Conductivity behaviour of a cubic/tetragonal phase stabilized nanocrystalline La2O3-ZrO2

La₂O₃ doped nanocrystalline zirconia (ZrO₂) was prepared by chemical co-precipitation method for the 3, 5, 8, 10, 15, 20 and 30 mol.% concentrations of La₂O₃. Structural studies were performed using X-ray diffraction (XRD). All the as-synthesized samples were found to be in monoclinic phase. As-synthesized samples were given heat treatment at higher temperatures for tetragonal/cubic structural phase stabilization. Sintering the samples at temperature 1173 K stabilized the tetragonal and cubic phases. A slight shift in the 100% peak of the cubic phase was observed towards the low diffraction angle indicating the substitution of the bigger La³⁺ ion into the ZrO₂ lattice. Grain sizes were found to lie between 10 and 13 nm. Electrical conductivity studies were performed on the cubic phase stabilized La₂O₃-ZrO₂ by complex impedance spectroscopy. The conductivity increases up to the dopant concentration 10 mol.% and then decreases with further increase in La₂O₃ concentration. Initial increase in conductivity is correlated to the stabilization of the cubic phase and the subsequent decrease in the conductivity with the dopant content is interpreted on the basis of the oxygen-ion movement model. Electrical conductivity has contributions from grain and grain boundary regions. But the grain boundary conductivity is slightly higher than the corresponding grain conductivity. Higher grain boundary conductivity shows higher diffusion coefficient for the atoms on the surface of the ZrO₂ grains. The possible mechanism of the oxygen ion conduction in the La₂O₃ stabilized zirconia (LSZ) is reported. The Barton, Nakajima and Namikawa (BNN) relation has been applied to the conductivity data and found that the d.c. and a.c. conductions have been correlated to each other by the same mechanism.     

Electrical and thermal properties in CuV2S4

The successive phase transitions of the cubic spinel structure CuV₂S₄ have been studied by the electrical resistivity and the specific heat. In the resistivity and the specific heat two anomalies have been observed at T₁～91 K and T₃≈55 K. The specific heat indicates that the phase transition at T₁ is in the vicinity of a tricritical point, where the resistivity has a small sharp peak. On the other hand, the specific heat shows a step at T₃, where a hysteresis of the resistivity indicates the existence of the first-order phase transition.     

Disorder-order phase transition induced by size effect in bulk La2/3Sr1/3MnO3

Bulk La_2/3Sr_1/3MnO₃ ceramic samples prepared by thermal decomposition are investigated using transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM). An abnormal phenomenon, where three kinds of La_2/3Sr_1/3MnO₃ phases with different structures and the same composition coexist in the same grain, has been observed. Besides the stable rhombohedral majority phase, the two other phases are a simple cubic structure with a=0.389 nm and a new hexagonal structure with a=0.544 nm, c=0.668 nm. The simple cubic phase is a residual phase of high-temperature due to the size effect and bondage of twin boundary. Image simulations have suggested that the new hexagonal phase is the La-Sr ordered structure with space group , which is converted from the disordered simple cubic phase. The formation mechanism of the ordered phase is explained from volume energy and interface energy considerations.     

Superprotonic solid solutions between CsHSO4 and CsH2PO4

Solid solutions of (CsHSO₄)_1 − x(CsH₂PO₄)_x (x = 0.25-0.75) were synthesized by mechanical milling method over a wide range of compositions. Superprotonic cubic phase was confirmed for all these samples between 293 and 420 K depending on its composition. These superprotonic phases have primitive cubic structure similar to that of CsH₂PO₄. The kinetic stability of the supercooled cubic phase depends both on the composition x and the humidity of surrounding atmosphere. The most stable composition of the cubic phase was found around x = 0.67 and could be maintained for several days even under ambient atmosphere. The ionic conductivities of these superprotonic phases reached 10^− 2–10^− 3 S∙cm^− 1 at 450 K. With increasing x the ionic conductivity at the superprotonic phase decreased continuously associated with the increase of the activation energy. These findings suggest that the average number of the hydrogen bonds between XO₄ (X = S, P) units plays an important role on the stability of the cubic phase and also on the conductivity.     

Semiconductor-metal transition in novel Cd2Os2O7

Cd₂Os₂O₇ has been prepared for the first time and has the pyrochlore structure with a cubic cell edge of 10.17 Å at room temperature. Electrical, magnetic, and DSC measurements on single crystals of this compound show a sharp transition at 225 K which we interpret to be an electronic, second-order, metal-semiconductor transition. The low-temperature semiconducting phase is probably antiferromagnetic.     

Soft mode and structural phase transition in the cubic elpasolite Cs2NaNdCl6

Inelastic neutron scattering measurements have been performed on the elpasolite Cs₂NaNdCl₆ in the cubic phase. It is found that the cubic-to-tetragonal phase transition at 137 K is driven by a zone-center soft phonon mode. The mode is of symmetry Λ^′₁₅ and corresponds to a rotation of the Cl₆ octahedra. The characteristics of the phase transition are similar to those observed in some compounds of the perovskite and antifluorite structures.     

Pressure-induced structural phase transition in rare-earth trihydrides. Part I. (GdH3, HoH3, LuH3)

High-pressure X-ray diffraction studies of gadolinum, holmium and lutetium trihydrides have been carried out in a diamond anvil cell up to 30 GPa at room temperature. A reversible structural phase transformation from the hexagonal to cubic phase has been observed for all the hydrides investigated. These results confirm our first discovery of the hexagonal to cubic phase transition in erbium trihydride published recently [T. Palasyuk, M. Tkacz, Solid State Commun. 130 (2004) 219. [1]]. The lattice parameters of the new cubic phases and the volume changes at transition points were determined for SmH₃, GdH₃, and HoH₃. The parameters of the equation of state for all the hexagonal and cubic phases of the investigated compounds have been determined.     

A lattice dynamical investigation of the Raman and the infrared frequencies of the cubic Y2Ru2O7 pyrochlore

A short-range force constant model has been applied for the first time to investigate the Raman and the infrared frequencies in Y₂Ru₂O₇ pyrochlore in its cubic phase of space group Fd3m. The calculations of zone center phonons have been made with four stretching and three bending force constants. The calculated values of Raman and infrared frequencies are in good agreement with the observed ones.     

Structural transformation in Mg2NiH4

X-Ray diffraction measurements show that on heating Mg₂NiH₄ in a 1 atm pressure H₂ atmosphere, above ～250°C it transforms into a cubic structure, metal atoms in CaF₂ arrangement, a = 6.525 Å. It is concluded that the H atoms are in tetrahedral clusters, and that the structure is only weakly ionic. This conclusion is also supported by NMR measurements. The 20°C structure of Mg₂NiH₄ is shown to be describable primarily as a slight monoclinic distortion of the cubic unit cell; a = 6.594 Å, b = 6.412 Å, c = 6.490 Å and β = 93.1°. However, weak small angle lines show that a longer range order exists and that the true unit cell, which we have not determined, must be very large. To what extent the cubic phase should be considered a high temperature and/or low concentration (Mg₂NiH_4??) phase is not resolved.     

Hydrothermal synthesis, characterization and Raman studies of Eu activated Gd2O3 nanorods

Eu³⁺ (8 mol%) activated gadolinium oxide nanorods have been prepared by hydrothermal method without and with surfactant, cityl trimethyl ammonium bromide (CTAB). Powder X-ray diffraction (PXRD) studies reveal that the as-formed product is in hexagonal Gd(OH)₃:Eu phase and subsequent heat treatment at 350 and 600 °C transforms the sample to monoclinic GdOOH:Eu and cubic Gd₂O₃:Eu phases, respectively. The structural data and refinement parameters for cubic Gd₂O₃:Eu nanorods were calculated by the Rietveld refinement. SEM and TEM micrographs show that as-obtained Gd(OH)₃:Eu consists of uniform nanorods in high yield with uniform diameters of about 15 nm and lengths of about 50-150 nm. The temperature dependent morphological evolution of Gd₂O₃:Eu without and with CTAB surfactant was studied. FTIR studies reveal that CTAB surfactant plays an important role in converting cubic Gd₂O₃:Eu to hexagonal Gd(OH)₃:Eu. The strong and intense Raman peak at 489 cm⁻¹ has been assigned to A_g mode, which is attributed to the hexagonal phase of Gd₂O₃. The peak at ∼360 cm⁻¹ has been assigned to the combination of F_g and E_g modes, which is mainly attributed to the cubic Gd₂O₃ phase. The shift in frequency and broadening of the Raman modes have been attributed to the decrease in crystallite dimension to the nanometer scale as a result of phonon confinement.     

Microstructure characterization and phase transformation kinetic study of ball-milled m-ZrO2–30 mol% a-TiO2 mixture by Rietveld method

High-energy ball milling of monoclinic ZrO₂–30 mol% anatase TiO₂ mixture at different durations results in the formation of m-ZrO₂–a-TiO₂ solid solution from which the nucleation of nanocrystalline cubic (c) ZrO₂ polymorphic phase sets in. Post-annealing of 12 h ball-milled sample at different elevated temperatures for 1 h results in almost complete formation of c-ZrO₂ phase. Microstructure of the unmilled, all the ball milled and annealed samples has been characterized by Rietveld's X-ray powder structure refinement method. Particle size, rms lattice strain, change in lattice parameters and phase content of individual phases have been estimated from Rietveld analysis, and are utilized to interpret the results. In course of milling, (1 1 1) of cubic lattice became parallel to () plane of monoclinic lattice due to the orientation effect and cubic phase may have been formed on the (0 0 1) of the m-ZrO₂–a-TiO₂ solid solution lattice. A comparative study of microstructure and phase transformation kinetics of ZrO₂–10, 20 and 30 mol% a-TiO₂ ball-milled and post-annealed samples reveals that rate of phase transformation m→c-ZrO₂ increases with increasing a-TiO₂ concentration and 30 mol% of nanocrystalline c-ZrO₂ phase can be obtained within 4 h of milling time in the presence of 30 mol% of a-TiO₂. The post-annealing treatment at 773, 873 and 973 K for 1 h duration each reveals that rate of c-ZrO₂ formation with increasing temperature is retarded with increasing a-TiO₂ concentration but the amount of c-ZrO₂ becomes almost equal (95 mol%) at 973 K. It suggests that almost fully stabilized nanocrystalline c-ZrO₂ can be formed by adding a tetravalent solute to m-ZrO_2.     

Structural relation and epitaxial properties of hexagonal InN and oxidized cubic In2O3

The epitaxial properties and structural relation between hexagonal InN and cubic In₂O₃ phases were studied by synchrotron X-ray scattering and X-ray photoelectron spectroscopy. The cubic bixbyite In₂O₃ phase on the sapphire(0001) substrate was formed after an annealing time of 10 min at 10⁻⁵ Torr after the hexagonal InN film was grown at 550 °C, above the dissociation temperature of InN, by RF-magnetron sputtering. The crystal orientation was cubic In₂O₃(222), parallel to Al₂O₃(0001) and parallel to hexagonal InN(0002) before the oxidation process. The cubic In₂O₃ phase was believed to be formed layer by layer by the oxidation of the hexagonal InN phase.     

Photoluminescence of cubic and monoclinic Gd2O3:Eu phosphors prepared by flame spray pyrolysis

In this paper, europium-doped gadolinium phosphor, which is a potentially bifunctional material with both fluorescent and magnetic properties, has been prepared in a one-step procedure via flame spray pyrolysis, and its crystal structure, morphology, and PL intensity were investigated. All the prepared phosphors were submicron-sized with spherical shapes and either a pure cubic or pure monoclinic phase. In order to observe the effects of temperature on the crystal phases of the prepared phosphors, we applied a H₂ vs. N₂/O₂ diffusion flame, with the maximum flame temperature ranging from T_max=1375 to 2050 K. The temperature profiles under various flame conditions are also reported herein to further elucidate the rapid synthesis process. The PL intensity in the cubic phase improved linearly with increasing flame temperature until the transition to a monoclinic phase. The peak of the photoluminescence(PL) spectrum from the phosphors prepared at T_max=1733 K in the cubic phase was narrower and twice as strong as the peak of the PL spectrum from the phosphors prepared at T_max=2050 K in the monoclinic phase. This paper provides important data showing the relationship between the synthesis temperature and the phase transition in Gd₂O₃:Eu in the continuous one-step use of flame spray pyrolysis.     

Order-disorder phase transition in ZrV2D3.6

The deuterated C15-type Laves phase ZrV₂D_3.6 undergoes a structural phase transition near room temperature (T ≈ 325 K). In the cubic high-temperature phase the deuterium atoms are disordered over two types of tetrahedral interstices, the centres of which are 1.3 Å apart. In the tetragonal low-temperature phase the D atoms are ordered and occupy only the energetically more favourable interstices. The tetragonal structure is isotypic with the low-temperature phase of HfV₂D₄. The shortest D—D distance is 2.1 Å.     

Structural stability and electronic properties of Co2N, Rh2N and Ir2N

The structural stability and electronic properties of Co₂N, Rh₂N and Ir₂N were studied by using the first principles based on the density functional theory. Two structures were considered for each nitride, orthorhombic Pnnm phase and cubic Pa3¯ phase. The results show that they are all mechanically stable. Co₂N in both phases are thermodynamically stable due to the negative formation energy, while the remaining two compounds are thermodynamically unstable. The calculated properties show that they are all metallic and non-magnetic. Ir₂N at Pnnm phase is a potentially hard material. The bonding behavior is analyzed.     

Magnetic structure of the cubic U2Te3 with a non-stoichiometric Th3P4 type of structure

The neutron diffraction patterns of the cubic U₂Te₃ have been obtained at 15 and 150 K. There are no extrapeaks of magnetic origin below the Curie point T_c = 70 ± 5 K. Thus the ordering corresponds to a collinear ferromagnetic structure. The value of the magnetic moment is 1.78 μ_B which is close to those values determined for a few cubic uranium pnictides and chalcogenides.     

Spectroscopic studies of interfacial structures of CeO2-TiO2 mixed oxides

We have investigated the geometric and electronic structures of the cerium oxide (CeO₂)-titanium dioxide (TiO₂) mixed oxides with various Ce/TiO₂ weight ratios prepared by the sol-gel method in detail by means of X-ray diffraction (XRD), high-resolution X-ray photoelectron spectroscopy (XPS), Raman spectroscopy excited by 325 and 514.5 nm lasers, and scanning electron microscope (SEM). Existence of cerium effectively inhibits the phase transition of TiO₂ from the anatase phase to the rutile phase. XRD peaks of TiO₂ anatase attenuate continuously with the increasing amount of CeO₂ in the mixed oxide, but the XRD peaks of cubic CeO₂ appear only after the weight ratio of Ce/TiO₂ reaches 0.50. The average crystalline sizes of TiO₂ anatase and cubic CeO₂ in CeO₂-TiO₂ mixed oxides are smaller than those in the corresponding individual TiO₂ anatase and cubic CeO₂. Raman spectroscopy excited by the 514.5 nm laser detects CeO₂ after the weight ratio of Ce/TiO₂ reaches 0.70 whereas Raman spectroscopy excited by the 325 nm laser detects CeO₂ after the weight ratio of Ce/TiO₂ reaches 0.90. XPS results demonstrate that Ti exists in the form of Ti⁴⁺ in the CeO₂-TiO₂ mixed oxide. Ce is completely in the form of Ce³⁺ in the mixed oxides with a 0.05 weight ratio of Ce/TiO₂. With the increasing weight ratio of Ce/TiO₂, Ce⁴⁺ dominates. On basis of these results, we proposed that CeO₂ initially nucleates at the defects (oxygen vacancies) within TiO₂ anatase, forming an interface bridged with oxygen between CeO₂ and TiO₂ anatase. At the interface, Ce species cannot substitute Ti⁴⁺ in the lattice of TiO₂ anatase whereas Ti⁴⁺ can substitute Ce⁴⁺ in the lattice of cubic CeO₂. The decreasing concentration of oxygen vacancies, the Ti-O-Ce interface, and the decreasing average crystalline size of TiO₂ anatase act to inhibit the phase transformation of TiO₂ anatase. With the increasing amounts of CeO₂, the CeO₂ clusters continuously grow and form cubic CeO₂ nanocrystals. Spectroscopic results strongly demonstrate that the surface region of CeO₂-TiO₂ mixed oxide is enriched with TiO₂.     

Inelastic neutron scattering from transverse acoustic modes in K2SnCl6

In cubic K₂SnCl₆ the dispersion curve für q q; [110] of [1$\text{1}$0] polarized acoustic phonons has been measured at three temperatures near the phase transition temperature T_c1. The acoustic branch shows no temperature dependence in the low wave vector region and stiffens slightly near the X-point of the fcc-Brillouin zone as the temperature approaches the phase transition T_c1= 262 K from above. The results support a previously developed model on acoustic anomalies in this compound.     

α-Fe2O3-In2O3 mixed oxide nanoparticles synthesized under hydrothermal supercritical conditions

α-Fe₂O₃-In₂O₃ mixed oxide nanoparticles system has been synthesized by hydrothermal supercritical and postannealing route, starting with (1−x)Fe(NO₃)₃·9H₂O·xIn(NO₃)₃·5H₂O aqueous solution (x=0-1). X-ray diffraction and Mössbauer spectroscopy have been used to study the phase structure and substitutions in the nanosized samples. The concentration regions for the existence of the solid solutions in the α-Fe₂O₃-In₂O₃ nanoparticle system together with the solubility limits of In³⁺ ions in the hematite lattice and of Fe³⁺ ions in the cubic In₂O₃ structure have been evidenced. In general, the substitution level is considerably lower than the nominal concentration x. A justification of the processes leading to the formation of iron and indium phases in the investigated supercritical hydrothermal system has been given.     

Low temperature phase transition in cubic elpasolithe crystal Cs2NaBiCl6

The structural properties of the cubic compound Cs₂NaBiCl₆ have been investigated. X-ray diffraction patterns were observed from 300 to 7 K. On lowering the temperature, this compound undergoes a structural transformation starting at 90 K. This structural evolution was monitored by the thermal behavior of the 400 and 440 reflections. The crystallographic data was completed by Raman scattering measurements on an oriented sample. The phase transformation involves only the external mode corresponding to the Cs⁺ translation. The lattice instability of Cs₂NaBiCl₆ appears to be related to the size of the cesium ion site. Comparison with results obtained for isomorphous compounds strongly supports our interpretations.