Influence of Rb,Cs, and Ba on the superconductivity of magnesium diboride

Magnesium diboride has been thermally treated in the presence of Rb, Cs, and Ba. The magnetic susceptibility shows the possible onsets of superconductivity in the resulting samples at 52 K (Rb), 58 K (Cs), and 45 K (Ba). Room-temperature ¹¹B NMR indicates the cubic symmetry of the electric field gradient at the boron site for the samples reacted with Rb and Cs, in contrast to the axial symmetry in the initial MgB₂ and in the sample treated with Ba. The text was submitted by the authors in English.     

A nuclear magnetic resonance study of the phase transitions and electric quadrupole Raman processes of M5H3(SO4)4·H2O (M=Na, K, Rb, and Cs) single crystals

The spin–lattice relaxation times and spin–spin relaxation times for ¹H and M in M₅H₃(SO₄)₄·H₂O (M=Na, K, Rb, and Cs) single crystals grown using the slow-evaporation method were measured as functions of temperature. Two kinds of protons were identified in the M₅H₃(SO₄)₄·H₂O structure: acid protons and water protons. Our experimental results show that the acid and water protons in Cs₅H₃(SO₄)₄·H₂O are involved in phase transitions of this crystal, whereas neither type of proton is involved in the phase transitions of the other three crystal type (M₅H₃(SO₄)₄·H₂O; M=Na, K, and Rb). Moreover, the relaxation times for the M (=Na, K, and Rb) nuclei in these crystals were found to decrease with increasing temperature and can be described with (k=2). The T₁ results for M (=Na, K, and Rb) in M₅H₃(SO₄)₄·H₂O crystals can be explained in terms of a relaxation mechanism in which the lattice vibrations are coupled to the nuclear electric quadrupole moments.     

Modeling of lattice constant and their relations with ionic radii and electronegativity of constituting ions of A2XY6 cubic crystals (A=K, Cs, Rb, Tl; X=tetravalent cation, Y=F, Cl, Br, I)

In the present paper a new empirical model is proposed to describe and predict the lattice constants for a series of cubic crystals, all of which have the A₂XY₆ composition (A=K, Cs, Rb, Tl; X=tetravalent cation, Y=F, Cl, Br, I). The model is based on a thorough analysis of structural properties of 85 representative crystals from this group. It was shown that the lattice constant is a linear function of the ionic radii and electronegativity of the constituting ions. A simple empirical equation was obtained as a result of the performed analysis. It gives very good agreement between the experimental and modeled values of the lattice parameters, with an average error of 1.05%. The developed approach can be efficiently used for a simple, fast, and reliable prediction of lattice constants and interionic distances in isostructural materials having a similar composition.     

Phase transitions in the oxyfluoride (NH<Subscript>4</Subscript>)<Subscript>3</Subscript>NbOF<Subscript>6</Subscript>

(NH₄)₃NbOF₆ single crystals were grown, polarization-optical studies were performed, and birefringence was measured over the temperature range 90–500 K. A sequence of first-order structural phase transitions was found at temperatures T _1↓ = 259.7 K and T _2↓ = 257.7 K with temperature hysteresis δT ₁ = 0.9 K and δT ₂ = 1.9 K. The transitions are accompanied by twinning and the following change in the crystal symmetry: cubic ? tetragonal ? monoclinic. Optical second harmonic generation is found to occur at room temperature, which indicates that the cubic phase is not centrosymmetric. It is assumed that the phase transitions are ferroelastic and ferroelectric in nature.     

Structural phase transitions in Fe3+ -doped ferroelectric TlGaSe2 crystal

This paper presents the results of dielectric constant and Electron Paramagnetic Resonance (EPR) investigations of Fe³⁺-doped TlGaSe₂ single crystals in the temperature range of 15–300 K. The influence of Fe impurities on dielectric properties and phase transitions of TlGaSe₂ crystal has been studied. The results were considered in comparison with earlier observed results from pure TlGaSe₂ compounds. We observed the considerable decrease of the dielectric constant as well as the change of the shape of the temperature dependence of the dielectric constant in doped crystals. Some certain significant changes of EPR spectra, which are associated with a strong splitting and appearance of additional resonance lines, were observed at the temperatures below 110 K. Such transformations are considered as the result of non-equivalent displacements of different groups of Tl atoms during the structural phase transitions.     

Structural mechanisms of proton conduction in MemHn(XO4)(m + n)/2 crystals

Investigations of K₃H(SO₄)₂ samples, which belong to the family of Me _m H _n (XO₄)_{(m + n)/2} (Me = K, Cs, Rb, NH₄; X = S, Se, As) crystals, revealed temperature anomalies in the dielectric and optical properties and in the heat capacity upon phase transitions. X-ray diffraction studies confirmed that K₃H(SO₄)₂ crystals undergo a structural phase transition from the monoclinic phase to the trigonal phase C2/c → R m and that the high proton conductivity in the high-temperature phases of crystals belonging to this family is due to the formation of a qualitatively new system of hydrogen bonds. Original Russian Text ? A.A. Simonov, I.P. Makarova, V.V. Grebenev, 2009, published in Fizika Tverdogo Tela, 2009, Vol. 51, No. 8, pp. 1477–1479.     

Physical properties of several M2Mo6X6 compounds (M = GROUP IA METAL; X = Se,Te)

We report the physical properties of the pseudo one dimensional ternary molybdenum chalcogenides M₂Mo₆X₆ (M = K, Rb,Cs,Tl;X = Se, Te) measured on single crystals grown at high temperature. For Group IA metals (Rb,..,Cs) the transport properties evolve from a metallic to a semiconducting-like behavior on decreasing the temperature. Over the same temperature range the Group IIIA compound (Tl₂Mo₆Se₆) remains metallic and even superconducts at 5.1K. The susceptibility of these materials is weakly diamagnetic and does not reveal anomalied correlated to the onset of the broad metal-nonmetal transition, except perhaps for Cs₂Mo₆Te₆. A variation of the electronic interchain coupling is proposed to explain the difference between the Group IA and IIIA metal compounds. In the absence of evidence of three dimensional ordering at low temperature, we suggest that the broad metal-nonmetal transition is due to a fluctuating Pierls gap that is uncorrelated from one Mo chain to the next.     

Temperature calibration for high-temperature MAS NMR to 913 K: 63Cu MAS NMR of CuBr and CuI, and 23Na MAS NMR of NaNbO3

The solid-state phase transitions of CuBr, CuI and NaNbO₃ can be readily observed using ⁶³Cu and ²³Na high-temperature magic-angle spinning nuclear magnetic resonance spectroscopy. Temperature has large, linear effects on the peak maximum of ⁶³Cu in each solid phase of CuBr and CuI, and there is large jump in shift across each phase transition. The ²³Na MAS NMR peak intensities and the line widths in NaNbO₃ also clearly show its high-temperature transition to the cubic phase. These data can be used to calibrate high-temperature MAS NMR probes up to 913 K, which is two hundred degrees higher than the commonly-used temperature calibration based on the chemical shift of ²⁰⁷Pb in Pb(NO₃)₂.     

Structural behaviour of AgNO3 at low temperatures by neutron diffraction

Structural behaviour of silver nitrate (AgNO₃) at low temperatures has been investigated by neutron powder diffraction and differential scanning calorimetry (DSC). Analysis showed abnormal changes in the rotations of nitrate (NO₃) anions and thermal displacement parameters of the atoms near 220 K and 125 K. However, the basic lattice is compatible with the orthorhombic symmetry (space group Pbca) till 12 K. The fine, small-scale structural anomalies probably originate from freezing of reorientation of NO₃ ions from high-temperature disordered phase.      

Electronic Structure of Rhombohedral Oxyanion Crystals

In the context of the theory of the local electron density functional, the band structure, density of states, and electron density are calculated by the pseudopotential method in the basis of the sp ³ d ⁵ numerical atomic pseudoorbitals for MCO₃ (M: Mg or Ca), MNO₃ (M: Li, Na, K, or Rb), MClO₃ (M: Rb or Tl), and MBrO₃ (M: K or Tl) crystals. The nature of the quantum states of the valence band and the character of hybridization between them are elucidated, and on their basis, the series dependences of the band structure parameters are examined.     

Phase transitions in AgTaO3 single crystals

AgTaO₃ single crystals have been obtained by the molten salt method; two different solvents, AgCl and V₂O₅, were used. X-ray investigations have been carried out in the temperature region from 300 K to 800 K. At room temperature AgTaO₃ possesses a pseudocubic perovskite-type unit cell with rhombohedral distortion. Two structural phase transitions, to tetragonal at 650 K and to cubic symmetry at 770 K, have been observed. In the tetragonal phase a jump of the lattice constants has been observed at approximately 680 K. DTA and domain structure investigations confirm the presence of these phase transitions.     

Calorimetric and optical studies of orthorhombic and cubic CsLiCrO4 crystals

Careful calorimetric and polarization optical studies of a metastable cubic modification of a CsLiCrO₄ crystal (space group ( $F\overline 4 3m$ )) are performed. Anomalies of the heat capacity indicative of structural distortions at 92.4 and 69.1 K were revealed, and the values of the thermodynamic parameters of the phase transitions were determined. The crystal twinning in the intermediate phase was studied. A comparative analysis of the phase transitions occurring in a series of ALiMO₄ crystals (A = NH₄, Cs; M = S, Cr, Mo, W) was performed. First studies of the monotropic structural transformation $F\overline 4 3m$ → Pmcn and the enantiotropic phase transition Pmcn ? P112₁/n were carried out using scanning calorimetry, and the thermodynamic parameters of these transitions were determined.     

Investigation of phase transitions and thermal expansion of some complex tungsten-containing oxides

The phase transitions have been investigated and the thermal expansion coefficients have been determined in compounds with a structure of brannerite, defect pyrochlore, and tungsten bronze of the general formula M ^I A ^VWO_{6 − δ} (M ^I = □, H₃O, Li, Na, K, Rb, and Cs; A ^V = V, Nb, Sb, and Ta; δ = 0, 0.5) by high-temperature X-ray diffraction and differential thermal analysis. It has been shown that brannerites and tungsten bronze do not undergo phase transitions and the compounds are characterized by a significant anisotropy of the thermal expansion, whereas pyrochlores undergo phase transitions of three types, and thermal deformations in them are determined by the size of M ^I atoms.     

Raman scattering in A3B2C9 ferroelectric crystals

Raman spectra of some A₃B₂C₉ ferroelectric crystals (here A=Cs, Rb; B=Sb, Bi; C=Br) have been obtained, and a number of high-frequency bands have been assigned. The Rb₃Bi₂Br₉ and Rb₃Sb₂Br₉ crystals are shown to differ in structure from Cs₂Bi₂Br₉. The qualitative changes in the spectra in the 77–300 K temperature interval can be associated not only with structural phase transitions, but with the effect of the anharmonic Fermi resonance between one-and two-phonon excitations as well. Fiz. Tverd. Tela (St. Petersburg) 39, 1452–1455 (August 1997)     

Raman spectra of cadmium titanate

Polarized Raman spectra of CdTiO₃ single crystals are recorded for the first time over the frequency range 5 < ν < 1000 cm^?1 at temperatures of 10 to 1200 K. The emphasis was on the low-frequency range, where an anomalous temperature dependence of a few phonon modes was observed. At high temperatures, four phonon modes exhibiting a behavior typical of soft modes were found to exist. These phonon modes are assumed to restore the cubic symmetry of the lattice. Their extrapolated temperature dependences suggest that there exists a sequence of three hypothetical high-temperature phase transitions analogous to those observed in the genuine perovskite CaTiO₃. At temperatures below 78 K, the Raman spectrum exhibits new lines associated with polar distortions of the unit cell. At low frequencies, three lines are observed whose parameters exhibit an anomalous behavior typical of soft modes in a ferroelectric phase. Several different polar states are assumed to exist at low temperatures.     

Effect of cation substitution in fluorine-oxygen molybdates (NH4)2 ? xAxMoO2F4

Thermophysical and structural studies of (NH₄)_{2 − x} A _x MoO₂F₄ (A = Cs, Rb, K) solid solutions of oxyfluorides have been performed. The character of the influence of cation substitutions on the stability of the initial phase (space group Cmcm) and on the mechanism of phase transitions has been elucidated.     

Diserine sulfate monohydrate: Symmetry, piezoelectric properties, and phase transitions

A new compound, diserine sulfate monohydrate, was synthesized, and single crystals of this compound were grown. X-ray diffraction studies were carried out, and the temperature dependences of the piezoelectric response of these crystals were measured. A conclusion was drawn that the crystals are orthorhombic with the space symmetry group C _1v -Pmm2 and that they apparently undergo phase transitions at 340 and 255 K.     

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.     

Role of the TiO6 octahedra on the ferroelectric and piezoelectric behaviour of the poled PbMg1/3Nb2/3O3-xPbTiO3 (PMN-PT) single crystal and textured ceramic

Field cooling (FC) poled/unpoled PMN-29%PT single crystal and room temperature (RT) poled/unpoled PMN-34.5%PT textured ceramic were investigated between ∼0 and 300 °C by thermal expansion, dielectric and Raman spectroscopy. New phase transitions are evidenced at 40, 91 and 180 °C in the case of FC PMN-29%PT as well as at 70 and 200 °C for RT PMN-34.5%PT and their order is discussed. The physical properties of the textured ceramics are rather similar to the ones observed for the single crystals that make them low-cost alternative for a wide range of applications. However, the temperatures and character of the phase transitions strongly depend on the kind of the poling conditions. Temperature dependences of the Raman line parameters show that the NbO₆ octahedra remain stable during temperature increase, while TiO₆ ones evolve quasi-continuously. The step transitions of the Pb²⁺ ion sublattice are evidenced. This suggests that the TiO₆ and Pb²⁺ sublattices are especially coupled. The role of the TiO₆ clusters on the structural phase transitions and dielectric properties of the PbMg_1/3Nb_2/3O₃-xPbTiO₃ (PMN-PT) system is discussed. The presence of the Raman modes above the maximum dielectric permittivity reveals that the local symmetry is lower than the cubic one (Pm3m). The decrease of the Raman line intensities vs. temperature indicates precisely the continuous evolution of the local symmetry towards the cubic one. The temperature evolution of the Rayleigh wing parameters appears sensitive to the phase transitions’ presence.     

Crystal stability and the theory of ferroelectricity part II. Piezoelectric crystals

In Part I the dielectric properties of cubic crystals with atoms in special positions were discussed, with particular reference to crystals which become unstable against a transverse optic mode of vibration of long wavelength. These considerations are now extended to crystals of general symmetry, and it is shown that the anomalous temperature dependence of certain dielectric, piezoelectric, and elastic constants in the paraelectric phase of ferroelectric crystals can be described and correlated in a very natural way in terms of crystal stability. A formula relating the dispersion frequency of the anomalous dielectric constant to the spontaneous polarization and the displacements of the atoms in a ferroelectric transition, previously derived for barium titanate, is generalized. The transitions in KH₂PO₄ and in NH₄H₂PO₄, and the ordering of the hydrogen atoms in these crystals, are discussed qualitatively in terms of the stability of normal modes of vibration.