Effect of processing temperature on the superconducting properties of acetone doped MgB2 tapes

Correlation of phase formation, critical transition temperature T_c, microstructure, and critical current density J_c with sintering temperature has been studied for acetone doped MgB₂/Fe tapes. Sintering was performed at 600–850 °C for 1 h in a flowing Ar atmosphere. High boron substitution by carbon was obtained with increasing the sintering temperature; however, the acetone doped samples synthesized at 800 °C contain large size MgB₂ grains and more MgO impurities. Incomplete reaction for the acetone doped samples heated at 600 °C result in bad intergrain connectivity. At 4.2 K, the best J_c value was achieved in the acetone doped sample sintered at 700 °C, which reached 24,000 A/cm² at 10 T and 10,000 A/cm² at 12 T, respectively. Our results indicate that the small grain size and less impurity were also important for the improvement of J_c–B properties besides the substitutions of B by C.     

Structural and magnetic properties of thin epitaxial Fe films on (1 1 0) GaAs prepared by metalorganic chemical vapor deposition

Iron films have been grown on (1 1 0) GaAs substrates by atmospheric pressure metalorganic chemical vapor deposition at substrate temperatures (T_s) between 135°C and 400°C. X-ray diffraction (XRD) analysis showed that the Fe films grown at T_s between 200°C and 330°C were single crystals. Amorphous films were observed at T_s below 200°C and it was not possible to deposit films at T_s above 330°C. The full-width at half-maximum of the rocking curves showed that crystalline qualities were improved at T_s above 270°C. Single crystalline Fe films grown at different substrate temperature showed different structural behaviors in XRD measurements. Iron films grown at T_s between 200°C and 300°C showed bulk α-Fe like behavior regardless of film thickness (100–6400 Å). Meanwhile, Fe films grown at 330°C (144 and 300 Å) showed a biaxially compressed strain between substrate and epilayer, resulting in an expanded inter-planar spacing along the growth direction. Magnetization measurements showed that Fe films (>200 Å) grown at 280°C and 330°C were ferromagnetic with the in-plane easy axis along the [1 1 0] direction. For the thinner Fe films (⩽200 Å) regardless of growth temperature, square loops along the [1 0 0] easy axis were very weak and broad.     

Superconductivity in bulk T′-(La,Sm)2CuO4 prepared via a molten alkaline hydroxide route

We have synthesized La_2?xSm_xCuO₄ (0 ? x ? 2.0) with the Nd₂CuO₄ structure via a molten alkaline hydroxide route at temperatures as low as 400–480 °C. After reduction heat treatment in vacuum at 600–750 °C for removal of excess oxygen atoms at the interstitial apical site, superconductivity with T_c = 20–24 K was observed in the samples with x = 0.05–1.0. The superconducting volume fraction is nearly 100% for x = 0.3–0.7. Our results demonstrate that La_2?xSm_xCuO₄ with no nominal carrier doping is a bulk superconductor.     

Polymorphic phase transition and thermal stability in squaric acid (H2C4O4)

Phase transformations in squaric acid (H₂C₄O₄) have been investigated by thermogravimetry and differential scanning calorimetry with different heating rates β. The mass loss in TG apparently begins at onset temperatures T_di=245±5 °C (β=5 °C min^?1), 262±5 °C (β=10 °C min^?1), and 275±5 °C (β=20 °C min^?1). A polymorphic phase transition was recognized as a weak endothermic peak in DSC around 101 °C (T_c⁺). Further heating with β=10 °C min^?1 in DSC revealed deviation of the baseline around 310 °C (T_i), and a large unusual exothermic peak around 355 °C (T_p), which are interpreted as an onset and a peak temperature of thermal decomposition, respectively. The activation energy of the thermal decomposition was obtained by employing relevant models. Thermal decomposition was recognized as a carbonization process, resulting in amorphous carbon.     

Low-temperature preparation and properties of ceramics with composition (1−x)CaTiO3−xPbF2−xLiF

Fluorinated ceramics with initial composition (1−x)CaTiO₃+xPbF₂+xLiF were sintered at 950 °C. The X-ray diffraction (XRD) patterns of the samples showed the formation of a novel solid solution in the initial composition range 0⩽x⩽0.125. SEM observations were performed on fractured ceramics and DSC analyses were carried out from room temperature up to 600 °C. Three second-order phase transitions were detected for all the samples. Capacitors were prepared from the pre-sintered ceramics then dielectric measurements were performed as a function of temperature in the frequency range 10²–4×10⁷ Hz. The ε′_r−T curves exhibit the profile of dielectrics for class I capacitors, however the values of tan δ are too high (tan δ⩾1%).     

Experimental investigation of flame spreading over pure methane hydrate in a laminar boundary layer

Flame spreading over pure methane hydrate in a laminar boundary layer is investigated experimentally. The free stream velocity (U_∞) was set constant at 0.4 m/s and the surface temperature of the hydrate at the ignition (T_s) was varied between ?10 and ?80 °C. Hydrate particle sizes were smaller than 0.5 mm. Two types of flame spreading were observed; “low speed flame spreading” and “high speed flame spreading”. The low speed flame spreading was observed at low temperature conditions (T_s = ?80 to ?60 °C) and temperatures in which anomalous self-preservation took place (T_s = ?30 to ?10 °C). In this case, the heat transfer from the leading flame edge to the hydrate surface plays a key role for flame spreading. The high speed flame spreading was observed when T_s = ?50 and ?40 °C. At these temperatures, the dissociation of hydrate took place and the methane gas was released from the hydrate to form a thin mixed layer of methane and air with a high concentration gradient over the hydrate. The leading flame edge spread in this premixed gas at a spread speed much higher than laminar burning velocity, mainly due to the effect of burnt gas expansion.     

A 48% Ni–Fe alloy of low coercivity and improved corrosion resistance in a cyclic damp heat test

Electric arc 30t melts, deoxidised with Mn and Si, are compared to melts additionally deoxidised with cerium. In a cyclic damp heat test the melts with Ce show better corrosion behaviour. μ₄ (DC) and H_c of samples of 1.0 mm thickness after heat treatment at 1080°C vary in the same range of values for both categories of melts. After heat treatment at 1080°C or 1180°C μ₄ (50 Hz) and H_c of samples of 0.2 mm thickness are impaired by 20% or more for melts with Ce. For melts with Ce the strong binding of the sulphur to the deoxidiser impedes desulphurization. With small strip thicknesses, the strong binding energy of Ce to oxygen causes additional internal oxidation during heat treatment . Both deteriorate the magnetic properties. At the larger thickness of 1.0 mm there is no noticeable internal oxidation and/or desulphurization in both categories of melt due to the strip thickness.     

Cathodoluminescence studies of un-doped and (Cu,Fe, and Co)-doped tin dioxide films deposited by spray pyrolysis

Un-doped and (Cu, Fe, and Co)-doped SnO₂ were studied using films deposited by spray pyrolysis. Room temperature cathodoluminescence (CL) was measured. Differences in CL spectra were observed as a function of deposition parameters (T_sub-350–550 °C), the nature and concentration of dopants (0–16 at.%), and the resulting high annealing temperature (T_an = 700–950 °C). A possible luminescence mechanism has been discussed. It was established that changes taking place in CL spectra were caused by the change of both the grain size and crystallinity (stoichiometry) of the surface layer. It was concluded that radiative recombination occurs through shallow donor levels associated with O-vacancies and trapped centers. It was assumed that in SnO₂ there are apparently three types of defects forming deep levels located at 0.8–0.9, 1.3–1.4, and ∼1.6 eV from the top of the valence band.     

Preparation of phase pure and well-crystallized Li4Ti5O12 nanoparticles by precision control of starting mixture and calcining at lowest possible temperatures

In an attempt to obtain spinel Li₄Ti₅O₁₂ with smallest possible grain size and highest possible phase purity via a solid state route, we tried to elevate reactivity of the reactant mixture by mechanical activation and appropriate choice of the starting materials. From the stoichiometric mixture comprising Li₂CO₃ and 150 nm anatase, we needed to heat at 950 °C for 1 h to obtain 81–88% phase purity (PhP) of Li₄Ti₅O₁₂ with its average grain size ca 600 nm. After mechanical activation with a multi-ring mill for 30 min, 850 °C was enough to obtain 85–87% pure 500 nm spinel. From a combination of LiNO₃ and 50 nm anatase, 90–91% phase pure product with its grain size 240 nm was obtained at 750 °C due to fusion of the nitrate and shorter diffusion path. By using CH₃COOLi.2H₂O and 50 nm anatase we obtained 130 nm Li₄Ti₅O₁₂ with its PhP ca 90% by milling the mixture preliminarily calcined at 500 °C for 1 h and heating subsequently at 700 for 1 h.     

Effects of Y2O3 additions on the oxygen diffusion in top-seeded melt growth processed YBa2Cu3O7−y superconductors

To understand the effect of Y₂BaCuO₅ (Y211)/YBa₂Cu₃O_7?y (Y123) interfaces on the oxygen diffusion in single grain YBa₂Cu₃O_7?y superconductors, single grain Y123 superconductors with 0.05 and 0.3 moles of Y₂O₃ additions were fabricated by a top-seeded melt growth (TSMG) process. Y123 compacts with Y₂O₃ additions were subjected to melt growth heating cycles with a cooling rate of 1 °C/h through a peritectic temperature (1015 °C) and then annealed at 450 °C for 200 h in flowing oxygen. The superconducting temperature (T_c) and critical current density (J_c) were estimated for the three different regions (top surface (s), intermediate (i) and center (c)) of samples. The amount of Y211/Y123 interface area in single grain Y123 superconductors was successfully controlled by Y₂O₃ additions. The T_c values of s regions were higher than those of i and c regions, which indicates the presence of more oxygen at the sample surfaces. In addition, the T_c values of i and c regions of the Y123 sample with 0.3 mole Y₂O₃ addition were higher than those of the same regions of the Y123 sample with 0.05 mole Y₂O₃ addition due to the promoted oxygen diffusion through Y211/Y123 interfaces and other related defects. In spite of the promoted oxygen diffusion by Y₂O₃ addition, the large T_c difference among the regions still existed, which suggests sluggish oxygen diffusion into single Y123 grains.     

Growth of Cu0.5Tl0.5Ba2Ca3Cu4−yZnyO12−δ superconductor with optimum carriers

We have tried to vary the carriers concentration in Cu_0.5Tl_0.5Ba₂Ca₃Cu_4?yZn_yO_12?δ (y = 0, 1, 1.5, 2, 2.5) superconductor with the help of post-annealing experiments carried out in nitrogen, oxygen and air and to investigate its effects on the superconductivity parameters. The zero resistivity critical temperature [T_c(R = 0)], the magnitude of diamagnetism and critical current [I_c(H = 0)] are found to increase in Zn free samples after post-annealing in oxygen and air, while these superconducting properties have been suppressed after post-annealing in nitrogen at 550 °C for 6 h. The post-annealing of Zn-doped samples in air has marginally increased the superconducting properties, while these properties have been suppressed after post-annealing in nitrogen and oxygen. These studies have led us to the definite conclusion that the Zn-doped material has grown with optimum carriers concentration.     

Thermal and sonochemical synthesis of porous (Ce,Zr)O2 mixed oxides from metal β-diketonate precursors and their catalytic activity in wet air oxidation process of formic acid

Porous (Ce_0.5Zr_0.5)O₂ solid solutions were prepared by thermolysis (T = 285 °C) or sonolysis (20 kHz, I = 32 W cm⁻², P_ac = 0.46 W mL⁻¹, T = 200 °C) of Ce(III) and Zr(IV) acetylacetonates in oleylamine or hexadecylamine under argon followed by heat treatment of the precipitates obtained in air at 450 °C. Transmission Electron Microscopy images of the samples show nanoparticles of ca. 4–6 nm for the two synthetic approaches. The powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray and μ-Raman spectroscopy of solids obtained after heat treatment indicate the formation of (Ce_0.5Zr_0.5)O₂ solid solutions with a metastable tetragonal crystal structure for the two synthetic routes. The specific surface area of the samples varies between 78 and 149 m² g⁻¹ depending on synthesis conditions. The use of Barrett–Joyner–Halenda and t-plot methods reveal the formation of mixed oxides with a hybrid morphology that combines mesoporosity and microporosity regardless of the method of preparation. Platinum nanoparticles were deposited on the surface of the mixed oxides by sonochemical reduction of Pt(IV). It was found that the materials prepared by sonochemistry exhibit better resistance to dissolution during the deposition process of platinum. X-ray photoelectron spectroscopy analysis shows the presence of Pt(0) and Pt(II) on the surface of mixed oxides. Porous (Ce_0.5Zr_0.5)O₂ mixed oxides loaded with 1.5 %wt. platinum exhibit high activity in catalytic wet air oxidation of formic acid at 40 °C.     

Sputtered magnesium diboride thin films: Growth conditions and surface morphology

Magnesium diboride (MgB₂) thin films were deposited on C-plane sapphire substrates by sputtering pure B and Mg targets at different substrate temperatures, and were followed by in situ annealing. A systematic study about the effects of the various growth and annealing parameters on the physical properties of MgB₂ thin films showed that the substrate temperature is the most critical factor that determines the superconducting transition temperature (T_c), while annealing plays a minor role. There was no superconducting transition in the thin films grown at room temperature without post-annealing. The highest T_c of the samples grown at room temperature after the optimized annealing was 22 K. As the temperature of the substrate (T_s) increased, T_c rose. However, the maximum T_s was limited due to the low magnesium sticking coefficient and thus the T_c value was limited as well. The highest T_c, 29 K, was obtained for the sample deposited at 180 °C, annealed at 620 °C, and was subsequently annealed a second time at 800 °C. Three-dimensional (3D) AFM images clearly demonstrated that the thin films with no transition, or very low T_c, did not have the well-developed MgB₂ grains while the films with higher T_c displayed the well-developed grains and smooth surface. Although the T_c of sputtered MgB₂ films in the current work is lower than that for the bulk and ex situ annealed thin films, this work presents an important step towards the fabrication of MgB₂ heterostructures using rather simple physical vapor deposition method such as sputtering.     

Structural stability and oxygen permeability of cerium lightly doped BaFeO3−δ ceramic membranes

The structural stability under reducing environment and oxygen permeation fluxes of perovskite-type BaCe_xFe_1−xO_3−δ (0 ≤ x ≤ 0.15) ceramic membranes were investigated. The XRD results showed that 5% of cerium doping into the perovskite B-site can make the BaFeO_3−δ transform from the hexagonal structure to the cubic structure, and make the structure stable under 10% H₂–Ar mixed gas at 900 °C for 1 h, but breaks down after 5 h. Lattice parameters and oxygen non-stoichiometry of the as-prepared and reduced samples were measured. Oxygen permeation fluxes of the membranes were measured between 700 and 950 °C. Oxygen permeation during the cooling and heating circles showed that 5% of cerium doping into the perovskite B-site can avoid the phase transformation. The optimum cerium-doped amount on the B-sites was found to be 10%.     

Densely mapping the phase diagram of cuprate superconductors using a spatial composition spread approach

A novel spatial composition spread approach was used successfully to deposit a 52-member library of La_2?xSr_xCuO₄ (0 ? x ? 0.18) using magnetron sputtering combined with physical masking techniques. Two homemade targets of La₂CuO₄ and La_1.82Sr_0.18CuO₄ were sputtered at a power of 41 W RF and 42 W DC, respectively, in a process gas of 15 mTorr argon. The libraries were sputtered onto LaSrAlO₄ (0 0 1), SrTiO₃ (1 0 0) and MgO (1 0 0) substrates through a 52-slot shadow mask for which a ?20 V substrate bias was applied to prevent resputtering. The resulting amorphous films were post-annealed (800 °C for 1 h then at 950 °C for 2 h) in a tube sealed with oxygen gas. Wavelength Dispersive Spectroscopy (WDS) analysis revealed the expected linear variation of Sr content from 0 to 0.18 with an approximate change of 0.003 per library member. Transport measurements revealed superconducting transitions as well as changes in the quasiparticle scattering rate. These transitions and scattering rate changes were mapped to produce the T-hole concentration phase diagram.     

Synthesis of smooth and superconducting (Cu, C)–Ba–O/CaCuO2/(Cu, C)–Ba–O films using SrCuO2 buffer

Artificially stacked structures of [(infinite layer CaCuO₂)_k/(superconducting (Cu, C)Ba₂CuO_x:(Cu, C)-1201)_l]_m were fabricated on SrCuO₂ buffer layer by means of sequential deposition of each block using pulsed laser deposition. Smooth and epitaxial growth all over the deposition cycles of (Cu, C)-1201 and CaCuO₂ were confirmed by streak patterns of in situ RHEED. In comparison with (Cu, C)-1201 single layer films, the artificial stacking resulted in a rise of superconducting properties, T_c-onset and T_c(ρ=0) up to 95 K and 65 K, respectively.     

Thermal annealing of GaSb quantum dots in GaAs formed by droplet epitaxy

We investigate effects of annealing on GaSb quantum dots (QDs) formed by droplet epitaxy. Ga droplets grown on GaAs are exposed to Sb molecular beam and then annealed at T_a=340–450 °C for 1 min to form GaSb QDs. An atomic force microscope study shows that with the increase of T_a, the average diameter of dots increases by about 60%, while their density decreases to about 1/3. The photoluminescence (PL) of GaSb QDs is observed at around 1 eV only for those samples annealed above T_a=380 °C, which indicates that the annealing process plays an important role in forming high quality GaSb QDs.     

Dielectric,optical and structural properties of Bi4V2−xSrxO11−δ (0.05≤x≤0.20)

Composition Bi₄V_2−xSr_xO_11−δ (0.05≤x≤0.20) is synthesized by melt quench technique followed by heat treatment at 800 °C for 12 h. These compounds are characterised by X-ray diffraction, Fourier transform infrared (FTIR) spectroscopy, UV–visible spectroscopy, impedance spectroscopy and scanning electron microscopy. X-ray diffraction patterns of all the samples show γ-phase stabilization at room temperature except x=0.05 heat treated sample. The optical band gap of all the samples is observed in semiconducting range. The lowest and the highest optical band gap is 2.39 eV and 2.57 eV for x=0.10 heat treated and x=0.20 quenched samples, respectively. The highest value of dielectric constant is obtained ~10⁷ with very low dielectric loss for x=0.15 and 0.20 samples at ~350 °C and below 10 Hz. The grain size increases with dopant concentration leads to increase the dielectric constant.     

XRD and EPR structural investigation of some zinc borate glasses doped with iron ions

Glasses in the system xFe₂O₃·(100?x) [45ZnO·55B₂O₃] (0≤x≤10 mol%) have been prepared by melting at 1200 °C and rapidly cooling at room temperature. The obtained samples were submitted to an additional thermal treatment at 570 °C for 12 h in order to relax the glass structure as well as to improve the local order. The as cast and heat treated samples were investigated using X-ray diffraction (XRD) and electron paramagnetic resonance (EPR) measurements. The XRD patterns of all the studied samples show their vitreous nature. Structural modifications occurring in the heat treated samples compared to the untreated ones have been pointed out. EPR spectra of untreated and heat treated samples revealed resonance absorptions centered at g≈2.0, g≈4.3 and g≈6.4. The compositional variation of the line intensity and linewidth of the absorptions from g≈4.3 and g≈2.0 have been interpreted in terms of the variation in the concentration of the Fe³⁺ ions and the interaction between the iron ions. The EPR spectra of the untreated samples containing 5 mol% Fe₂O₃ have been studied at different temperatures (110–290 K). The line intensity of the resonance signals decreases with increase in temperature whereas the linewidth is found to be independent of temperature. It was also found that the temperature variation of reciprocal line intensity obeys the Boltzmann law.     

Superconducting properties of the pyrochlore oxide Cd2Re2O7

We report the superconducting properties of the pyrochlore oxide Cd₂Re₂O₇. The bulk superconducting transition temperature T_c is about 1.0 K, and the upper critical field H_c2 determined by the measurement of specific heat under magnetic fields is 0.29 T. The superconducting coherence length is estimated to be 34 nm. Specific heat data measured on single crystals suggest that the superconducting gap of Cd₂Re₂O₇ is nodeless.