Phase transition of cadmium fluoride under high pressure

We investigated the high pressure phases of CdF₂ by a joint theoretical and experimental study. The structural and electronic properties of CdF₂ were extensively explored to high pressure by ab initio calculations based on the density functional theory. A structural phase transition from the fluorite-type  (Fm-3m, Z=4) structure to the cotunnite-type (Pnma, Z=4) structure was estimated below 8 GPa, and this phase transition was examined by the high pressure experiments up to 35 GPa at room temperature. Both high pressure angle dispersive X-ray diffraction and Raman spectroscopy experiments provided convincing evidence to verify the phase transition. Our work makes clear pressure-induced phase transitions and structural information of CdF₂ under high pressure.     

X-ray diffraction and spectroscopic investigations of phase transitions in linear chain compounds M2 [Pt(CN)4]3 · 21H2O,with M = Dy, Er,Tb, Y

Phase transitions of single-crystal M₂ [Pt(CN)₄]₃ · 21H₂O are investigated under temperature variation using X-ray diffraction, polarized emission and DSC-measurements. At a temperature T_trans a jump was observed in lattice parameters and in optical transition energies. The transition is connected with an occurence of a latent transition enthalpy. This indicates a displacive phase transition of first order. Optical and X-ray data can be correlated.     

Crystal structure and cation distribution in the solid solution series 2(ZnX)-CuInX2 (X=S, Se, Te)

The solid solution series (2ZnX)_x (CuInX₂)_1−x (X=S, Se, Te) were studied by the combination of laboratory and synchrotron X-ray and by neutron powder diffraction. Within the homologous series the tetragonal distortion ¼-u increases in the sequence S→Se→Te whereas the tetragonal deformation η=c/2a decreases. Besides that, with increasing 2ZnX content in CuInX₂ the anion position parameter u increases as expected. The cation site occupancy in the chalcopyrite type phase of single phase tetragonal samples was obtained by Rietveld analysis of the neutron diffraction data. A non-statistic Zn distribution could be deduced for all three systems. The high temperature in situ diffraction experiments with synchrotron radiation on CuInX₂ powder samples revealed the Cu-In anti-site occupation as the driving force of the temperature dependent phase transition from the chalcopyrite to the zinc-blende type structure.     

Variable-temperature Raman scattering and X-ray diffraction studies of Bi3.25Nd0.75Ti3O12 ceramics

Neodymium-substituted bismuth titanate (Bi_3.25Nd_0.75Ti₃O₁₂, BNT_0.75) ceramics was prepared by chemical co-precipitation along with calcinations. The lattice instability has been investigated by variable-temperature Raman scattering and X-ray diffraction. The results showed that there was an orthorhombic to pseudo-tetragonal phase transition at about 695 K, in terms of the evolution of temperature dependence of Raman scattering frequencies. Some changes at about 695 K in the XRD lines, the lattice parameters (a, b, and c) as well as the orthorhombic distortion b/a have been detected in the high temperature X-ray diffraction, which confirmed the conclusion that the BNT_0.75 ceramics undergoes a ferroelectric to paraelectric phase transition at about 695 K.     

Structure and dielectric properties of PZT-type ceramics with the diffuse phase transition

In the present work the (Pb_0.84Ba_0.16)(Zr_0.54Ti_0.46)O₃ (PBZT) solid solution has been synthesized. The process of preparation was investigated by simultaneous thermal analysis (STA) and X-ray diffraction method. The hot pressing method was utilized for densification of ceramic samples. Dielectric properties of donor- and acceptor-doped PZT-type ceramics were measured within the temperature range including the phase transition region. Frequency-dependent relaxation behaviour in PBZT ceramics was found. The structural phase transition at T?=?(517?±?3)?K was determined by X-ray diffraction method. Arrhenius plot of total conductivity derived from ac impedance spectroscopy measurements was used for characterisation of phase transition. Changes in activation energy were found characteristic of phase transition in PBZT ceramics.     

Influence of Pr dopant on the dielectric properties and Curie temperatures of Ba1−3x Pr2x Ti0.95Sn0.05O3 (0.01≤x≤0.05) ceramics

Three perovskite-structured ceramic phases Ba_1?3x Pr_2x Ti_0.95Sn_0.05O₃ (BPTS-x) with x=0.01, 0.03, and 0.05 have been synthesized by solid-state reaction method. Obtained BPTS-x ceramics were investigated by X-ray diffraction and dielectric properties measurements. Analysis of all the ceramic samples using X-ray diffraction method at room temperature and its Rietveld refinement inferred rhombohedric structure with the space group $R\bar{3}c$ . The temperature variation of real permittivity gives evidence of the ferroelectric phase transition and of the relaxation behavior. With increasing Pr concentration, the degree of diffuse phase transition was enhanced, and a linear reduction in the transition temperature was produced. The conductivity spectra have been investigated by the Jonscher universal power law (σ(ω)=σ _dc+Aω ^s ) and attributed to hopping conduction mechanism.     

High-temperature structural phase transition in the LiCu2O2 multiferroic

The results of thermogravimetric, X-ray diffraction, and electrical studies of LiCu₂O₂ single crystals in the temperature range 300–1100 K are presented. A reversible first-order phase transition between the orthorhombic and tetragonal phases is found to occur in these single crystals at T = 993 K. A pronounced peak on a differential thermal analysis curve and jumps in the unit cell parameters and the electrical resistivity are detected at the phase-transition temperature. The data on the crystal structure of LiCu₂O₂ and the phase transition-induced change in the entropy determined in this work are used to conclude that the revealed phase transition is caused by the ordering-disordering of Li⁺ and Cu²⁺ cations in their structural positions.     

Phase transition, order parameter, and their manifestation in optical spectra of Hg2Cl2

This paper reports on a high-precision study of the effects induced by the phase transition in Raman spectra of Hg₂Cl₂ crystals. The odd (acoustic and IR-active) phonons, including the soft modes, from the Brillouin zone (BZ) X points of the paraphase of these crystals, which are induced by the phase transition, unit cell doubling, and the X ?? ?? BZ folding, have been investigated both theoretically and experimentally. The temperature dependences of the intensities of these phonons, complemented by a theoretical analysis, have yielded the first information on the behavior of the transition order parameter. The corresponding critical exponents have been derived, which correlate in magnitude with the data obtained from X-ray diffraction measurements and, thus, imply the closeness of the phase transition in these crystals to the tricritical point.     

Study of phase transitions and properties of tetragonal (Pb,La)(Zr,Ti)O3 ceramics—I: Phase diagram and β-phase

The phase diagram (T?x plot) of thermally depoled tetragonal PLZT materials has been investigated by means of X-ray diffraction, Capacitance and DSC measurements. Materials with a low La content show a classical Fe_t?PE_c transition. This transition has first or second order character, dependent on the Zr/Ti ratio.Materials with a medium and high La content show a diffuse transition from the cubic high temperature phase to a tetragonal, so called β phase. This β phase has no clear FE properties and a spontaneous transition to the FE_t phase on lowering the temperature only takes place for materials with a medium La content. For materials with a high La content a spontaneous β_t→ FE_t transition is not observed.     

Structural phase transition in YBa2Cu3O7−δ: the role of dimensionality for high temperature superconductivity

We have performed detailed high temperature X-ray diffraction to study the nature of the structural phase of YBa₂Cu₃O_7−δ. The results indicate the existence of a reversible orthorhombic to tetragonal phase transition at a temperature close to 750°C. If the high temperature tetragonal phase is quenched-in at low temperatures the critical superconducting temperature is considerably reduced from 92.5 K. This suggests that the one dimensional CuO chains present in the orthorhombic structure are necessary for high temperature superconductivity.     

The influence of Al substitution on the phase transitions and magnetocaloric effect in Ni43Mn46Sn11−xAlx alloys

The effects of Al substitution on the phase transitions and magnetocaloric effect of Ni₄₃Mn₄₆Sn_11−xAl_x (x=0-2) ferromagnetic shape memory alloys were investigated by X-ray diffraction and magnetization measurements. With the increase of Al content, the cell volume decreases due to the smaller radius of Al, and the martensitic transformation temperature increases rapidly, while the Curie temperature of austenitic phase shows a small increase. A large positive and a negative magnetic entropy change were observed near the first-order martensitic transition and the second-order magnetic transition, respectively. The magnetic entropy changes, hysteresis behavior, and refrigerant capacity near the two transitions are compared.     

High-pressure Raman and X-ray studies of barite,BaSO4

High-pressure Raman spectroscopic and X-ray diffraction experiments of barite, BaSO₄, were carried out in a diamond anvil cell up to 25?GPa at room temperature. On the basis of the changes in the diffraction patterns and the variation of lattice parameters with pressure, it is inferred that barite undergoes a phase transformation at 10?GPa. The phase transition accompanies the change in the force constant of vibrational modes in barite. Further compression beyond the phase transition causes the distortion of SO₄ tetrahedron as indicated by the splitting in the SO₄ stretching modes. Both X-ray and Raman data support that the phase transition in BaSO₄ is reversible. The compression data yield a bulk modulus of 63?±?2?GPa for barite. Barite shows anisotropic compressibility along three crystallographic axes with c being the most compressible axis.     

High temperature structural studies of SrRhO3

High resolution X-ray powder diffraction studies have shown SrRhO₃ to transform from an orthorhombic Pnma structure at room temperature through an intermediate Imma phase to a tetragonal I4/mcm structure near 800 °C. The orthorhombic Imma phase exists over a very limited temperature range, of less than 20°. The diffraction data suggests the Pnma to Imma transition is continuous and demonstrates that the Imma-I4/mcm transition is first order.     

外加热型金刚石对顶压砧高压装置及高温下的压力测量

 本文报导了一种外加热型金刚石对顶压砧装置的高温高压技术，装置的压力可达20 GPa，温度可达350 ℃。采用本装置对六角结构的α-LiIO₃进行了高温高压X射线衍射实验，获得的四方结构高压相与用淬火卸压所得的ε相结构一致；建立了高温下的红宝石测试技术。发现可以根据由此法测定的Δγ_p-T曲线初步判别样品是否存在伴随有体积变化的结构相变，并可估计出该相变的压力、温度范围及相变造成的压力下降值。     

Phase transitions in PbSc0.5Ta0.5O3

Ordered and partially ordered PbSc_0.5Ta_0.5O₃ ferroelectric single crystals are studied by diffraction, electrophysical, and optical methods. X-ray diffraction and electrophysical methods indicate the presence of a phase transition in the low-temperature range (at T = ?40°C).     

Effects of the phase transition in Hg2(Br,I)2 crystals

The effects of the phase transition in Hg₂(Br,I)₂ crystals have been investigated over a wide range of temperatures by the Raman scattering spectroscopy and X-ray diffraction analysis. The overtones (at the X point of the Brillouin zone boundary) and the fundamental tones (at the center of Brillouin zone) of soft modes are found in the Raman spectra of these crystals and studied in detail. The density of one-phonon states of the soft TA branch manifests itself in the Raman spectra of mixed crystals. The potentialities of the soft-mode spectroscopy are realized in full measure. Analysis of the ratio between intensities of overtones and fundamental tones of the soft modes has demonstrated the applicability of the Landau phenomenological theory of phase transitions. The orthorhombic splitting of the reflections corresponding to the basal plane is revealed in the X-ray diffraction patterns and thoroughly explored. The temperature dependences of the isotropic and shear spontaneous strains are obtained. It is shown that the shear spontaneous strain plays a decisive role. The critical indices are determined and the model of the improper ferroelastic phase transition D _4h ¹⁷ → D _2h ¹⁷ in the vicinity of the tricritical point is corroborated.     

Birefringence,X-ray and neutron diffraction measurements on the structural phase transitions of (CH3NH3)2 MnCl4 and (CH3NH3)2FeCl4

We used optical birefringence, X-ray and neutron diffraction methods with single crystals to study the structural phase transitions of the perowskite-type layer structures of (CH₃NH₃)₂MeCl₄ with Me=Mn, Fe. The Mn-compound shows the following structural transitions at 394 K — a continuous order-disorder phase transition from tetragonal symmetry $\text{I4}\text{mmm}$ to orthorhombic space group Abma (Cmca in reference 10); at 257 K — a discontinuous transition to a second tetragonal modification; at 95 K — a discontinuous transition to a monoclinic phase. For the Fe-compound the corresponding transition temperatures are 328 K and 231 K, respectively. A low temperature monoclinic phase could not be observed. The lattice parameters of the different modifications were determined as a function of temperature. The temperature dependent course of the order parameter has been investigated for the order—disorder transition. For both compounds, all the methods used gave the same value for the critical exponent of β = 0.315.     

Superstructure and phase transitions in CsPbCl3

Superstructure of CsPbCl₃ is investigated by X-ray diffraction experiments. In the room temperature phase, three types of superlattice reflections are observed which correspond to the X, M and R points of the cubic Brillouin zone. On heating from room temperature, an integrated intensity of the X point reflection exhibits a discontinuous decrease at 37°C, while the R and M point reflections disappear at 42 and 47°C respectively. Explanations of these phase transitions in terms of condensation of soft-zone boundary phonon modes are presented.     

Structural aspects of the antiferroelectric-paraelectric phase transition in double perovskite Pb2MgWO6 at high pressures and temperatures

The crystal structure of antiferroelectric Pb₂MgWO₆ has been studied using neutron diffraction at high pressures to 5.4 GPa at room temperature and energy-dispersive X-ray diffraction at high pressures to 4 GPa in the temperature range 300–400 K. At normal conditions, in Pb₂MgWO₆, there is an antiferroelectric phase with the crystal structure described by the orthorhombic symmetry with space group Pnma. At temperature T = 313 K and normal pressure or at room temperature and pressure P ～ 0.9 GPa, the crystal under-goes a structural phase transition to the cubic phase with space group $Fm\bar 3m$ (paraelectric phase). The temperature and pressure dependences of the lattice parameters, unit cell volume, and interatomic bond lengths have been obtained, and the thermal expansion coefficients and the bulk moduli have been calculated for the antiferroelectric and paraelectric phases of Pb₂MgWO₆.     

Structural and magnetic properties of the phase transition in absorbed and non-absorbed copper(II) trans-1,4-cyclohexanedicarboxylate

A large amount of toluene can be absorbed into the 1-dimensional tunnels in copper(II) trans-1,4-cyclohexane dicarboxylate (Cu(trans-1,4-OOCC₆H₁₀C)) at room temperature, and it can be desorbed by evacuation at elevated temperatures. The reversible absorption/desorption behavior of toluene was studied by magnetic susceptibility measurements using SQUID magnetometer and by powder X-ray diffractometry with high-energy synchrotron radiation at SPring-8, Japan. The first order phase transition was observed at 160 K in the magnetic susceptibility curve for the empty (non-absorbed or desorbed) sample, and the structural difference between the low and high temperature phases was detected in the powder X-ray diffraction patterns. On the other hand, no phase transition was observed in fully toluene-absorbed sample, and the structure was similar to that of the low temperature phase of the empty sample. The absorption/desorption behavior observed in the present study coincides with the results of heat capacity measurements by adiabatic calorimetry reported previously.