The CoO/Co3O4 phase transition studied by PAC

The hyperfine environment of¹¹¹Cd nuclei formed in the radioactive decay of¹¹¹In ions implanted into CoO was studied via the PAC method. The quadrupole coupling constants measured in isochronal and isothermal annealing treatments at various oxygen pressures were related to the initial stages of the CoO→Co₃O₄ phase transition and interpreted as the successive trapping of cation vacancies at the¹¹¹In probe. The phase transition was confirmed by X-ray diffraction, RBS and a PAC measurement on¹¹¹Cd in spinel type Co₃O₄.     

Structural phase transition in LiFeSi2O6 from ab initio calculations

The changes in crystal structure of LiFeSi(2)O(6) induced by the phase transition between the high-temperature C2/c and low-temperature P2(1)/c phase are studied using the density functional theory. For both monoclinic phases, the phonon dispersion curves and phonon density of states are calculated. The infrared absorption coefficients are obtained and analyzed in both structural phases of LiFeSi(2)O(6). The soft mode inducing the phase transition is revealed at the Z point of the Brillouin zone of the high-symmetry C2/c phase. The pressure dependence of the soft mode is studied and the mechanism of the structural phase transition in LiFeSi(2)O(6) is discussed.     

Structural transition and pair formation in Fe3O2BO3

We observe for the first time a structural phase transition in the oxyborate Fe3O2BO3 which occurs along three leg ladders present in this material. X-ray diffraction shows that this transition at 283 K is associated with a new phase where atomic displacements occur in alternate directions perpendicular to the axis and within the plane of the ladders. Magnetic data show that these displacements lead to the formation of singlet pairs which dissociate close to the structural transition. Anomalies in the transport properties also occur close to 283 K showing that the structural transition is related to a charge ordering phenomenon in a low dimensional structure.     

The ferroelectric phase transition in tridymite type BaAL2O4 studied by electron microscopy

The paraelectric-ferroelectric (PE-FE) phase transition in stuffed tridymite BaAl₂O₄ was studied in situ by transmission electron microscopy. Electron diffraction revealed that the PE and FE phases have hexagonal symmetry. The PE-FE phase transition is accompanied by a doubling of the cell dimensions in the a-b plane. The transition is reversible, takes place over a wide temperature range (400–670 K.) and the interfaces related to the transition have a fluctuating character. The crystal structure of the high temperature PE phase was determined by high resolution electron microscopy. The structures of the PE phase (space group P6₃22, a≈ 5.22 Å, c ≈ 8.8 Å) and of the FE phase (space group P6₃, a= 10.4469(1)Å, c = 8.7927(1)Å) differ mainly by the configuration of the Al-O strings oriented along the c-axis. In the PE phase all the strings are equivalent whereas straight and corrugated strings alternate in an ordered manner in the FE phase resulting in doubling of the a and b cell parameters. Translation and orientation domains due to the decrease of the translation and point symmetry were frequently observed.     

Structural phase transition in Bi2Te3 under high pressure

Structural change in Bi₂Te₃ under high pressure up to 16.6 GPa has been studied by powder x-ray diffraction. We observed two times of phase transitions at room temperature at the pressures of 8 and 14 GPa, respectively. According to our preliminary result on electrical resistance, it is reasonable to suppose that superconducting transition with T _c =2.8 K at the pressures of 10.2 GPa is observed in phase II. On the other hand, we found anomalies of the pressure dependences of lattice parameters and volume at around 2 GPa, which probably means the change in electrical structure on the Fermi surface.     

HighT c superconductivity in YBa2Cu3O7−x studied by PAC and PAS

HighT _c superconductivity has been investigated in YBaCuO by both perturbed angular correlation and positron annihilation spectroscopy techniques as a function of temperature from 77 to 300 K. An abrupt change has been observed in the positron lifetime and Doppler broadening and the electric field gradient and its asymmetry parameter acrossT _c, indicating a transition of two- to one-dimensional Cu-O-Cu chain structure and a charge transfer from CuO layers to CuO chains. An anomaly of the normal state has been demonstrated around 125 K, which is attributed to the structural instability.     

Structural phase transition due to La substitution in Bi4Ti3O12

The structure of Bi_4?x La _x Ti₃O₁₂ (BLaTx) as a function of La content from x = 0.00 to 1.25 was studied by Raman spectroscopy and X-ray diffraction (XRD). It was observed that the Raman modes evolve discontinuously at about x = 1.00, which indicates a structural phase transition. Specifically, the B _2g and B _3g Raman modes shown evidences to coalesce into E _g modes with increasing La content. The evolution of Raman modes corresponds to the weakening of ferroelectric orthorhombic lattice distortion with increasing La substitution when x ≤ 1.00 and the final transition into the paraelectric tetragonal structure at higher La content. XRD and electrical measurement results confirm this phase transition by the observation that diffraction peaks from (200) and (020) planes of BLaT0.75 coalesce into one peak in BLaT1.25 and by the corresponding disappearance of remanent polarisation. The impact of La substitution on electrical properties of BLaTx is discussed briefly.     

Structural phase transition in elpasolite-like (NH4)2KWO3F3

A new chemical compound, (NH₄)₂KWO₃F₃, was synthesized. The Rietveld-refined crystal structure was found to be cubic at room temperature and to belong to the elpasolite family (space group ). The heat capacity and unit cell parameters were studied within a broad temperature range. A second-order phase transition was found to occur at 235.4 K and to be well described in terms of phenomenological theory. Hydrostatic pressure broadens the temperature interval of stability of the cubic phase (dT₀/dp = −10.8 K GPa⁻¹). A possible model of structural ordering based on a comparison of the entropy parameters and electron density distribution in oxygen and fluorine atoms is discussed.     

Ferroelastic phase transition in CaCl2 studied by Raman spectroscopy

CaCl₂ undergoes a second-order proper ferroelastic phase transition from the tetragonal rutile type to the orthorhombic calcium-chloride type structure atT _c 490 K. The transition is of the optical type and induced by an order parameter ofB _1g symmetry. An underdamped soft mode exists above and belowT _c , the frequency and intensity of which have been measured by Raman spectroscopy. Due to a strong coupling to strain the softening is incomplete and a transverse acoustical mode is predicted to become soft. The frequency of the optical soft mode, _s, exhibits a classical Landau behavior in a remarkably large temperature range. The unusual value of the ratio of _s ² / below and aboveT _c of about –6.5 can be accounted for by appropriate terms of the thermodynamical potential. The Raman active hard modes show no significant anomaly atT _c .     

Antiferromagnetic phase transition in garnet-type AgCa2Mn2V3O12 and NaPb2Mn2V3O12

Ferrimagnetism has been extensively studied in garnets, whereas it is rare to find the antiferromagnet. Present work will demonstrate antiferromagnetism in the two Mn–V-garnets. Antiferromagnetic phase transition in AgCa₂Mn₂V₃O₁₂ and NaPb₂Mn₂V₃O₁₂ has been found, where the magnetic Mn²⁺ ions locate only on octahedral A site. The heat capacity shows sharp peak due to antiferromagnetic order with the Néel temperature T_N=23.8 K for AgCa₂Mn₂V₃O₁₂ and T_N=14.2 K for NaPb₂Mn₂V₃O₁₂. The magnetic entropy change over a temperature range 0–50 K is 13.9 J K^?1 mol-Mn²⁺-ions^?1 for AgCa₂Mn₂V₃O₁₂ and 13.6 J K^?1 mol-Mn²⁺-ions^?1 for NaPb₂Mn₂V₃O₁₂, which are in good agreement with calculated value of Mn²⁺ ion with spin S=5/2. The magnetic susceptibility shows the Curie–Weiss behavior over the range 29–350 K. The effective magnetic moment μ_eff and the Weiss constant θ are μ_eff=6.20 μ_B Mn²⁺-ion^?1 and θ=?34.1 K (antiferromagnetic sign) for AgCa₂Mn₂V₃O₁₂ and μ_eff=6.02 μ_B Mn²⁺-ion^?1 and θ=?20.8 K for NaPb₂Mn₂V₃O₁₂.     

Catalytic ignition of light hydrocarbons over Rh/Al2O3 studied in a stagnation-point flow reactor

The ignition (light-off) temperatures of catalytic oxidation reactions provide very useful information for understanding their surface reaction mechanism. In this study, the ignition behavior of the oxidation of hydrogen (H₂), carbon monoxide (CO), methane (CH₄), ethane (C₂H₆), and propane (C₃H₈) over Rh/alumina catalysts is examined in a stagnation-point flow reactor. The light-off temperatures are identified by means of the sudden increase of the catalyst temperature when linearly heating the catalyst for various fuel/oxygen ratios. For hydrogen and all hydrocarbons studied, the results show a rise of ignition temperature with increasing fuel/oxygen ratio, whereas the opposite trend is observed for the light-off of CO oxidation. Hydrogen oxidation, however, shows an opposite trend compared to previous investigations, performed on platinum [1], [2].     

Optical study of the antiferromagnetic-paramagnetic phase transition in chromium oxide Cr2O3

Abstract

Optical effects of the first and second order with respect to the order parameter (1 is antiferromagnetic vector) have been studied in Cr₂O₃ around its phase transition at T_N = 306 K from the antiferromagnetic to paramagnetic state. The magnetic linear birefringence is characterized by a rather large magnitude Δn _sp ? 10^?3 and by a large contribution of fluctuations of the order parameter to the birefringence. The study of the nonreciprocal optical rotation induced by an electric field has shown that the phase transition has a well defined first-order character. This result is also supported by the observation of a nonlinear (quadratic in the electric field) nonreciprocal rotation in a narrow temperature region ΔT = 0.15 K around T_N . The temperature variation of the order parameter l(T) below T_N is well described by a power low l where τ^β = (T_N - T)/T_N and β = 0.355. We also observed a very reproducible effect of the rotation of the optical indicatrix in opposite directions for two types of antiferromagnetic domains. The possible explanation of this effect could be related to the so-called gyrotropic birefringence, an effect related to k_il_i terms in the dielectric permeability.     

Low-temperature phase transition in Ba2TiGe2O8

Previous work on Ba₂TiGe₂O₈ crystals has shown an unusual low-temperature (～ 223 K on cooling, ～ 273 K on heating) phase transition. Precession x-ray photographs on Ba₂TiGe₂O₈ single crystals show an incommensurate modulation along b*, and, for the first time, also along a*. Single crystal intensity data confirm the average structure in space group Cmm2. There is positional disorder in the pyrogermanate groups, and this is the probable cause for the modulated structure. The low-temperature phase transition is proposed to be a lock-in transition, with the modulation along a* locking in at a value of 1/3. Several properties, as well as other unusual features of the low-temperature phase transition, are discussed in light of the proposed lock-in transition. Domain studies show that the ferroelastic domains are unstable in the low-temperature phase.     

Precision PAC measurements in Er2O3 and Ho2O3 single crystals and structure refinement

The structure of C-form Ho₂O₃ and Er₂O₃ single crystals and powder samples was investigated by the electric quadrupole hyperfine interaction of¹¹¹In(EC)¹¹¹Cd probe ions using the perturbed - angular correlation method (PAC). The resulting set of refined atomic coordinates is compared to X-ray data and used to calculate the orientations of the electric field gradients (EFG) which are reproduced by the PAC measurements in single crystals. The temperature dependence of the coordinates was measured for both substances.     

Cooperative Jahn-Teller phase transition in LaMnO3 studied by X-ray absorption spectroscopy

The local structure of LaMnO3 across the Jahn-Teller (JT) transition at T(JT)=750 K was studied by means of x-ray absorption near edge structure and extended x-ray absorption fine structure at the Mn K-edge. Our results indicate a similar electronic local structure for Mn atoms above and below T(JT) and a dynamical tetragonal JT distortion of MnO6 octahedra above T(JT). The structural transition is originated by the ordering of tetragonally distorted octahedra. The entropy content of the transition is analyzed within the framework of the three-state Potts model with nearest neighbor antiferrodistortive coupling.     

Structural phase transition in the 2D spin dimer compound SrCu 2 ( BO 3 ) 2

A displacive, 2nd order structural phase transition at T _s = 395 K from space group I 2 m below T _s to I 4/m c m above T _s has been discovered in the two-dimensional spin dimer compound SrCu₂(BO₃)₂. The temperature evolution of the structure in both phases has been studied by X-ray diffraction and Raman scattering, supplemented by differential scanning calorimetry and SQUID magnetometry. The implications of this transition and of the observed phonon anomalies in Raman scattering for spin-phonon and interlayer coupling in this quantum spin system will be discussed. Received 24 July 2000 and Received in final form 2 November 2000     

Effect of pressure on cubic (C-type) Eu2O3 studied via Eu3+ luminescence

Abstract

Luminescence spectra from Eu³⁺ ion in C-type Eu₂O₃ under high pressures have been obtained. The spectral shifts can be used to study the effect of pressure on the spin-orbit and the Coulomb interactions of the 4f electrons, which are correlated with expansion of the 4f-electron wave functions. This expansion with the application of pressure results in both the variation of the electronegativity and radius of the Eu³⁺ ion and, ultimately, the phase transformation from C-to B-type Eu₂O₃. Therefore, core 4f-electrons can thus be thought of as quasivalence electrons.     

Triangular to square flux lattice phase transition in YBa2Cu3O7

We have used the technique of small-angle neutron scattering to observe magnetic flux lines directly in a YBa2Cu3O7 single crystal at fields higher than previously reported. For field directions close to perpendicular to the CuO2 planes, we find that the flux lattice structure changes smoothly from a distorted triangular coordination to nearly perfectly square as the magnetic induction approaches 11 T. The orientation of the square flux lattice is as expected from recent d-wave theories but is 45 degrees from that recently observed in La(1.83)Sr(0.17)CuO(4+delta).     

High-pressure phase transition of Bi2Fe4O9

The high-pressure behaviour of Bi2Fe4O9 was analysed by in situ powder and single-crystal x-ray diffraction and Raman spectroscopy. Pressures up to 34.3(8) GPa were generated using the diamond anvil cell technique. A reversible phase transition is observed at approximately 6.89(6) GPa and the high-pressure structure is stable up to 26.3(1) GPa. At higher pressures the onset of amorphization is observed. The crystal structures were refined from single-crystal data at ambient pressure and pressures of 4.49(2), 6.46(2), 7.26(2) and 9.4(1) GPa. The high-pressure structure is isotypic to the high-pressure structure of Bi2Ga4O9. The lower phase transition pressure of Bi2Fe4O9 with respect to that of Bi2Ga4O9 (16 GPa) confirms the previously proposed strong influence of cation substitution on the high-pressure stability and the misfit of Ga3+ and Fe3+ in tetrahedral coordination at high pressure. A fit of a second-order Birch–Murnaghan equation of state to the p–V data results in K0 = 74(3) GPa for the low-pressure phase and K0 = 79(2) GPa for the high-pressure phase. The mode Grüneisen parameters were obtained from Raman-spectroscopic measurements.