Phase transitions in [Ni(NH3)6](NO3)2

Electric permittivity ^* = ′ − i″ of nickel-hexammino nitrate (NHN) has been measured within the range of temperature from 9 to 300 K at a frequency of 8.8 GHz (X-band). It has been found that the phase transitions at T_k1 = 247 K and T_k2 = 90 K are discontinuous structural transitions between centrosymmetric phases, whereas the transition at T_c = 63 K is a continuous phase transition (glass?).     

A new high-Tc superconducting Tl-Pb-Ca-Sr-Cu-O system

A new family of high-T_c superconducting material in the Tl-Pb-Ca-Sr-Cu-O system has been synthesized. Multiple phases with two-step superconducting transitions around 110 K and 80 K were observed resistively and magnetically. The 80 K phase has been tentatively identified to be (Tl, Pb)₂Sr₂CuO_y by X-ray diffraction analysis. This material appears to have a relatively high flux pinning.     

Kinetics of glass transition and thermal stability of?Se58Ge42?xPbx?(9≤x≤20) glasses

Se₅₈Ge_42−x Pb _x (9≤x≤20) glasses have been prepared using conventional melt quenching technique. Differential Scanning Calorimetric (DSC) measurements show single glass transition and double crystallization, which indicate the occurrence of phase separation in the samples. The phases present in the samples were identified using XRD. The kinetics of the glass transition has been studied in terms of the variation of glass transition temperature with composition and heating rate. In addition to this, activation energy of the glass transition (E _t ) has also been evaluated and its composition dependence is also investigated. The thermal stability of these glasses has been investigated using various stability criteria: Deiztal first glass criterion, ΔT, Saad and Poulain weighted thermal stability, H′ and the S-parameter. The values of these parameters were obtained using various characteristic temperatures such as the glass transition temperature, T _g , the onset temperature of crystallization, T _c , and the peak crystallization temperature, T _p . The values of stability parameters show that the phase corresponding to second crystallization is more stable than the phase corresponding to first one. The stability in terms of the lead (Pb) content has been determined considering the values of stability parameters of the phase corresponding to second peak. It was found that the stability increases with the lead content.     

Multicomponent GeSe2-CdI2-TeO2 (Bi2O3) systems: glass formation and properties

The glass-forming regions of the GeSe₂-CdI₂-TeO₂ (I), GeSe₂-CdI₂-Bi₂O₃ (II) and GeSe₂-TeO₂-Bi₂O₃ (III) systems have been determined. The obtained glassy phases have been characterized by their basic physicochemical parameters such as temperatures of glass transition, crystallization, and melting, density and microhardness. The phase T-X diagram of the GeSe₂-CdI₂ system, which is the basic joint line for systems I and II, has been specified. Three non-variant equilibria (two eutectic and one syntectic) have been observed at temperatures 350, 280 and 375 °C for compositions containing 15, 95 and 33.3 mol% GeSe₂, respectively. A new intermediate phase with probable composition of 2CdI₂·GeSe₂ has been formed.     

Superconductivity and magnetic properties of Nb—Al phases: Nb2Al and NbAl3

Magnetic properties of tetragonal phases in Nb—Al system have been investigated down to 0.42°K. It has been found that the-phase (Nb₂Al) and the intermetallic compound NbAl₃ are superconductors with superconducting transition temperature 0.74°K and 0.64°K, respectively. Magnetic susceptibility of the investigated phases does not depend on temperature within the range 4.2°K–300°K, and is equal =(1.0±0.1) × 10^–6 emu)/g for Nb₂Al, and =(0.9±0.03) × 10^–6 emu/g for NbAl₃.On leave of absence from Institute for Solid State Physics of Bulgarian Academy of Sciences, Sofia, Bulgaria     

Chiral superconducting phase transition in 3-K phase of Sr2RuO4

We have investigated the transports of micro-fabricated sample of 3-K phase superconductivity (T_c  3 K) in Sr₂RuO₄–Ru eutectic system in order to clarify the pairing symmetry. Up to now, pure Sr₂RuO₄ (T_c = 1.5 K: 1.5-K phase) is widely recognized to be a spin-triplet odd-parity superconductor. However, the enhancement mechanism of T_c up to 3 K and the pairing symmetry of the 3-K phase have not been cleared yet. By using micro fabrication technique with focused ion beam, we have succeeded to extract individual superconducting channels for the 3-K phase in which only a few pieces of Ru inclusions are contained. Multiple kink structures observed in differential resistance–current (dV/dI − I) characteristics indicate serially connected superconducting filaments in the 3-K phase. We confirm that the 3-K phase is an odd-parity superconductor similar to pure Sr₂RuO₄ from the monotonous temperature dependence of the critical currents. In addition, we observed a quite unusual hysteresis in dV/dI − I below 2 K, which suggests the internal degrees of freedom in the superconducting state: the most probably the chiral p-wave state.     

Crystal chemistry of the Tl2−xBa2Ca n Cu n+1O2n+6 (n=0, 1, 2) high-T c superconductors

We report on a comparative crystal chemical study of the Tl_2–xBa₂Ca _n Cu _n+1O_2n+6(n=0, 1, 2) high-T _c superconductors. Superconducting properties were determined by DC-conductivity and-susceptibility measurements. An X-ray diffraction analysis reveals the nonstoichiometry of the compounds as a link between structural and superconducting behavior. A comparison of the different structures gives evidence that T1 deficiency in the TlO double layers increases with increasingn; this deficiency causes apparent Cu valences larger than 2+in the superconducting phases thus maintaining the charge balance. By extracting appropriate chemical formulas and performing a bond strength calculation we obtained the mixed-valent oxidation state of copper for the superconducting tetragonal phases as being 2.17+(n=0), 2.25+(n=1) and 2.31+(n=2) respectively; for the non-superconducting orthorhombic phase Tl_2–xBa₂CuO_6–y a Cu valence of about 2+is suggested.     

The reaction process of the Bi-Sr-Ca-Cu-O system and the forming mechanism of the 2212 superconducting phase

The reaction process and the reaction behavior of each component in the Bi-Sr-Ca-Cu-O system are presented in this paper. It reveals that the reaction is carried out in three different stages: forming of an insulating interphase at 680°C–790°C, forming of the 2212 superconducting phase at 790°C–860°C and forming often semiconducting phases in the presence of the liquid phase at 860°C–970°C. It is also confirmed that the 2212 superconducting phase (T _c=85 K) is formed by the reaction of a trinary interphase together with CuO, SrO and CaO. A new two-step method is presented to prepare the 2212 superconducting phase by a presynthesized interphase.     

Kramers-Kronig analysis of the reflectance spectra of Pb-doped Bi-4334 type glass and the corresponding glass-ceramic superconductor

The room temperature reflectance spectra in UV-VIS-NIR region (energy range of 0.6 to 6.2 eV) for glassy, partially crystalline and its fully crystalline superconducting ceramic phases of Bi_3.9Pb_0.1Sr₃Ca₃Cu₄O _x have been studied by Kramers-Kronig (KK) analysis. A comparative study of the energy loss function [− Im (1/ε)] and the absorption coefficient [α(E)] has been done. Excitions in the superconducting phase hitherto evidenced by the authors are located in the polarizable layers of the superconducting cuprate and their implications for superconductivity have been pointed out. An estimate of the optical band gap energy (E _g) has also been made from the linear fit ofα ² vs.E curve for the superconducting phase. Jezierski’s method ofR-extrapolations in the higher energy has been used to show that both methods yield results that agree quantitatively and can be relied upon.     

A new 1223-type high Tc cuprate (Tl,V) Sr2Ca2Cu3O9

A new 1223-type (Tl, V)-based superconducting layered cuprate (Tl_1–x V _x ) Sr₂Ca₂Cu₃O₉ withx=0.25 and 0.50 has been successfully synthesized in the nearly-pure form and identified by powder X-ray diffration analyses. An excessive quantity of Tl is necessary for the preparation of the (Tl, V)-based 1223-type compound. Resistance and ac susceptibility measurements showed that the new (Tl, V)-based 1223 cuprate exhibits T_c above 110 K.     

Crystallization of amorphous Fe100−xPx (13x24) alloys

A study of the structure change with temperature in amorphous Fe₁₀₀−xP_x (13 x 24) alloys was carried out by measuring magnetization and thermal expansion and also by structural analysis using X-ray diffraction and differential thermal analysis (DTA). The structure of the amorphous alloys relaxes (the decrease of excess free volume) at temperatures 100–150 K below the crystallization temperatures. The alloys with x 15 transform into (α-Fe + amorphous) at about 600 K. The alloys with x15 transform into (α-Fe+amorphous+Fe₃P) at about 600 K. With further heating, the alloys transform into (α-Fe+Fe₃P) both of which are stable phases from the equilibrium phase diagram.     

TlBaCaCuO superconducting thin films via metal-organic chemical vapour deposition (MOCVD) and thallium vapour diffusion

Summary Superconducting thin films of the TlBaCaCuO family have been prepared through a combined approach of MOCVD and thallium vapour diffusion. A three-step process has been adopted involving i) the synthesis of Ba−Ca−Cu−O films by MOCVD using ?second-generation? barium and calcium sources, ii) the hydrolysis of the fluoride phases by annealing in water vapour-saturated oxygen and iii) the annealing in the presence of a thallium source. Reproducible results, in terms of phase formation, are discussed depending on the different conditions of the preannealing process. The superconducting films consist predominantly of single-phase Tl₂Ba₂Ca₂Cu₃O _x (2223). Preferential orientation of the crystallitec-axes perpendicular to the substrate surface has been observed. The films exhibit superconducting onset temperatures of 115–120 K with zero resistance higher than 100 K. Paper presented at the ?VII Congresso SATT?, Torino, 4–7 October 1994.     

Kinetics of nonisothermal crystallization in Sn<Subscript>10</Subscript>Sb<Subscript>20−<Emphasis Type="Italic">x</Emphasis></Subscript>Bi<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Se<Subscript>70</Subscript> glassy semiconductors

The crystallization kinetics of Sn₁₀Sb_20−x Bi _x Se₇₀ (x=0,2,4,6,8) chalcogenide system has been studied. Crystallization studies using differential scanning calorimetry under nonisothermal conditions with different heating rates are reported. The glass transition temperature is found to increase with the increase in heating rate as well as with the addition of bismuth. The apparent activation energy for glass transition and that for crystallization have been determined using the Kissinger equation. Thermal stability and glass forming tendency have also been studied.     

Phases and phase transitions of (NaCl)1−x(NaCN)x

(NaCl)_1–x(NaCN)_x mixed crystals with CN-concentrationsx of 0.87, 0.76, 0.71 and 0.65 have been investigated by X-ray powder diffraction. Apart from the cubic room temperature phase, a rhombohedral and an orthorhombic phase have been identified. In addition a glass state has been observed which is characterized by a strong broadening of the cubic powder lines. The phase diagram shows a wide coexistence gap between the non-cubic phases and the glass state.     

Copper Defects and Conductivity in Bi—Pb—Sr—Ca—Cu—O Glasses

Glass ceramics of the composition (Bi_0.8Pb_0.2)₄Sr₃Ca₃Cu₄O₈ prepared by the melt quenching technique and the crystalline phases produced by the rapid thermal annealing have been studied by electrical resistivity and electron paramagnetic resonance (EPR) measurements in the temperature range from liquid helium up to room temperature. The concentration of the EPR active Cu^2? paramagnetic centers decreases as conductivity increases for the glass ceramics and disappears after crystallization and the growth of superconducting phases, similar to bulk high-T_c superconductors. The KPR spectra of both glass and crystallized ceramics after short-time annealing indicate the coexistence of Cu^2? paramagnetic ions and the exchange coupled clusters.     

On a quantum theory of superconducting glasses and other impure superconducting phases

We review and extend a previous electronic mean field theory of superconducting glass phases. These phases are defined by vanishing ensemble averaged BCS-order parameter and non-vanishing Edwards-Anderson type averages of the inhomogeneous superconducting order parameter. Solutions are worked out for the replica symmetric case, but the possibility of replica symmetry breaking and hence ergodicity breaking is also discussed in the field theory. The order parameter for Ising-like, anisotropic and isotropicXY-like superconducting glass phases are identified by their spontaneous symmetry breaking effect in the action of the discorder ensemble. The isotropicXY-like phase is found to allow superconductivity in arbitrary strong magnetic fields. Generally the results show that: the occurrence of superconducting glass phases is supported by strong local attractive electron-electron coupling together with a high probability of nonsuper-conducting areas, the vicinity of a metal-insulator transition or the presence of a magnetic field. We suggest that for strong coupling the theory is applicable to HighT _c superconductors like Ba–La–Cu–O.A first result beyond mean field approximation displays at one loop order quantum fluctuation contributions to the density of states in the superconducting glass phases. We suggest that these phases may show an infinite nonlinear dc conductivity in higher order response.Dedicated to Professor Harry Thomas on the occasion of his 60th birthday     

The double-phase transition of ErFe4Ge2. An XRPD study

High-quality powder XRD data of the compound ErFe₄Ge₂ collected in the ESRF beam line BM16, are presented for the entire magnetically ordered regime (T_N=44 K). The data analysis reveals the occurrence of a double symmetry breaking at the magnetic transition. This experiment has allowed us to distinguish between structural and magnetic satellites, both present in the neutron patterns, and to demonstrate the interdependence of structural and magnetic transitions. The high-temperature (HT) phase disproportionates by a first-order transition into two distinct phases: P4₂/mnm (T_c, T_N=44 K)→Cmmm (majority LT phase)+Pnnm (minority IT Phase) which coexist in proportions varying with temperature down to 4 K. The phase diagram comprises three temperature regions: (a) the HT range with T>T_N for the tetragonal P4₂/mnm phase; (b) the IT (intermediate temperature) range, 20 K<T<T_N, where the two phases coexist in strongly variable proportions and the Pnnm phase reaches its highest concentration (≈31%) around 30 K and (c) the LT (low temperature) range, 1.5–20 K, where the Cmmm phase is dominating (up to 95%). We suggests that this phenomenon is the result of competing magneto-elastic mechanisms involving the Er crystal field anisotropy, the Er–Er, Er–Fe and the Fe–Fe exchange interactions and their coupling with the lattice strains.     

An evidence for a microscopic phase separation in AsSeAg glasses revealed by thermal and structural investigations

Alternating Differential Scanning Calorimetric (ADSC) studies show that Se rich As₂₀Se_80-xAg_x (0 ≤ x ≤ 15) glasses exhibit two endothermic glass transitions and two exothermic crystallization peaks; the observed thermal behavior has been understood on the basis that As₂₀Se_80-xAg_x glasses are microscopically phase separated, containing Ag₂Se phases embedded in an As-Se backbone. With increasing silver concentration, the Ag₂Se phase percolates in the As-Se matrix, with a well-defined percolation threshold at x = 8. A signature of this percolation transition is shown up in the thermal behavior, as sudden jumps in the composition dependence of non-reversing enthalpy, ΔH_nr obtained at the second glass transition reaction. Scanning Electron Microscopic (SEM) studies also confirm the microscopic phase separation in these glasses. The super-ionic conduction observed earlier in these glasses at higher silver proportions, is likely to be associated with the silver phase percolation.     

Formation region of amorphous thin CoZr and CuZr films prepared by cocondensation on hot substrates

The glass formation ranges of thin CoZr and CuZr films condensed on cold and hot substrates (10–800 K) are experimentally determined by X-ray diffraction. The maximum substrate temperatures allowed to condense amorphous films are only slightly below the crystallization temperatures of the amorphous phases. These experimental results are compared with predictions of the glass formation ranges from thermodynamic calculations and instability models. At low substrate temperatures, where no phase separation is possible due to kinetic restrictions, the amorphous phase is favoured in the range between theT _o lines which are the stability limits of the extended solid solutions on both sides of a metastable binary phase diagram. For high substrate temperatures, where at least one species of the binary alloy is able to move, the amorphous state can be described to be in a metastable equilibrium with the extended solid solutions neglecting the intermetallic compounds. Therefore, the single-phase amorphous state is restricted to the range between theT _ml lines which are the metastable liquidus temperatures.     

Orthorhombic structure: a necessity in superconducting 1-2-3 compounds

X-ray and resistivity measurements on YBa₂Cu₃O_7−δ (1-2-3) samples show that for the same but low oxygen concentration,δ⋍0·55, no superconducting transition down to 4·2 K is observed for the tetragonal phase samples while the orthorhombic phase shows aT _c ∼ 31 K. The effect of oxygen concentration onT _c is isolated.T _c=91±1 K has, however, been observed continuously for the normal oxygen annealed samples,δ⋍0·07. The experimental results suggest strongly the necessity of the 1-2-3 compound to be in the orthorhombic phase for the superconducting mechanism to be operative.