Phase diagrams of YBa2Cu4O8 and YBa2Cu3.5O7.5 in the pressure range 1 bar≤PO2≤3000 bar

The P-T-x phase diagram of the pseudobinary system (Y-Ba-Cu-O)-O₂ has been further investigated in the oxygen pressure range between 1 and 3000 bar. The stability ranges of the phases YBa₂Cu₄O₈ (124), YBa₂Cu_3.5O_7.5−x (123.5) and YBa₂Cu₃O_7−x (123) have been determined. Long duration experiments showed that the 123 phase is not stable at least down to 7 bar≤P≤20 bar oxygen and 900°C. It is not clear whether at lower pressures and temperatures the 123 phase is thermodynamically stable or metastable due to low reaction rates. In the presence of excess CuO, the 124 is the stable phase. The melting of 124 pellets at P_O2=2800 bar shows that even at this pressure the 124 compound melts incongruently. Using the phase diagram data we could change the T_c of 123.5 from 16 to 70 K by varying systematically the nonstoichiometry. Due to a narrow homogeneity range the T_c of 124 remained constant but is different for powder pellets (81 K) and for crystals (70 K), probably due to the influence of the flux. Single crystals of both 124 and 123.5 with dimensions up to 4 mm were grown from the flux under high oxygen pressure.     

Study on the superconducting composite material formation in the system Bi2Sr2CaCu2O8+x/Al-containing phases

Phase evolution in the Bi---Sr---Ca---Cu---Al---O system was studied. Two Al-containing phases BiSr_1.5Ca_0.5Al₂O_z and (Sr_1−xCa_x)₃Al₂O₆ (x = 0.4 − 0.45) were determined to be chemically compatible with Bi_2.18Sr₂CaCu₂O_8+x (Bi-2212) at temperatures of the samples processing. The phase equilibria in the title system were investigated above the solidus temperature. The BiSr_1.5Ca_0.5Al₂O_z was found to be in equilibrium only with the melt and the (Sr_1−xCa_x)₃Al₂O₆ phase. This latter aluminate equilibrated with Ca,Sr cuprates, CaO, the Cu-free phase, and the liquid. The melting and solidification in Bi-2212, doped with the aluminate, corresponded to the reversible reaction Bi-2212 + BiSr_1.5Ca_0.5Al₂O_z ↔ (Sr_1−xCa_x)₃Al₂O₆ + liquid. Two sets of superconducting composite materials with initial compositions Bi-2212 + nBiSr_1.5Ca_0.5Al₂O_z and Bi-2212 + m(Sr_1−xCa_x)₃Al₂O₆ were prepared by solidification from the partial melt. The former material was composed mostly of large Bi-2212 lamellas separated by the BiSr_1.5Ca_0.5Al₂O_z phase, which destroyed superconducting links between Bi-2212 grains. The latter material consisted of a Bi-2212 polycrystalline matrix with high concentration of small (ca. 3 μm) grains of (Sr_1−xCa_x)₃Al₂O₆ imbedded in Bi-2212 lamellas. The Bi-2212 + m(Sr_1−xCa_x)₃Al₂O₆ materials displayed a trend to enhance flux pinning at T = 60 K with the increase of aluminate phase content.     

An electrochemical investigation of Li intercalation in the sol-gel LiMn2O4 spinel oxide

An alternative approach for obtaining the LiMn₂O₄ spinel phase is provided by the use of the sol-gel method in aqueous solution. The main electrochemical properties of the sol-gel LiMn₂O₄ phase are reported. In addition to chronopotentiometric and voltammetric experiments, the kinetics of the electrochemical insertion–extraction of lithium in Li_xMn₂O₄ (0.25<x<1) has been investigated using ac impedance spectroscopy. The strong variation of the chemical diffusion coefficient D_Li vs x, in the range 10⁻⁸–10⁻¹¹ cm² s⁻¹ (D_Li is found to be maximum for x=0.55) is critically discussed.     

Electrical transport and superconductivity in the Al2O3-Bi2Sr1.8Ca1.2Cu2Oy and MgO-Bi2Sr1.8Ca1.2Cu2Oy composites

We have measured the resistivities of Al₂O₃-Bi₂Sr_1.8Ca_1.2Cu₂O_y and MgO-Bi₂Sr_1.8Ca_1.2Cu₂O_y composites with the nominal Bi₂Sr_1.8Ca_1.2Cu₂O_y volume fraction, ₂₂₁₂, ranging from 0.15 to 1.00. For the Al₂O₃-Bi₂Sr_1.8Ca_1.2Cu ₂O_y composites, we find for the samples with ₂₂₁₂≥0.6 that the superconducting transition temperature, T_c, is not disturbed by the addition of Al₂O₃. For ₂₂₁₂<0.3, no zero-resistivity state is observed. For the MgO-Bi₂Sr_1.8Ca_1.2Cu₂O_y composites, T_c is barely disturbed for the samples with ρ₂₂₁₂≥0.7. No superconducting state is observed for the samples with ρ₂₂₁₂<0.35. The variation of (300 K) with ρ₂₂₁₂ indicates a three-dimensional percolating Bi-Sr-Ca-Cu-O matrix occurring at ρ₂₂₁₂≈0.19 and ≈0.15 in Al₂O₃-Bi₂Sr_1.8Ca_1.2 Cu₂O_y and MgO-Bi₂Sr_1.8Ca_1.2Cu₂O_y, respectively. Both resistivity and magnetization measurements suggest that the reactions of Bi₂Sr_1.8Ca_1.2Cu₂O_y with MgO are weaker than with Al₂O₃.     

Disruption of antiferromagnetic order in Zn-doped La2CuO4

The magnetic phase diagram of La₂(Cu_1−xZn_x)O₄ has been determined from zero-field muon-spin-rotation (ZF-μSR) data taken at LAMPF for 0 ≤ x ≤ 0.10. Antiferromagnetic onset temperatures follow T_N(x) from susceptibility measurements on the same samples. However, the order becomes long range, as evidenced by a well-defined internal magnetic field, only at temperatures well below T_N. Extrapolation of our results yields T_N → 0 K at x = 0.11 for a single (Cu_1−xZn_x)O₂ plane, and comparison with YBa₂(Cu_1−xZn_x)₃O₆ implies identical disruption of magnetism by Zn doping in the single- and double-plane systems.     

Ionic conductivity of crystalline and glassy Mg4.5Na7(P2O7)4

In our work single crystals of Mg_4.5Na₇(P₂O₇)₄ were prepared, pulverized, pressed into pellets and sintered in order to measure the electrical conductivity of polycrystalline specimens. The conductivity was also measured on glassy specimens obtained by the melting of previously prepared crystals. The electrical conductivities at 25°C with values of the order of 10⁻¹⁶ Ω⁻¹ cm⁻¹ for polycrystalline samples and a value of the order of 10⁻¹⁴ Ω⁻¹ cm⁻¹ for glass, show that the glassy phase of Mg_4.5Na₇(P₂ because of its greater molar volume and loosely packed structure, is a better matrix for ionic motion.     

A new layered cuprate superconductor: GaSr2(Y, Ce)2Cu2O9−δ

A new layered cuprate compound with a nominal composition of GaSr₂Y_2−xCe_xCu₂O_9−δ has been prepared. It crystallizes in a tetragonal lattice with cell parameters: a = 3.812 Å, c = 28.16 Å. The structure of the compound belongs to the same family of 1222 phase and is derived from that of GaSr₂LnCu₂O₇ by replacing the single Ln³⁺ layer with a double fluorite (Y, Ce)₂O₂ layer. Like other parent cuprate compounds of superconductors, the as-prepared samples showed antiferromagnetic and semiconducting behavior. After treatment under high oxygen pressure, the samples exhibited bulk superconductivity with transition temperatures between 12–14 K.     

Lithium insertion to ReO3-type metastable phase in the Nb2O5–WO3 system

Lithium insertion to distorted ReO₃-type metastable solid solution Nb_xW_1−xO_3−x/2 (0≤x<0.25) has been studied by chemical and electrochemical methods. In the course of lithium insertion into tetragonal compounds, transition to a cubic phase was found to occur in the region where values of y (in Li_yNb_xW_1−xO_3−x/2) fall between 0.2 and 0.3, and the phase transition was found to depend on the conditions of the reaction. Changes in OCV and lattice parameters in tetragonal region (y<0.2) were discussed from the viewpoint of the ordering of lithium ions. Also, the component diffusion coefficient of lithium in tetragonal compounds Li_0.1Nb_xW_1−xO_3−x/2 (0≤x≤0.23) was found to increase with niobium content when x≤0.10, and to saturate at 4×10⁻⁹ cm²/s.     

Superconductivity at 27 K in Nb-1222 cuprate: NbSr2(GdCe)2Cu2Oy

Samples of NbSr₂Gd_2−xCe_xCu₂O_y have been prepared by solid state reaction. The X-ray powder diffraction patterns show that a single phase can be formed in the composition range of 0.49<x<0.51 that has TaSr₂ (NdCe)₂Cu₂O_y structure [1], the cell parameters being a=3.8669±0.0046 Å and c=28.742±0.0048 Å. Superconductivity was found by resistance measurements in the sample of NbSr₂Gd_1.5Ce_0.5Cu₂O_y: the onset transition temperature is 27.4 K, and zero resistance appears at approximately 13 K.     

The crystallographic symmetries of single BaPb1−xBixO3 crystals grown from BaCO3-PbO2-Bi2O3 solutions

Single crystals of Perovskite-type oxide BaPb_1−xBi_xO₃ are grown from BaCO₃-PbO₂-Bi₂O₃ solutions which are weighed in two kinds of mixing ratios: X/2 mol % BaCO₃ − (100−X) mol % PbO₂ − X/2 mol % Bi₂O₃ and (10+X/2) mol % BaCO₃ − (90−X) mol % PbO₂ − X/2 mol % Bi₂O₃ These room temperature crystal structures are examined by using an X-ray powder diffraction method. The crystals grown from X/2−(100−X)−X/2 mol % solutions are orthorhombic at room temperature, while the structures are tetragonal with crystals grown from relatively Ba rich and Pb poor ( (10+X/2)−(90−X)−X/2 mol % ) solutions. This result indicates that the difference in the mixing ratio of the initial materials brings about a drastic structural change. The orthorhombic and the tetragonal crystals of x0.25 exhibit superconducting transition at 10K and 12K, respectively. The transition temperature in the latter is 2K higher than the former. In the light of this result, some difference between orthorhombic and tetragonal crystals is considered to influence superconductivity in this system.     

Realization and properties of ramp-type YBa2Cu3O7−δ/Au/Nb junctions

All-thin-film ramp type Josephson junctions between YBa₂Cu₃O_7−δ and Nb have been fabricated. This procedure allows connections between high-T_c and low-T_c superconductors at different crystal sides of the high-T_c superconductor on one chip, which is of great interest for novel phase devices. A thin Au layer is incorporated as a chemical barrier to avoid oxygen transfer from the YBa₂Cu₃O_7−δ to the Nb. Critical current densities up to 600 A/cm² are obtained at T=4.2 K, with typical R_nA values of 0.8 μΩ cm². The variation of the magnetic field dependence of the critical current with the angle between the junction barrier and the YBa₂Cu₃O_7−δ crystal axes is explained by considering a predominant d_x²−y² order parameter symmetry of the YBa₂Cu₃O_7−δ. The successful fabrication of these junctions allows the implementation of novel superconducting electronics, such as complementary Josephson circuitry or proposed qubit concepts, using the unconventional order parameter symmetry of the high-T_c superconductor.     

Specific heat and anisotropic superconducting and normal-state magnetization of HoNi2B2C

The magnetization of single-crystal HoNi₂B₂C has been measured as a function of applied field (H) and temperature in order to probe the interplay between superconductivity and magnetism in this complex layered system. The normal-state magnetic susceptibility of HoNi₂B₂C is highly anisotropic with a Curie-Weiss-like temperature dependence for H applied perpendicular to the c-axis and with a much weaker temperature dependence for H applied parallel to the c-axis, indicating that the Ho⁺³ magnetic moments lie predominately in the tetragonal a−b plane below 20 K. High-field magnetization (2000 Oe), low-field magnetization (20 Oe) and zero-field specific heat all give an antiferromagnetic ordering temperature of T_N=5.0 K. Remarkably, in 20 Oe applied field both superconductivity (T_c=8.0 K) and antiferromagnetism (T_N=5.0 K) clearly make themselves manifest in the magnetization data. From these magnetization data a phase diagram in the H−T plane was constructed for both directions of applied field. This phase diagram shows a non-monotonic temperature dependence of H_c2 with a deep minimum at T_N=5 K. The high-field magnetization data for H applied perpendicular to the c-axis also reveal a cascade of three phase transitions for T < 5 K and H < 15 000 Oe, contributing to the rich H versus T phase diagram for HoNi₂B₂C at low temperatures.     

Phase transitions and electrical properties of CsH(SO4)0.76(SeO4)0.24 mixed crystals

The study by X-ray diffraction, calorimetry, vibrational and impedance spectroscopy of CsH(SO₄)_0.76(SeO₄)_0.24 new solid solution is presented. Crystals of this composition undergo two phase transitions at T = 333 and 408 K. The last one at 408 K is a superionic-protonic transition (SPT) related to a rapid [HS(Se)O₄⁻] reorientation and fast H⁺ diffusion. A sudden jump in the conductivity plot confirms the presence of this transition. Above 408 K, this high temperature phase is characterized by high electrical conductivity (7 × 10^t-3 Ω⁻ cm⁻¹) and low activation energy (E_a < 0.3 eV).     

Temporary phase segregation processes during the oxidation of (Fe0.7Mn0.3)0.99O in N2---H2O atmosphere

A two-step thermochemical cycle with the ternary metal oxide system (Fe_{1 − x}Mn_x)₃O₄/(Fe_{1 − x}Mn_x)_{1 − y}O is applied to convert solar energy to chemical energy. Experimental investigations on the water splitting reaction of (Fe_{1 − x}Mn_x)_{1 − y}O revealed temporary formation of a manganese rich rock salt phase and an iron rich spinel phase due to phase segregation processes.     

Study of the ferroelectric–paraelectric phase transition of NaH3(SeO3)2 single crystals by H and Na NMR

The ¹H and ²³Na spin–lattice and spin–spin relaxation times of NaH₃(SeO₃)₂ single crystals grown using the slow-evaporation method were measured as functions of temperature and frequency in the ferroelectric and paraelectric phases. The changes in the symmetry of the (SeO₃)²⁻ dimers as a result of the ferroelectric–paraelectric phase transition are associated with large changes in the spin–lattice and spin–spin relaxation times, and in the number of resonance lines. The large changes in the relaxation times at 195 K indicate that the H and Na ions are significantly affected by this transition. The change in the number of resonance lines for the ¹H and ²³Na nuclei means that the orientations of the (SeO₃)²⁻ dimers and the environments of the Na ions change at T_C. Therefore, the orientations of the (SeO₃)²⁻ dimers and the environments of the Na ions play important roles in the phase transitions. In conclusion, the ferroelectric–paraelectric phase transition of NaH₃(SeO₃)₂ is accompanied by changes in hydrogen-bond structure and distortions of the (SeO₃)²⁻ and Na⁺ ion lattices, which form a slightly distorted octahedron.     

Properties of rubidium nitrate in ion-conducting RbNO3-Al2O3 nanocomposites

Properties of RbNO₃ in (1 − x)RbNO₃-xAl₂O₃ nanocomposites were studied by X-ray powder diffraction, electron diffraction, conductivity measurements, infrared and Raman spectroscopy, and differential scanning calorimetry. All the experimental techniques used indicate the presence of an amorphous RbNO₃ layer at the RbNO₃---Al₂O₃ interface in addition to a crystalline RbNO₃ phase. Its concentration was determined from the phase transition enthalpies. The amorphous layer thickness estimated by means of a simple brick-wall model is 4 nm.     

Superconducting Nd1.85Ce0.15CuO4 films grown by the pulsed electron deposition technique

Nd_1.85Ce_0.15CuO_4−δ superconducting thin films were prepared on (1 0 0) SrTiO₃ substrates by pulsed electron deposition technique without reducing atmosphere. Oxygen content is finely controlled by high temperature vacuum annealing, and optimal superconductivity has been obtained. The deposition conditions of the film are discussed in details. Higher deposition temperature and lower gas pressure result in the loss of copper and the appearance of the foreign phase Ce_0.5Nd_0.5O_1.75. High quality Nd_1.85Ce_0.15CuO_4−δ epitaxial films are deposited at 840–870 °C in the mixed gas with a ratio of O₂:Ar = 1:3.     

An XPS study of SO2 ON A CaO surface derived from Ca(OH)2

The adsorption of SO₂ on a CaO surface derived from Ca(OH)₂ has been studied by X-ray photoelectron Spectroscopy. It is shown that SO₂ adsorbs molecularly on the CaO surface forming SO₃²⁻ and SO₄²⁻. The adsorbate SO₃²⁻ species shift the Ca2p core levels about 2 eV toward higher binding energy. However, the formation of SO₄²⁻ species does not induce any further observable changes in the Ca core line spectra. These results are explained and discussed in terms of an electronic charge transfer from the substrate metal atoms to the adsorbed molecules and vice versa.     

Systematic thermopower measurements of the thallium cuprates Tl(Ba,Sr)2Cam−1CumO2m+3−δ and Tl2Ba2Cam−1CumO2m+4+δ

The thermoelectric power (TEP) S versus temperature has been systematically investigated for several series of the superconducting cuprates Tl(Ba,Sr)₂Ca_m−1Cu_mO_2m+3−δ (m = 2, 3) and Tl₂Ba₂Ca_m−1Cu_mO_2m+4+δ (m = 1, 2, 3). The consideration of the S(T_c) curves allows two important points to be found evidence for. The first one deals with the fact that all these superconducting thallium cuprates are systematically overdoped whatever T_c, and whatever the number of Cu or Tl layers; no underdoped superconducting cuprate could be obtained. The second point shows that there exist two classes of Tl cuprates: the weakly overdoped cuprates that exhibit a T_{c max} ≥ 100 K (all the triple copper layer cuprates and the 2212 cuprates) and those which can be heavily doped that exhibit a T_{c max} ≤ 90 K (the 2201 and the 1212 cuprates). The different behavior of thallium cuprates compared to YBa₂Cu₃O_7−δ and to bismuth cuprates is discussed.     

Interaction of CO2 with Cs-promoted Fe(110) as compared to Fe(110)/K+CO2

The interaction of CO₂ with Cs-promoted Fe(110) at 85 K as well as temperature-dependent reactions between 100 and 700 K have been studied by means of ultraviolet photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS). Several surface species could be detected at 85 K, i.e. carbon monoxide (CO), carbonate (COⁿ⁻₃), physisorbed linear carbon dioxide (CO^lin₂) and very small amounts of oxidic oxygen (O_ox). An oxalate species (C₂O^m−₄) could not be identified definitively, but from comparison with the literature there is evidence that C₂O^m−₄ is present. Increasing the temperature after saturation with CO₂ leads to a complicated reaction behaviour. CO₂ either desorbs or dissociates into CO and COⁿ⁻₃ or forms C₂O^m−₄ at temperatures between 85 and 160 K. Above 160 K C₂O^m−₄, decomposes in parallel reactions into CO₂, COⁿ⁻₃ and CO. Above 320 K, adsorbed CO either desorbs into the gas phase or dissociates into C and O. In the temperature region between 500 and 700 K a recombination of C and O to CO and the desorption of Cs take place. As in the case of Fe(110)/K+CO₂, at high alkali coverages two carbonate species could be detected which dissociate upon heating at different temperatures. The system Fe(110)/Cs+CO₂ is proved to be very similar to the system Fe(110)/K+CO₂.