Structural phase transitions in BaPrO3

The crystal structures adopted by BaPrO₃ at and above ambient temperature have been examined using a combination of synchrotron X-ray and neutron diffraction. BaPrO₃ has been established to undergo a series of phase transitions from cubic. BaPrO₃ is the second A²⁺B⁴⁺O₃ perovskite found to adopt rhombohedral symmetry in preference to the I4/mcm tetragonal structure. Analysis of the octahedral tilting through the rhombohedral to cubic phase transition indicates that this transformation is continuous and tricritical in nature. The tricritical behaviour of this transition is likely to be a result of the competition between tetragonal and rhombohedral structures to be the preferred phase, with the rhombohedral symmetry adopted by BaPrO₃ being stabilised by the unusually large B-site cation.     

Phase separation during the melting of oxide borates LnCa4O(BO3)3 (Ln=Y, Gd)

GdCa₄O(BO₃)₃ (GdCOB) and YCa₄O(BO₃)₃ (YCOB) single crystals have been grown from the melt by the Czochralski method. Subsequent DTA analysis of the single crystals showed different behavior for both substances. During the first heating both crystals showed a single sharp melting peak at 1490°C (GdCOB) or at 1504°C (YCOB), respectively. In subsequent heating/cooling runs only GdCOB shows one single peak, whereas YCOB shows five peaks. Moreover, phase separation of the melt can be observed by optical observation and by EDX measurements. This behavior can be explained by a miscibility gap in the YCOB melt. The YCOB crystal is formed from the stoichiometric melt by a monotectic reaction.     

New glasses within the Tl2O-Ag2O-TeO2 system: Thermal characteristics, Raman spectra and structural properties

Within the Tl₂O-Ag₂O-TeO₂ system, a large glass-forming domain was evidenced and is presented for the fist time. Densities, glass transition (T_g) and crystallization (T_c) temperatures of the relevant glasses were measured. A structural approach of these glasses as functions of the composition was performed using Raman scattering. The Raman spectra were analysed in terms of the structural modifications induced by the Tl₂O and Ag₂O modifiers. It has clearly evidenced a phase separation inherent in tellurite glasses with low valence cations (as Tl⁺ and Ag⁺). The glasses would be constituted of two phases only: one of pure TeO₂ and one of pure ortho-tellurite M₂TeO₃ (M = Ag, Tl) with the statistically mixed Ag-Tl cationic composition.     

Crystal structures and phase transitions in Ba2HoTaO6

The structure of the cation-ordered double perovskite Ba₂HoTaO₆ was examined using synchrotron X-ray powder diffraction at fine temperature intervals over the range of 90-300 K. Ba₂HoTaO₆ has a cubic structure in space group at room temperature. A proper ferroelastic phase transition to I4/m tetragonal symmetry occurs near approximately 260 K. Analysis of the spontaneous tetragonal strain versus temperature indicated that the phase transition is second order in nature.     

High temperature-induced phase transitions in Sr2GdRuO6 complex perovskite

The crystal structure behavior of the Sr₂GdRuO₆ complex perovskite at high-temperature has been investigated over a wide temperature range between 298 K ≤ T ≤ 1273 K. Measurements of X-ray diffraction at room-temperature and Rietveld analysis of the experimental patterns show that this compound crystallizes in a monoclinic perovskite-like structure, which belongs to the P2₁/n (#14) space group and 1:1 ordered arrangement of Ru⁵⁺ and Gd³⁺ cations over the six-coordinate M sites. Experimental lattice parameters were obtained to be a =5.8103(5) Å, b =5.8234(1) Å, c =8.2193(9) Å, V = 278.11(2) Å³ and angle β = 90.310(5)°. The high-temperature analysis shows the occurrence of two-phase transitions on this material. First, at 573 K it adopts a monoclinic perovskite-type structure with I2/m (#12) space group with lattice parameters a = 5.8275(6) Å, b = 5.8326(3) Å, c = 8.2449(2) Å, V = 280.31(3) Å³ and angle β = 90.251(3)°. Close to 1273 K it undergoes a complete phase-transition from monoclinic I2/m (#12) to tetragonal I4/m (#87), with lattice parameters a = 5.8726(1) Å, c = 8.3051(4) Å, V = 286.39(8) Å³ and angle β = 90.0°. The high-temperature phase transition from monoclinic I2/m (#12) to tetragonal I4/m (#87) is characterized by strongly anisotropic displacements of the anions.     

Subsolidus phase equilibria and the Li5Nd4FeO10 phase in the Li2O-Nd2O3-Fe2O3 system

A survey of the subsolidus phase equilibria in the system Li₂O-Nd₂O₃-Fe₂O₃ was made at subsolidus temperatures in the range 1000-1050 °C. A ternary phase was identified. The phase is centered on Li₅Nd₄FeO₁₀, with a cubic lattice a = 11.9494 Å. The compound melts incongruently at 1105 °C. The magnetic susceptibility was measured in the temperature range 4-300 K. The compound is paramagnetic in the temperature range 150-300 K and follows the Curie-Weiss law. At about T_N = 10 K, a long-range magnetic ordering is observed.     

Study of crystallization kinetics and structural relaxation behavior in phase separated Ag33Ge17Se50 glassy alloys

We report on the crystallization processes and structure (crystal phases) of Ag₃₃Ge₁₇Se₅₀ glassy alloy using differential scanning calorimetry and x-ray diffraction techniques, respectively. The devitrification that gives rise to the first exothermic peak results in the crystallization of Ag₂Se and Ag₈GeSe₆ phases, while the growth of GeSe₂ accompanied by the transformation of Ag₈GeSe₆ to Ag₂Se phase occurs during the second crystallization process. Different theoretical models are used to elucidate various kinetic parameters for the crystallization transformation process in this phase separated system. With annealing below the glass transition temperature, an inverse behavior between the variation of the optical gap and the band tailing parameter is observed for the thermally evaporated films. These results are explained as the mixing of different clusters/species in the amorphous state and/or changes caused by structural relaxation of the glassy network for the thermally evaporated films.     

Abnormal electrocaloric effect of Na0.5Bi0.5TiO3–BaTiO3 lead-free ferroelectric ceramics above room temperature

We demonstrate the electrocaloric effect (ECE) of Na_0.5Bi_0.5TiO₃–BaTiO₃ (NBT–BT) lead-free ferroelectric ceramics, which were fabricated by the solid-state reaction method. Based on a Maxwell relation, the ECE was characterized via P–T curves under different electric fields. The polarization of NBT increases monotonically within the temperature range of 25–145 °C. It indicates that the NBT has an abnormal ECE with a negative temperature change (ΔT₁₄₀ = −0.33 K at E = 50 kV/cm) opposite to that of the normal ferroelectrics. The 0.92NBT–0.08BT composition near the morphotropic phase boundary has a normal ECE under low electric fields and an abnormal ECE under high electric fields. The abnormal ECE character originates from the relaxor characteristic between ferroelectric and antiferroelectric phases, while the common ECE is always related to the normal ferroelectric–paraelectric phase transition.     

New quenched-in fluorite-type materials in the Bi2O3-La2O3-PbO system: Synthesis and complex phase behaviour up to 750 °C

New quenched-in fluorite-type materials with composition (BiO_1.5)_0.94−x(LaO_1.5)_0.06(PbO)_x, x = 0.02, 0.03, 0.04 and 0.05, were synthesised by solid state reaction. The new materials undergo a number of phase transformations during heating between room temperature and 750 °C, as indicated by differential thermal analysis. Variable temperature X-ray diffraction performed on the material (BiO_1.5)_0.92(LaO_1.5)_0.06(PbO)_0.02 revealed that the quenched-in fcc fluorite-type material first undergoes a transformation to a β-Bi₂O₃-type tetragonal phase around 400 °C. In the range 450-700 °C, α-Bi₂O₃-type monoclinic, Bi₁₂PbO₁₉-type bcc and β₁/β₂-type rhombohedral phases, and what appeared to be a ?-type monoclinic phase, were observed, before a single-phase fluorite-type material was regained at 750 °C.     

Subsolidus phase equilibria in the RuO2-Bi2O3-ZrO2 system

Subsolidus equilibria in air in the RuO₂-Bi₂O₃-ZrO₂ system were studied with the aim of obtaining information on possible interactions between a Bi₂Ru₂O₇-based cathode and a ZrO₂-based solid electrolyte in solid-oxide fuel cells (SOFCs). No ternary compound was found in the system. The tie lines are between Bi₂Ru₂O₇ and ZrO₂, and between Bi₂Ru₂O₇ and gamma-Bi₂O₃—the ZrO₂ stabilised Bi₂O₃ phase, stable at temperatures over 710 °C.     

Thermochemical studies on SrFe12O19(s)

The citrate-nitrate gel combustion route was used to prepare SrFe₁₂O₁₉(s) powder sample and the compound was characterized by X-ray diffraction analysis. A solid-state electrochemical cell of the type: (−)Pt, O₂(g)/{CaO(s) + CaF₂(s)}//CaF₂(s)//{SrFe₁₂O₁₉(s) + SrF₂(s) + Fe₂O₃(s)}/O₂(g), Pt(+) was used for the measurement of emf as a function of temperature from 984 to 1151 K. The standard molar Gibbs energy of formation of SrFe₁₂O₁₉(s) was calculated as a function of temperature from the emf data and is given by: (SrFe₁₂O₁₉, s, T)/kJ mol⁻¹ (±1.3) = −5453.5 + 1.5267 × (T/K). Standard molar heat capacity of SrFe₁₂O₁₉(s) was determined in two different temperature ranges 130-325 K and 310-820 K using a heat flux type differential scanning calorimeter (DSC). A heat capacity anomaly was observed at 732 K, which has been attributed to the magnetic order-disorder transition from ferrimagnetic state to paramagnetic state. The standard molar enthalpy of formation, (298.15 K) and the standard molar entropy, (298.15 K) of SrFe₁₂O₁₉(s) were calculated by second law method and the values are −5545.2 kJ mol⁻¹ and 633.1 J K⁻¹ mol⁻¹, respectively.     

In situ observation of the change in domain structure due to phase transformation in a perovskite La2MnGaO6

The microstructure of a perovskite, La₂MnGaO₆, was studied by Transmission Electron Microscopy (TEM). An idiomorphic grain exhibited a domain structure at ambient temperature, and each domain possessed a common b-axis and axial relation, [1 0 0]//[0 0 1]. When the grain was heated by a convergent electron beam, the domains vanished after the orthorhombic to rhombohedral phase transformation taking place at 423 K. The domains reappeared when cooled, although domain boundaries moved and the domains rotated by 90° with respect to the b-axis.     

Subsolidus phase equilibria in the Al2O3-CeO2-PbO and Al2O3-CeO2-RuO2 systems

The subsolidus phase equilibria in air for the Al₂O₃-CeO₂-PbO and Al₂O₃-CeO₂-RuO₂ systems were studied with the aim of obtaining information on possible interactions between a CeO₂-based solid electrolyte in solid-oxide fuel cells (SOFCs) and other oxides. No ternary compound was found in either of the systems. The tie line in the Al₂O₃-PbO-CeO₂ system is between Al₂Pb₂O₅ and the CeO₂.     

Development of perovskite in Fe-substituted Pb(Zn1/3Ta2/3)O3 and dielectric characteristics

Pb(Zn_1/3Ta_2/3)O₃ ceramics, compositionally modified by the incorporation of Fe to the octahedral lattice sites, were prepared and characterized in terms of perovskite development, dielectric properties, as well as microstructure evolution. The powders of the B-site precursor compositions were synthesized separately and reacted with PbO to form Pb[(Zn_1/3Ta_2/3),(Fe_1/2Ta_1/2)]O₃. The perovskite contents increased continuously with the Fe concentration. The maximum dielectric constant values of the ceramics increased tremendously with the fraction of Fe, whereas the dielectric maximum temperatures were rather insensitive to the compositional change.     

The mechanism of accelerated phase formation of MgB2 by Cu-doping during low-temperature sintering

Thermal analysis, phase identification and microstructure observation were adopted to explore the accelerating sintering effect of Cu-doping on the low-temperature formation of MgB₂ below Mg melting. It is found that the Cu-doping sintering of MgB₂ bulk followed an activated sintering mechanism and thus obviously promoted the reaction between Mg and B forming bulk MgB₂. Accordingly, dense MgB₂ bulks with excellent T_c and J_c were successfully synthesized by the Cu-doping sintering at 575 °C for only 5 h. Further, a sintering model was proposed to illuminate the Cu-doping activated sintering mechanism. It is found that during the Cu-doping activated sintering process, the local Mg-Cu liquid generates firstly and then segregates to the interface between Mg and B particles, which can wet Mg particles and provide a rapid transport for the diffusion of neighboring Mg atoms into B particles resulting in the accelerated formation of MgB₂ phase.     

TG/DSC analysis of Fe8(OOH)16Cl1.3 nanospindles

The thermal analysis of Fe₈(OOH)₁₆Cl_1.3 (Akaganeite-M) nanospindles prepared by the hydrolysis of FeCl₃ solutions are determined by thermogravimetric analyses and differential scanning calorimetry (TG/DSC), in conjunction with field-emission scanning electron microscopy (FE-SEM), and X-ray diffraction (XRD). Different products are formed after Fe₈(OOH)₁₆Cl_1.3 nanospindles are calcined at different temperatures for 30 min in N₂ atmosphere: Fe_1.833(OH)_0.5O_2.5 and magnetite obtained at 250 °C; pure magnetite (Fe₃O₄) obtained at 630 °C; and magnetite containing some iron nitrides (Fe₂N and Fe₄N) obtained at 800 °C. The calcination of Fe₈(OOH)₁₆Cl_1.3 provides a new method to prepare pure magnetite.     

Synthesis and properties of GeS2-Ga2S3-PbI2 chalcohalide glasses

The glass-forming region in the GeS₂-Ga₂S₃-PbI₂ system was determined and the basic parameters of thermal and optical properties (glass transition temperature, density, microhardness and transmission window) for these glasses have been measured. Better thermal stability originated from their larger difference between T_x and T_g in the range of 107-161 °C, higher glass transition temperatures between 252 and 398 °C and wide optical transmission window from 0.5 to 12.7 μm make these glasses the promising candidate materials for rare earth doped fiber amplifiers and nonlinear optical devices.     

Powder X-ray diffraction study of the rhombohedral to cubic phase transition in TiF3

Synchrotron powder diffraction has been used to examine the crystal structure of the TiF₃ between 20 and 450 K with emphasis on the cubic to rhombohedral structural phase transition near 370 K. This transition involves an apparently continuous reduction in the tilts of the TiF₆ octahedra. A remarkable difference in the thermal expansion coefficients in the two phases is observed.