Phase fronts at the NaNbO3P-⇌ NaNbO3 R phase transition

The structural phase transition between phase P and phase R in NaNbO₃ single crystals was studied by an optical method. It was found that this transition is similar to the martensitic transformation and that the phase fronts are formed by crystallographic planes having indices close to {0.2.11}. Behind the simple phase front a monodomain state arises. The polydomain state is the resultant of complex phase fronts.     

Diffuse phase transition from the superionic to non-superionic state in Cu1.8Se single crystal

The phase transition from the superionic to non-superionic state in a Cu_1.8Se single crystal is studied by neutron diffraction. In the superionic state, a diffuse halo related to the disordering of the cation subsystem is observed. It is established that the phase transition from the superionic to non-superionic state is the diffuse first-order phase transition occurring in the temperature range 250–180 K.     

Pressure Dependence of the Metal-Insulator and Superconducting Phase Transitions in (TMTSF)2 Reo4

Measurements of the pressure and temperature dependence of the a-axis resistivity of (TMTSF) ₂ReO₄, are presented. The metal-insulator transition seen in this material at the remarkably high temperature of ～180 K at ambient pressure and which is associated with an ordering of the ReO₄, anions is suppressed under pressure. For pressures above ～9.5 kbar we observe a superconducting transition near 1.3 K. There is a narrow intermediate pressure regime about 2.5 kbar in width in which both superconductivity and effects of anion ordering are observed. In this regime (i) a superconducting transition is seen near 1.3 K even though ρ just above the transition can be up to 10-100 times greater than ρ(300 K), and (ii) there is an extraordinarily large hysteresis in p below ～ 100 K with the possibility of varying the resistance of the low temperature state by several orders of magnitude by appropriate temperature cycling. These results establish the first order character of the transition. We suggest that at high pressures the anions remain frozen in a metastable disordered state to low temperatures.     

Zum chemischen Transport der Übergangsmetalldioxide mit Tellurhalogeniden

The thermodynamic relationship between the transition metal dioxides and their tetrahalogenides is demonstrated, and a comprehensive survey on the thermodynamic values of the compounds is given. – All dioxides of the transition metals existing to 1000°C in the solid state are transportable by TeCl₄. Only those dioxides are transported by TeBr₄ which have corresponding oxide-bromides existing in the gaseous phase. – The forms of crystallographic growth are very similar. The favoured growth direction is [001], the crystal faces are {110}- and {100}-prisms, {101}- and {111}-pyramids, respectively.     

Stability of amorphous SETE mixtures under pressure

A sharp semiconductor-metal transition is observed for a-Se₈₀Te₂₀ mixture at about 90 kbar. The resistance for the specimen which experiences the semiconductor-metal transition is recovered after releasing pressure. The sharp semiconductor-metal transition is reproducible in the second compression. X-ray diffraction measurements reveal that the amorphous specimen is transformed into the crystal with layer structure on the transition to metallic state and on releasing pressure the specimen is transformed again into the amorphous state. A brief comment is given for the interesting phenomena that the high-pressure crystalline phase can be recovered to the amorphous phase on releasing pressure.     

Study of ion transport in Li<Subscript>2</Subscript>ZrO<Subscript>3</Subscript> solid electrolytes with different lithium isotope ratios

Lithium ionic conductivity and spin-lattice relaxation rates were measured in Li₂ZrO₃ solid electrolytes with different ⁶Li and ⁷Li ratios. It is found that single-isotope electrolytes undergo a transition to the superionic state in the temperature range of 430–450 K, accompanied by an abrupt increase in conductivity. As a result of introduction of the other type of the isotope, the conductivity jump disappears in this temperature range. The transition to the superionic state is attributed to the redistribution of lithium ions over energetically nonequivalent lattice sites.     

Structural behavior of amorphous and liquid metallic alloys at elevated temperatures

The thermal behavior of the short-range order of Pd₄₀Cu₃₀Ni₁₀P₂₀ bulk metallic glasses has been investigated in situ by means of high-temperature X-ray synchrotron diffraction. The dependence of the X-ray structure factor S(q) of the glassy state on temperature follows the Debye theory up to the glass transition. Above the glass transition temperature T_g, the temperature dependence of S(q) is altered toward a continuous development of structural changes in the liquid state with temperature. The behavior of the structure factor during heating and cooling through the glass transition gives experimental evidence for melting the glass, and for freezing the liquid, respectively at the caloric glass temperature.     

Magnetic phase transitions in LaMnO3+λ

Magnetic properties of nonstoichinometric lanthanum manganite LaMnO_3+λ as a function of the Mn⁴⁺ concentration (from 0 to 27%) and temperature (from 77 to 300 K) are investigated. The Mn⁴⁺ ions concentration depends on the degree of oxidation λ. It is shown that at 0–10% Mn⁴⁺ there exists an antiferromagnetic ordering and at 10–14% — mixed ferro-antiferromagnetic ordering, while at Mn⁴⁺ concentration exceeding 14% the ferromagnetic ordering takes place. The concentrational antiferromagnetic-ferromagnetic transition at 14% Mn⁴⁺ is due to the crystal structural O' — O orthorhombic transition. In ferromagnetic O-orthorhombic lanthanum manganite the phase ferromagnetic-paramagnetic transition occurs via intermediate magnetic state where in the paramagnetic matrix there are noninteracting ferromagnetic impurity clusters. The presence of such magnetic state gives rise to anomalous behaviour of magnetic and galvanomagnetic properties of LaMnO_3+λ near Curie temperature.     

Unusual Glassy Smectic-G Liquid Crystal: Heat Capacity of N-p-n-Pentyloxybenzylidene-p'-n-butylaniline between 11 and 393 K

Abstract

The heat capacities of the title compound (C₃H₁₁,O—C₆H₄,- CH=N—C₆H₄,—C₄H₉, abbreviation 5O ? 4) with a purity of 99.92 mole percent have been measured with an adiabatic-type calorimeter between 11 and 393 K. The transition temperature and the enthalpy and entropy of phase transition for stable crystal → S_G, S_G → N and N → isotropic liquid were T _c = 299.69 K/ΔH = 22.68 kJ mol^?1/ΔS = 75.70 JK^?1 mol^?1, 325.72/7.11/21.79 and 342.48/1.78/5.22, respectively. The crystal which melts at 285.5 K is a metastable modification. The S_A phase hitherto reported in between S_G and N does not exist. The glassy So state was realized by rapid cooling of the specimen from the So phase. The molar enthalpy of the glassy S_G state at 0 K was by (10.1±0.1) kJ mol^?1 higher than that of the stable crystalline state and the residual entropy of the glassy state was (9.40±0.83) JK^?1 mol^?1. The relaxational heat-capacity anomaly was observed from as low as 100 K and double glass transition phenomenon occurred around 200 K; a quite unusual phenomenon which has never been observed for the glassy states of nematic and cholesteric liquid crystals. The present results give a fair evidence that the unusual glass transition phenomenon previously found for the S_G state of 6O?4 (a homologous compound) is not exceptional at all but common to the smectic glasses; at least common to the glassy S_G states. Two possible origins responsible for the double glass transitions have been discussed.     

Ferromagnetic insulating and reentrant spin glass behavior in Mg doped La0.75Sr0.25MnO3 manganites

In this study, the effect of Mg substitution on structural, magnetic and electrical properties of La_0.75Sr_0.25Mn_1?xMg_xO₃ and La_0.75Sr_0.25?xMg_xMnO₃ (nominal compositions) samples are investigated by XRD, Ac susceptibility and electrical resistivity measurements. It is found that Mg does not replace La in the perovskite lattice. Also the results show that by increasing Mg doping levels, the paramagnetic–ferromagnetic and metal–insulator transition temperatures decrease. The reason for decreasing transition temperatures with increasing Mg concentration is, that the long-range FM order has been destroyed by the Mg, which is randomly occupying Mn site. This leads to the suppression of double-exchange interaction in the Mn³⁺–O–Mn⁴⁺ networks. Also the reentrant spin glass (RSG) state accompanied by FM transition, exists in high doped samples. The RSG state could be understood on the basis of double exchange ferromagnetic interaction in Mn³⁺–O–Mn⁴⁺ and super-exchange antiferromagnetic interaction in the Mn⁴⁺–O–Mn⁴⁺ networks.     

Correlation between the residual resistivity ratio and the power‐law of the normal‐state resistivity in MgB2

MgB₂ polycrystalline superconducting specimens were irradiated with several doses of γ‐rays up to 100 MR. An increase in the normal state resistivity and a broadening of the resistive transition to the superconducting state were observed with increasing γ‐irradiation dose. Although very small changes to the superconducting transition temperature were obtained after γ‐irradiation, different temperature dependence of normal‐state resistivity and different residual resistivity ratios, RRR were obtained for different doses. We have found a correlation between RRR and the power law dependence of resistivity, n as the irradiation dose increases. This correlation may be an indication that the electron‐phonon interaction is important in these samples. These results are attributed to the disorder caused by γ‐rays. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

X-ray diffraction study of phase transitions in Na3Sc2(PO4)3 and Ag3Sc2(PO4)3 single crystals in temperature range from 160 to 500 K

Two phase transitions are revealed for the first time in Ag₃Sc₂(PO₄)₃ single crystals in the vicinity of the temperatures 303 and 165–180 K. It is established that the phase transition at 303 K corresponds to the well-known phase transition to the superionic state in Na₃Sc₂(PO₄)₃ single crystals in the temperature range 423–433 K, whereas the phase transition observed in the temperature range 170–180 K corresponds to the phase transition from the rhombohedral to monoclinic phase at about 320 K in the monoclinic Na₃Sc₂(PO₄)₃ single crystals. It is also established that rhombohedral Na₃Sc₂(PO₄)₃ single crystals undergo the second phase transition. __________ Translated from Kristallografiya, Vol. 50, No. 1, 2005, pp. 122–126. Original Russian Text Copyright ? 2005 by Shilov, Atovmyan, Kovalenko.     

Crystal Structures of D-N-(2-Adamantyl)phenylglycinol and L-N-(2-Adamantyl)diphenylphenylalinol: Chiral Amino Alcohols Utilized as Ligands for Catalytic Asymmetric Hydroamination

Amino alcohols are important ligands for the asymmetric catalytic hydroamination of aminoallenes to form chiral pyrrolidines. Herein, we report the crystal structures of two chiral amino alcohols, D-N-(2-Adamantyl)phenylglycinol and L-N-(2-Adamantyl)diphenylphenylalinol, that function as ligands within transition metal complexes that catalyze the hydroamination of aminoallenes. Both molecules crystallize in the noncentrosymmetric orthorhombic space group P2₁2₁2₁. Inter- and intramolecular hydrogen bonding plays an important role in stabilizing each alcohol in the solid state in the absence of a transition metal. The presence of these hydrogen bonds has been verified by single crystal X-ray diffraction and their overall strength determined by computational methods.     

Coefficient of volume expansivity and thermoacoustic parameters in certain alkoxybenzylidene butylanilines-IA

A number of thermoacoustic parameters including the Sharma constant S_o are evaluated in the homologous series of alkoxybenzylidene butylanilines with m = 4 to 7, to understand whether these parameters can be used to understand the anomalous behaviour at the phase transition temperatures and pretransitional effects on either side of the transition. The Sharma constant which was shown to be a constant in a number of non-mesomorphic systems is also found to be a constant for the mesogens belonging to this series both in their liquid crystalline as well as isotropic state. It is observed that almost all these parameters exhibit anomalous behaviour at the transition and pretransitional effects on either side of the transition. The results are discussed.     

Thermal Analysis of LiGaO2 and NaGaO2

The high-temperature thermal properties of the ternary oxides LiGaO₂ and NaGaO₂ are studied by simultaneous differential thermal analysis and thermogravimetry between room temperature and about 1700 °C. For the melting temperature of LiGaO₂ a value of 1595 ± 10 °C is determined. NaGaO₂ undergoes a solid state phase transition at 1280 ± 10 °C and melts at 1395 ± 10 °C.     

New family of LnBaMn2O6 − γ manganites (Ln = Nd, Sm, and Gd)

A new family of manganites, LnBaMn₂O_{6 ? γ}(Ln = Nd, Sm, and Gd), is obtained by the method of topotactic reactions. In these compounds, rare-earth and barium ions are ordered, which results in a dramatic increase in the temperature of transition to the paramagnetic state. Thus, a SmBaMn₂O₆ compound with a disordered arrangement of Sm and Ba ions is a spin glass with the freezing temperature of magnetic moments T _f = 40 K, whereas in the state with an ordered Sm and Ba arrangement, the Curie temperature T _C, is ～ 280 K. Below T _C, a maximum in resistivity and magnetoresistance is observed. The possible models of magnetic ordering are discussed.     

Control of the Discotic to Isotropic Transition in Alkoxy-Substituted Silicondihydroxo-Phthalocyanines by Axial Substituents

The synthesis of a homologous series of octaalkoxy-substituted silicondihydroxo-phthalocyanines is described. The mesomorphic properties of these new materials were studied by DSC, optical microscopy and X-ray investigations. Compounds with n ≤ 4 (n is the number of carbon atoms in a single alkoxy side chain) show a discotic mesophase transition. A transition to the isotropic state is only observed when n ≤ 8. X-ray diffraction patterns of the mesophases confirm that all compounds form a hexagonal columnar mesophase of the type D_hd.     

Calorimetric investigations of 2-[4-n-alkylphenyl]-5-[4-n-alkyloxyphenyl]-pyrimidines

We investigated temperatures and enthalpies of the phase transitions by means of the calorimeter DSC-2. The kinetics of polymorphic transitions in the solid state, the pretransitional behaviour in the liquid crystalline phases and the transition enthalpies, ranging from 3 J/mol up to 50 kJ/mol, in relation to the occurrence of the liquid crystalline phase types S_G, S_F, S_C, S_A, and N are points of discussion.     

Crystal structure and magnetic properties of the LaCo0.5Fe0.5O3 perovskite

The magnetic and crystal structures of the LaCo_0.5Fe_0.5O₃ perovskite are investigated. It is established that the unit cell of this compound at room temperature is characterized by rhombohedral distortions. As the temperature decreases, the compound undergoes a structural phase transition from the rhombohedral phase to the orthorhombic phase in the temperature range 200–300 K. The LaCo_0.5Fe_0.5O₃ perovskite has an antiferromagnetic structure with the G _z spatial orientation of the antiferromagnetic vector. The magnetic properties of the LaCo_0.5Fe_0.5O₃ perovskite are interpreted within a model according to which the ground state of Co³⁺ ions is a low-spin state and the existence of the weak ferromagnetic component is associated with the exchange interactions between the Fe³⁺ ions.     

Superconductivity of Annealed and Consolidated Amorphous YNi2B2C Powders

Amorphous YNi₂B₂C powders have been produced by mechanical attrition. Superconductivity is absent in the amorphous state but recovers upon crystallization. However, the superconducting transition temperature TC is lower than that of the melted analogue. TC can be increased by increasing the annealing temperature. High temperature compaction leads to dense bulk superconducting samples. TC of these bulk samples can be optimised by annealing. Variations in TC are attributed to deviations from stoichiometry. Contamination of the powders with WC wear debris upon annealing may deteriorate the superconducting properties.