Enhancing the phase stability and ionic conductivity of scandia stabilized zirconia by rare earth co-doping

Effect of co-doping Yb, Gd and Ce in scandia stabilized zirconia (SSZ) on the phase stability, high temperature aging behavior and ionic conductivity was studied. Both binary (10 mol% SSZ) and the ternary (co-doped) compositions were found to be in single cubic phase in the as-processed condition. However, the binary composition exhibited the rhombohedral ‘β’ phase after sintering whereas the ternary compositions remained in the single cubic phase. The sintered pellets were aged at 900 °C for 500 h in air to study the phase stability at high temperature. Transmission electron microscopy revealed that the aged samples of Yb and Gd co-doped compositions contain small amount of the tetragonal phase which resulted in considerable degradation in conductivity (more than 20%). The Ce co-doped sample, on the other hand, was in single cubic phase after aging and this ensured that conductivity reduction was minimal in this composition. The co-doped samples however, showed higher conductivity before and after aging compared to the binary composition. The rhombohedral ‘β’ phase was absent in all the co-doped ternary compositions even after high temperature aging.     

Raman and X‐ray investigations of the incorporation of Ca2+ and Cd2+ in the ZrO2 structure

The formation of solid solution and ZrO₂ phase stabilization were investigated by Raman spectroscopy and X‐ray diffraction (XRD) in calcium‐containing and cadmium‐containing zirconium oxide samples heated at 1073 K in air. The adopted preparation procedure led to the incorporation of calcium and cadmium in solid solution into the zirconia structure. The solid solution favored the tetragonal and cubic zirconia phases at the expense of the thermodynamically stable monoclinic modification. Combined macro‐ and micro‐Raman spectroscopy disclosed that instead of forming a homogeneous phase t″, intermediate between the tetragonal t′ and the cubic phase, the tetragonal and cubic phases coexisted in the range 9.49–13.89 mol% for Ca and 11.88–17.23 mol% for Cd. At higher dopant contents the cubic form stabilized. The impurity content necessary to stabilize the high‐symmetry phases was defined. Copyright © 2007 John Wiley & Sons, Ltd.     

Characterization of laser sealed coatings of yttria partially stabilized zirconia

The present paper reports an experimental investigation based on X-ray diffraction (XRD), energy dispersive spectroscopy (EDS), and wavelength dispersive spectroscopy (WDS) analyses of phases formed after laser sealing of plasma sprayed coatings of 8.5 wt% yttria partially stabilized zirconia (YPSZ). X-ray diffraction and X-ray step-scanning analyses showed that the plasma sprayed and sealed coatings consisted mainly of t′ phase with a very small amount of monoclinic phase (m phase) in the plasma sprayed coatings. It was also found that the small amounts of m and cubic phases (c phase) present in the sealed coatings were dependent on laser processing specific energies (specific energy is equal to laser power/traverse speed x beam diameter). It was also found that rhombohedral (r) phase formed after laser sealing of coatings at higher specific energies. A direct relationship between c/a ratio of transformable tetragonal phase (t phase) produced by thermal treatment of sealed coatings and nontransformable tetragonal phase (t′ phase) and the amount of Yttria was obtained. A new equation was derived, which describes the relationship between Yttria concentration and the c/a ratio of tetragonal phases (t or t′).     

Effect of Ni doping on the phase stability and conductivity of scandia-stabilized zirconia

The effect of Ni doping on the phase stability and conductivity of scandia-stabilized zirconia (SSZ) thick film was studied. A free-standing 10SSZ thick-film (10 mol% Sc₂O₃-stabilized zirconia, ~ 10 μm thick) that was previously in contact with a Ni layer during co-firing was fabricated. The 10SSZ thick-film showed a cubic phase in contrast to the rhombohedral phase shown for a bulk 10SSZ sample. The Ni content in the SSZ thick film was ~ 1.7 mol%. The effect of Ni on the cubic phase formation was also confirmed by the similar observation of the cubic phase in the Ni-doped bulk 10SSZ sample. The observed conductivity behavior also supported the XRD observation. Ni was found to hinder the transformation of the cubic phase to the rhombohedral on cooling in 10SSZ samples after a reduction treatment.     

Mechanical properties of the alloy 36NKhTYu in relation to the mechanisms underlying the precipitation of the γ′-and η-phases

The kinetic characteristics of processes taking place during the aging of the alloy 36NKhTYu at 700–850?C were studied; these included an increase in the diameter of theγ′-phase particles formed in regions of continuous decomposition, an increase in the thickness of theγ′-lamellas formed in regions of discontinuous decomposition, and an increase in the volumetric proportion of material in which continuous precipitation of theγ′-phase was occurring. The formation of theη-phase was also studied (the degree of discontinuous precipitation of theη-phase depended on the quench temperature); interstitial stacking faults appeared, their formation and growth being associated with the precipitation of titanium carbide. With increasing period of aging the mechanism underlying the interaction of the dislocations with theγ′-particles changed; initially the particles were intersected by superdislocations; later they were encircled by single dislocations. The discontinuousγ′-phase precipitation which occurred on aging the material after quenching from 1280?C (in the case of fine-grained samples) was ascribed to the fact that insufficient carbon was available to provide carbide particles for pinning the grain boundaries.     

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.     

The effect of pressure on the Raman spectra of solids—IV. KSbF6 And CsSbF6

KSbF₆ has a tetragonal structure above 300 K, below 300 K. it is cubic and undergoes a phase transition at ∼ 3 kbar to a phase which is shown to be isostructural with that of rhombohedral CsSbF₆. Conclusive evidence is found in the polarized Raman spectra of single crystals of rhombohedral CsSbF₆ that they belong to the space group R3̄-C²_3i. The high-pressure Raman spectra of rhombohedral KSbF₆, TlSbF₆, and CsSbF₆ are compared and cationic effects are discussed.     

Mixed ionic conduction in solid KHF2

From EMF measurements it can be concluded that there is no significant electronic conductivity in KHF₂. In the relatively good conducting high temperature β-phase the following transport numbers are found: t_K≈0,25 and t_F≈0,75 while t_H≈0 as was concluded from changes in chemical composition on electrolysis in Hittorf-Tubandt type experiments. From current-time characteristics it follows that in the low-conducting low temperature α-phase, the proton is the only mobile charge carrier in this phase, i.e. t_H≈1. It also proved that the d.c. conductivity of single crystals measured with hydrogen permeable electrodes coincides with the zero-frequency conductivity found by extrapolation of a.c. data.     

Effect of Sr content on structure and electrical properties of La1−x Sr x MnO3 from ITSOFC cathode view point

The samples belonging to La_1−x Sr _x MnO₃ series, prepared by combustion route without using fuel, exhibit crystal structural phase transition with the change in Sr content. Less than 40 mol% Sr is partially substituted in the crystal structure of LaMnO₃. The structural phase transition from rhombohedral to cubic, cubic to tetragonal, and tetragonal to orthorhombic takes place on 40, 60, and 80 mol% addition of Sr. The highest electrical conductivity in La_0.4Sr_0.6MnO₃ is understood to be due to the maximum concentration of polaron. The polarons are formed due to the conversion of Mn³⁺ to Mn⁴⁺ so as to achieve electroneutrality after substitution of Sr²⁺ for La³⁺.     

129I-Mössbauer study of diffusion effects in the superionic conductor Ag3SI

The superionic conductor Ag₃SI was studied by¹²⁹I-Mössbauer spectroscopy in the rhombohedral γ-phase and in the cubic β-phase at temperatures between 4.2 K and 180 K. In the low-temperature γ-phase, one observes well below the γ-β phase transition at 157 K a motional-narrowing-like decrease of the electric-quadrupole interaction, roughly linear with temperature, which points to a diffusional motion of the Ag⁺ ions already in the γ-phase. Diffusional effects are also reflected by anomalous decrease of thef-factor in the same temperature region, which originates from a restricted short-range diffusional displacement of the iodide ions induced by the hopping Ag⁺ ions.     

Phase transformation in (0.90−x)Pb(Mg1/3Nb2/3)O3-xPbTiO3-0.10PbZrO3 piezoelectric ceramic: X-ray diffraction and Raman investigation

Piezoelectric ceramics with compositions of (0.90−x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃-0.10PbZrO₃, x=0.28, 0.31, 0.34, 0.37, 0.40 and 0.43, were prepared using the conventional columbite precursor method, and their structural phase transformation and piezoelectric behaviors near the morphotropic phase boundary (MPB) have been systematically investigated as a function of PbTiO₃ content. X-ray diffraction (XRD) results demonstrate that the structure of the ceramics experiences a gradual transition process from rhombohedral phase to tetragonal phase with the increasing of PbTiO₃ content, and that compositions with x=0.34-0.40 lie in the MPB region of this ternary system. A Raman spectra investigation of the ceramic samples testified to the transformation process of rhombohedral phase to tetragonal phase by comparing the relative intensities of tetragonal E(2TO₁) mode and rhombohedral phase R_h mode. The structure information was also correlated to the parabola change of the piezoelectric constant; the maximum piezoelectric constants were obtained near the MPB region.     

Magnetic properties of titanium vanadium hydrides

Measurements have been made of the magnetic susceptibility X in ternary titanium-vanadium hydrides Ti_1?yV_yH_x in the range 0<y< 0.5 and with a hydrogen to metal ratio from 1.6 to 1.92; they cover the temperature interval from 80 to 440 K. The x^?T curves of some of the ternary hydrides possess a maximum similar to that seen in binary hydrides. Its occurrence depends upon both hydrogen and vanadium concentration. Comparison with the lattice constants shows that this dependence is related to the transition from the cubic γ-phase to the tetragonal δ-phase. The x^?T curves of those samples showing the phase transition were extrapolated from the cubic phase down to lower temperatures. Conclusions were drawn from the measured and extrapolated susceptibility values, as to the influence of both hydrogen and vanadium concentrations on the electronic structure of these hydrides. The dependence of the magnetic susceptibility on the vanadium concentration shows that, in the cubic phase, the fermi energy lies on the increasing side of a maximum in the density of states curve. The degree of occupation of the conduction band does not depend on the hydrogen concentration. The rigid band model cannot be used in the hydrides studied here to account for the effects of varying their hydrogen concentration.     

Study of phase transitions and properties of tetragonal (Pb,La) (Zr,Ti)O3 ceramics—III: Transitions induced by electric fields

The phase diagram of electrically poled, tetragonal PLZT materials has been investigated. In the higher La concentration range, a tetragonal, so-called β-phase occurs, which has no clear FE properties. The transition to the FE_t phase has first order character and takes place only after a strong electric field has been applied to the material. The energetics of theβ_t ah FE_t transition were investigated in several ways. The heat-effects associated with this transition have a small value of 6–20cal/mol, dependent on composition. The transition β_t ah FE_t is accompanied by a relatively large activation energy ΔG₂. The ΔG₂(T) curve shows a minimum for materials, which do not show a spontaneous transition to the FE_t phase. This minimum value of $\text{ΔG}{}_2\text{(1–2.5}\text{cal}\text{mol}\text{)}$ is large in comparison to the average thermal energy kT and prevents the spontaneous transition from the β_t phase to the FE_t phase.     

High-pressure phases in the GaSb-Mn system

The effect of high pressure (6 GPa) on the formation of new phases in a polycrystalline mixture GaSb: Mn = 1: 1 upon heating was studied. Sphalerite-type solid solutions with a small amount of Mn form at temperatures below 520–600 K. At higher temperatures, new crystalline GaSbMn phases are synthesized: a phase with a simple cubic structure with a lattice parameter a = 2.946 ± 0.001 Å (at 620–670 K) and a phase with a tetragonal CuAl₂-type structure (space group I4/mcm) with lattice parameters a = 6.426 ± 0.004 Å and c = 5.349 ± 0.004 Å (at 690–870 K). These new phases are metastable under normal conditions and have magnetic properties. The structure, conductivity, and thermal stability of the synthesized phases are investigated, and the products of decomposition of these new phases upon annealing are analyzed.     

Influence of a strontium-enriched intergranular cluster network on the electrical conductivity of In2O3-SrO ceramics

A metastable hexagonal R-phase is revealed in polycrystalline In₂O₃-SrO samples, which has the form of a network made up of mesoscopic clusters (60–180 Å in size). The clusters arise from strontium-enriched regions near grain boundaries in the main cubic structure of indium oxide. It is shown that annealing in oxygen at T _a ? 300°C saturates dangling bonds between the R-phase and the matrix and makes the system metastable. This state shows up in the presence of (i) solitary diffuse maxima from the R-phase imposed on Debye lines from the main phase in the X-ray diffraction pattern and (ii) the electron cyclotron resonance (ECR) line with g = 1.875. In addition, the sample in this state acquires a high resistivity (ρ ～ 10⁶ Ω cm). Relaxation at T ? 300°C after annealing at T _a > 300°C disrupts bonds between the strontium-enriched clusters of the R-phase and the indium oxide matrix. This causes spatial separation of the clusters, disruption of their coherent bonds with the matrix structure, and escape of excess oxygen from the sample along grain boundaries. As a result, a new stable state forms, which is characterized by (i) a series of diffuse maxima from the R-phase imposed on lines assigned to the main phase, (ii) the presence of the ECR line with g = 2 with the line with g = 1.875 retained, and (iii) the transition of the sample to a low-resistivity state (ρ ～ 100 Ω cm).     

Critical behaviour in the shear elasticity of adamantane in the plastic phase

The elastic constants of the molecular crystal adamantane (C₁₀H₁₆) have been measured at 10 MHz as a function of temperature in the cubic plastic phase, with special attention given to the region just above the order-disorder transition into the tetragonal rigid phase. Both the velocity and attenuation of the C′ shear wave exhibit incipient critical behavior near this transition. The C′ stiffness also shows a pretransitional softening when this transition is approached by increasing the pressure along several isotherms.     

Study of phase transitions and properties of tetragonal (Pb,La)(Zr,Ti)O3 ceramics—II: Diffuse phase transitions and thermodynamics

The diffuse phase transition in tetragonal PLZT materials has been investigated. Strongly broadened permitivity curves were observed for materials with a relative high La content. Curie-Weiss behaviour in the permittivity curves is observed only at temperatures far above the apparent Curie temperature.A latent heat effect is observed at the sharp FE_t → PE_c transition in PLZT x/30/70 materials with a low La content (x<16 at° La). This heat effect decreases linearly with increasing La content. The diffuse tetragonal → cubic transition is attended with a very small heat-effect and a low value (≈0.04 cal/mol°C) for the entropy difference between high and low temperature phase could be determined.Consequently, polarisation fluctuations are possible in a certain temperature interval around the transition.     

Ferromagnetism in the high-pressure phases of (GaSb)1−x Mnx

The electrophysical and magnetic properties of recently discovered high-pressure phases in the GaSb-Mn system with simple cubic and tetragonal structures have been examined. It has been shown that samples with the primitive cubic structure for low temperatures are in the ferromagnetic state and the Curic temperature depends on the initial manganese content and reaches T _c = 280 K for x = 0.6. It has been shown that these samples for a manganese content x ≤ 0.5 are in the semiconducting state with large impurity conduction and pass to the metallic state as x increases. The GaSbMn phase with the tetragonal structure has ferromagnetic properties up to temperatures of T ～450 K (at which the phase begins to decay) and exhibits metallic properties. The magnetization at T = 77.3 K is equal to M = 0.58 μ_B and 0.28 μ_B per manganese ion for the simple cubic and tetragonal phases, respectively.     

Lattice dynamics and the phase transition from the cubic phase to the tetragonal phase in the LaMnO<Subscript>3</Subscript> crystal within the polarizable-ion model

The paper reports on the results of ab initio calculations of the static and dynamic properties of the LaMnO₃ crystal with a perovskite structure in the cubic, rhombohedral, and orthorhombic phases. The calculations are performed within the ionic crystal model, which takes into account the deformability and polarizability of the ions. It is revealed that the spectrum of lattice vibrations in the cubic phase contains unstable vibrational modes, which occupy the phase space in the entire Brillouin zone. The eigenvectors of the softest mode at the boundary point R of the Brillouin zone are associated with the displacements of the oxygen ions and correspond to the “rotation” of the MnO₆ octahedron. The condensation of one, two, and three components of this mode leads to the tetragonal, orthorhombic, and rhombohedral distortions of the structure. The structural phase transition is described in terms of the local mode approximation with the use of the double perovskite unit cell, in which the MnO₆ octahedron is explicitly separated. The parameters of the model Hamiltonian are determined. The static properties are investigated by the Monte Carlo method. The calculated temperature of the phase transition from the cubic phase (9800 K) is considerably higher than the melting temperature of the crystal under investigation. The calculated frequencies of long-wavelength lattice vibrations in the experimentally observed orthorhombic and rhombohedral phases are in reasonable agreement with experimental data.