2-xSrxRuO4

Metamagnetism in layered ruthenates has been interpreted as a novel kind of quantum critical behavior. In an external magnetic field, Ca_2-xSr_xRuO₄ undergoes a metamagnetic transition accompanied by a pronounced magnetostriction effect. In this paper we present a mean-field study for a microscopic model that naturally reproduces the key features of this system. The phase diagram calculated is equivalent to the experimental T-x phase diagram. The presented model also gives a good basis to discuss the critical metamagnetic behavior measured in the system.