Preparation of superconducting Bi-Sr-Ca-Cu-O ceramics by the sol-gel method

Superconducting Bi-(Pb)-Sr-Ca-Cu-O ceramics were prepared through the sol-gel method using an aqueous solution of metal acetates containing acetic acid and tartaric acid. The conditions of gelation and conversion of gel to Bi₂Sr₂CaCu₂O_x phase were studied by thermal analysis, infrared absorption spectroscopy and X-ray diffraction technique. It was found that transparent gels were obtained from the solutions containing tartaric acid, with a molar ratio of C₄H₆O₆/Cu of about 0.4. The gel matrix was assumed to be composed of carboxylate anions and metal cations. A gel of molar composition BiSrCaCu = 2223 was decomposed to CaCO₃, CaO, CuO and Bi_1-x Sr_xO_y (x = 0.2 to 0.3) at low temperatures of 270 to 600 ° C and produced Bi₂Sr₂CaCu₂O_x phase at 800 ° C via complex intermediate states. A rapid cooling of the heated product increasedT _c (end) in the gel of molar composition BiSrCaCu = 2223, while a slow cooling increasedT _c (end) in the lead-containing gel of molar composition BiPbSrCaCu = 1.850.351.92.03.1. The latter showedT _c (onset) at 115 K andT _c (end) at 105K.     

Investigations of the copper isotope effect in oxygen-deficient YBa2Cu3O7−δ

We present data on the copper isotope effect (⁶³Cu-⁶⁵Cu), C_u =-nT_c/nm_Cu, for two isotopic pairs of oxygen-deficient YBa₂Cu₃O_7–, where varies between 0.06 and 0.52. _Cu is below 0.01 at =0.06 (fully oxygenated), it takes values between –0.14 and –0.34 in the 60 K plateau. Larger negative values of _Cu are observed away from the plateau. The dependence of _Cu is similar to that of the pressure effect dnT_c/dP.     

Synthesis,characterization and electrical conductivity properties of homo- and hetero-di and trimetallic complexes of mixed azo dyes

The synthesis of seven new complexes of mixed ligands and metals are reported. Their stoichiometries (metals:ligands) were found to be 13, 22 and 32 corresponding to FeL₁2L₂H, M₂L₁L₂ and MM₂L₁L₂, respectively (where M = Cu²⁺, M = Cu²⁺, Co²⁺ or Ni²⁺; HL₁ = Methyl Red; H₂L₂ = Alizarin Yellow R). The complexes were characterized by elemental analysis, infrared and Nujol mull electronic spectra and magnetic moment measurements. The results of the electrical conductivity studies for the prepared complexes in the solid state (using compressed tablets) indicated reasonable semiconducting properties. The magnitude of these values, log₂₉₁ lay between –5.46 and –8.67, resulting from the structure and nature of the substituent of the two mixed ligands as well as the high metallic content of their complexes.     

Electrical properties of Si4+ substituted copper ferrite

The electrical resistivity, , and Seebeck coefficient, , for the system Cu_1+xSi_xFe_2–2xO₄ (where x = 0.05, 0.1, 0.15, 0.2 and 0.3) have been studied as a function of temperature. Temperature variation of the resistivity exhibits two breaks. Each break is associated with a change in activation energy. The conduction process at low temperature is governed by the reaction Cu _A ¹⁺ + Cu _A ²⁺ Cu _A ²⁺ + Cu _A ¹⁺ . However, at higher temperature, it is due to intersite cation exchange and reoxidation such as Cu _A ²⁺ + Fe _B ³⁺ Cu _B ²⁺ + Fe _A ³⁺ . Measurement of the Seebeck coefficient, , from room temperature to 800 K reveals n-type conduction for the sample with x= 0.05, while the measurements for other samples show p-type conduction for lower temperatures and n-type conduction at higher temperatures. The activation energies in the paramagnetic region are found to be less than those in the ferrimagnetic region.     

Transport property and battery discharge characteristic studies on 1−x(0.75Agl∶0.25AgCl)∶ xAl2O3 composite electrolyte system

Various experimental studies on a new fast Ag⁺ ion-conducting composite electrolyte system: (1–x) (0.75Agl0.25AgCl)xAl₂O₃ are reported. Undried Al₂O₃ particles of size <10 m were used. The conventional matrix material Agl has been replaced by a new mixed 0.75Agl0.25AgCl quenched and/or annealed host compound. Conductivity enhancements 10 from the annealed host and 3 times from the quenched host obtained for the composition 0.7(0.75Agl0.25AgCl)0.3Al₂O₃, can be explained on the basis of the space charge interface mechanism. Direct measurements of ionic mobility as function of temperature together with the conductivity were carried out for the best composition. Subsequently, the mobile ion concentration n values were calculated from and a data. The value of heat of ion transport q* obtained from the plot of thermoelectric power versus 1/T supports Rice and Roth's free ion theory for superionic conductors. Using the best composition as an electrolyte various solid state batteries were fabricated and studied at room temperature with different cathode preparations and load conditions.     

Superconducting properties of YBa2Cu3O7-Au composites

By X-ray diffraction and photoelectron spectroscopy, we have demonstrated that Au is incorporated in the YBCO lattice up to a concentration 0.1. An XPS study gave evidence for an electronic valence state Au¹⁺. Its replacement in the Cu(1) site appears questionable due to the large difference in ionic radii (Cu²⁺0.073 nm; Au¹⁺0.137 nm). The so called irreversibility lines determined by AC susceptibility measurements are strongly affected by the doping. Up to the limit of solubility in the grains, an improvement in intra and intergrain coupling and flux pinning energy is observed, showing the beneficial interest of YBCO-Au composites.     

Standard Gibbs' energies of formation of BaCuO2, Y2Cu2O5 and Y2BaCuO5

The Gibbs' energies of formation of BaCuO₂, Y₂Cu₂O₅ and Y₂BaCuO₅ from component oxides have been measured using solid state galvanic cells incorporating CaF₂ as the solid electrolyte under pure oxygen at a pressure of 1.01×10⁵ Pa BaO + CuO BaCuO₂ G _f,ox ^o (± 0.3) (kJ mol^–1)=–63.4–0.0525T(K) Y₂O₃ + 2CuO Y₂Cu₂O₂ G _f,ox ^o (± 0.3) (kJ mol^–1)=18.47–0.0219T(K) Y₂O₃ + BaO + CuO Y₂BaCuO₅ G _f,ox ^o (± 0.7) (kJ mol^–1)=–72.5–0.0793T(K) Because the superconducting compound YBa₂Cu₃O_7– coexists with any two of the phases CuO, BaCuO₂ and Y₂BaCuO₅, the data on BaCuO₂ and Y₂BaCuO₅ obtained in this study provide the basis for the evaluation of the Gibbs' energy of formation of the 1-2-3 compound at high temperatures.     

EPR study of polycrystalline superconductors with YBa2Cu3O7 structure

Electron paramagnetic resonance (EPR) of Gd³⁺, Eu²⁺, and copper ions has been investigated in the high-T_c superconductor with YBa₂Cu₃O_7– structure. It has been established that the system is heterogeneous at 0.150.5 and consists of metallic and dielectric regions. The former arises due to oxygen enrichment while the later due to oxygen deficiency. The integral of exchange interaction between Gd³⁺ localized moments and conduction electrons J_sf=0.016 eV has been determined from the normal state temperature dependence of Gd³⁺ EPR linewidth for metallic regions. T_c depression by gadolinium-localized moments for GdBa₂Cu₃O_7– was estimated to be T_c–2K. Anomalies in linewidth temperature dependence upon transition from the normal to the superconducting state have given information about the value and temperature behavior of the superconductor's energy gap. The model, which gives the opportunity to understand some peculiarities of the EPR signal for YBa₂Cu₃O_7– samples, is proposed in terms of several bottlenecked spinsubsystems: spin-liquid in CuO planes and Cu²⁺-O^– and Cu²⁺-O^2– fragments in CuO chains.     

Low-temperature synthesis,pyrolysis and crystallization of tantalum oxide gels

Tantalum oxide gels in the form of transparent monoliths and powders have been prepared from hydrolysis of tantalum pentaethoxide under controlled conditions using different mole ratios of Ta(OC₂H₅)₅C₂H₅OHH₂OHCl. Alcohol acts as the mutual solvent and HCl as the deflocculating agent. For a fixed alkoxide water HCl ratio, the time of gel formation increased with the alcohol to alkoxide molar ratio. Thermal evolution of the physical and structural changes in the gel has been monitored by differential thermal analysis, thermogravimetric analysis, X-ray diffraction, and infrared spectroscopy. On heating to 400 °C, the amorphous gel crystallized into the low-temperature orthorhombic phase -Ta₂O₅, which transformed into the high-temperature tetragonal phase -Ta₂O₅ when further heated to 1450 °C. The volume fraction of the crystalline phase increased with the firing temperature. The -Ta₂O₅ converted back into the low-temperature phase, -Ta₂O₅, on slow cooling through the transformation temperature of 1360 °C, indicating a slow but reversible transformation.     

A precipitate phase in AA2124

A new precipitate phase (designated X phase) other than the S(Al₂CuMg) precipitate phase has been discovered in the 2124 aluminium alloy. Using selected-area electron diffraction analysis, dynamical diffraction simulation, energy dispersion analysis of X-rays and high-resolution electron microscopy, it is suggested that the X phase has an orthorhombic crystal structure witha=0.492 nm,b=0.852 nm andc=0.701 nm. The space group of the phase is Cmmm. There are 10 atoms in a cell with AlCuMg=244. The orientation relationship between the X phase and the matrix is determined as (1–10)_m(010)_x, [–1–1–1]_m [001]_x.     

Electron spin resonance and optical absorption spectra of Cu2+ ions in Na2SO4-ZnSO4 glasses

Electron spin resonance (ESR) and optical absorption spectra of Cu²⁺ ions in Na₂SO₄-ZnSO₄ glasses have been studied. The ESR spectra of Cu²⁺ ion-doped glasses exhibited a pronounced peak atg=2.07 and a shallow quadruplet atg=2.35, the latter arising from the hyperfine splitting of g. ESR spectra of Cu²⁺ ion-doped glasses were also studied by varying the concentration of Cu²⁺ions, temperature and composition of the glasses. The optical absorption spectra exhibited a broad absorption band in the near infrared region, which is attributed to²B_1g²B_2g transition. By correlating the ESR and optical absorption data, the bonding orbital coefficients ² and ₁ ² for Cu²⁺ ions have been evaluated.     

63Cu NMR in the normal state of HgBa2Ca2Cu3O8+δ

We present a⁶³Cu NMR study of HgBa₂Ca₂Cu₃O₈₊ underdoped single crystals with T_c 115 K. While the uniform spin susceptibility decreases below T_o 370 K, relaxation rate measurements demonstrate the opening of a spingap at Q = (, ) below T* 230 K, the highest temperature reported so far. The characteristic energy of spin fluctuations is shown to be higher than in underdoped YBa₂Cu₃O_7–, and the analysis of the quadrupole and hyperfine couplings suggests that the in-plane Cu-O hybridization is also stronger. The T-dependence of T₁ is the same in the three CuO₂ planes which seems hardly compatible with the pure interlayer spin-pairing picture.     

Surface nucleation and cellular growth kinetics of cordierite glass ceramics containing 3 mol % Y2O3-ZrO2

Cordierite-based glass ceramics of the 2MgO2Al₂O₃5SiO₂ composition with t-ZrO₂ (3 mol% Y₂O₃-ZrO₂) and P₂O₅ addition, was heat-treated isothermally and isochronically for crystallization studies. Major crystalline phases incurred by the heat treatment were t-ZrO₂ and -cordierite. Surface nucleation predominated when edge and corner nucleation in these samples were suppressed regardless of their radii of curvature. Crystallization began with the formation of -quartz S.S. and its transformation to -cordierite was followed by prolonged heating. Cellular growth of -cordierite on the surface of the quenched glass plates, gave a linear kinetics. The activation energy for cellular growth was 410 kJ mol^–1.     

Phases on the “Perovskite Line” in the La-Sr-Cu-O System

Our recent research in the La-Sr-Cu-O system has revealed the existence of two new oxygendeficient compounds. One is (La_1–x Sr _x )₄Cu₄O₁₀ (x=0.135–0.15 4-4-10 phase), which has the same structure as CaMnO_2.5 and transforms to the well-known (La_1–x Sr _x )₈Cu₈O₂₀ (x=0.135–0.30 8-8-20 phase) at higher temperature. The other is (La_1–x Sr _x )₅Cu₅O₁₃ (x=0.125–0.1666 5-5-13 phase), which is synthesized under high oxygen pressure and is isostructural to La₄BaCu₅O₁₃ (4-1-5 phase). We have also studied the strontium-rich compound (La_1–x Sr _x )₈Cu₈O₁₆₊ (x=0.7–0.8 8-8-16+ phase) and isolated the semiconductor-like 8-8-16 phase (0.0) and the metallic 8-8-18 phase (>2.0). Cations (La and Sr) in several of these compounds on the (La+Sr)Cu=11 line, which we call the perovskite line, are distributed in a disordered manner and their crystal structures can be explained by the systematic removal of oxygen atoms from an ideal perovskite structure.     

The penetration depth of HgBa2CuO4+δ with 0.07 ≤ δ ≤ 0.35

The magnetic penetration depth (T) of three HgBa₂CuO₄₊ samples with 0.16 < 0.27 has been determined from the reversible magnetization. The obtained follows a BCS-like correlation of 1/² 1–(T/T_c)² over whole measured temperature range in an underdoped sample with T_c 90 K, but deviates significantly from similar fits in an overdoped sample with the same T_c and an optimum doped sample, whose 1/² 's depends on T nearly linearly below T_c/2. This asymmetry between the underdoped and overdoped samples suggests that the T-dependence of 1/² is affected by doping in a complicated way.     

Transport results from untwinned YBCO: Washboard frequency of the vortex lattice,and the quasiparticle mean free path

The washboard frequency of the moving vortex lattice in untwinned YBa₂ Cu₃ O_6.93 may be observed through mode-locking to an externally applied ac current of frequency _ext. The interference between and _ext results in jumps in the dc current-voltage characteristics when and _ext are harmonically related¹. The interference effect disappears in the vortex liquid state. The Hall conductivity _xy below T_c in YBCO contains contributions² from a positive quasiparticle (qp) term (H) and a negative vortex term (1/H). The qp term is surprisingly large well below T_c and implies a large gap anisotropy and a long qp mean free path (mfp). The thermal Hall effect³ _xy is closely related to the qp _xy; _xy is produced by asymmetric scattering of qp by pinned vortices. The qp mfp at H = 0, extracted from _xy and extended to low T by _xy, increases remarkably from 90 Å at T_c to more than 0.5m at 22 K.     

Microstructure and properties of supersaturated ZA27 alloy during natural ageing

The decomposition of the supersaturated solid solution of ZA27 alloy at room temperature has been investigated by X-ray diffraction, TEM and mechanical properties testing. Based on the results obtained, both continuous precipitation and cellular reaction occur during the decomposition process. The continuous precipitation follows the sequence: ₁ + spherical GP zones ₂ + elliptical GP zones ₃ + R + . The cellular reaction can be written: + + . The properties of the alloy depend on the microstructure. After 1 month of ageing, a series of changes of microstructure have taken place. The properties of the alloy are: _b=500 MPa, =13%,H _v=148.     

Fabrication of Bi2Sr2CaCu2Ox films on metal substrates by the chemical process using metal alkoxides

The formation behaviour of Bi₂Sr₂CaCu₂O_x from compounds prepared by hydrolysis of metal alkoxides was studied and Bi₂Sr₂CaCu₂O_x films on metal substrates were fabricated using a metal alkoxide solution. Bi₂Sr₂CaCu₂O_x was formed through intermediate phases such as Bi₂Sr₂Cu₁O_x, Bi₂CuO₄, SrCO₃, CaCO₃ and CuO. Bi₂CuO₄ was initially formed with SrCO₃, CaCO₃ and CuO, and then reacted with SrCO₃ to form Bi₂Sr₂Cu₁O_x. Bi₂Sr₂Cu₁O_x reacted with CaCO₃ and CuO to give Bi₂Sr₂CaCu₂O_x. Bi₂Sr₂CaCu₂O_x films were successfully fabricated on nickel substrates using the metal alkoxide solution at the nominal composition of BiSrCaCu=2223. Bi₂Sr₂CaCu₂O_x was precipitated on Ni substrates at firing temperature of 770 °C or above, and a sharp T _c was obtained at the firing temperature of 800 °C.     

The origins of mullite formation

The evolution of mullite formation has been studied from Al₂O₃-SiO₂ gels. The studies have established (a) the identity of the controversial cubic phase, (b) the chemical, structural and compositional continuity in the evolution of mullite formation, (c) the existence of solid solutions between (32) and (21) mullites, (d) the origins of the exotherms, and (e) the origins of mullite formation. The Al-Si spinel has a composition and structure similar to that of the (21) mullite, i.e. _x Al_16-x ^vi[Al _x Si_4-x ]^ivO₃₂.