MgB2 fabrication by diffusion-controlled three layered (B-Mg-B) technique

MgB₂ was successfully fabricated through diffusion-controlled three-layered (B-Mg-B) technique under high pressure. Due to melting temperature of Mg, the material was pre-heat treated at 600 °C between 1 and 48 h. Optimum pre-heat treatment condition was found to be 600 °C for 48 h. Then, the compacted material was grinded and pelletized under pressure of 2 ton. The pellets were heat treated at 600-900 °C for 1-48 h. Optimum heat treatment condition was determined to be 800 °C for 1 h for formation of almost pure MgB₂. Diffusion coefficient was determined with Fick's law and EDX data. Diffusion coefficient value for B in Mg matrix and Mg in B matrix was determined to be 1.66×10⁻⁷ and 3.14×10⁻⁸ cm²/sn, respectively. Best T_c value (39.4 K) was obtained for material heat treated at 800 °C for 1 h. A symmetric hysteresis was obtained for the best MgB₂ material and magnetization decreased with increase in the temperature and the applied magnetic field.     

Synthesis and utilization of Mg/Al hydrotalcite for removing dissolved humic acid

It has been synthesized Mg/Al layered double hydroxide anionic clay (Mg/Al hydrotalcite) through direct precipitation by adding 0.5 M NaOH solution into a mixed solution containing Mg(NO₃)₂ and Al(NO₃)₃ with molar ratio of 0.1:0.05 until the medium acidity reached pH 10.1. The synthesized Mg/Al hydrotalcite was then utilized to remove dissolved humic acid in aqueous medium. The humic acid was isolated from peat soil taken in Gambut District, South Kalimantan, Indonesia using the recommended procedure of IHSS (International Humic Substances Society). The removal of humic acid was mostly occurred through simple sorption process without accompanied by significant intercalation. The sorption was optimum at pH 9.0, with the first order rate constant, capacity and energy of sorption were 5.50 × 10⁻³ min⁻¹, 0.12 mmol g⁻¹ (69 mg g⁻¹), and 28.32 kJ mol⁻¹, respectively.     

Coating formation by plasma electrolytic oxidation on ZC71/SiC/12p-T6 magnesium metal matrix composite

Plasma electrolytic oxidation (PEO) of a ZC71/SiC/12p-T6 magnesium metal matrix composite (MMC) is investigated in relation to coating growth and corrosion behaviour. PEO treatment was undertaken at 350 mA cm⁻² (rms) and 50 Hz with a square waveform in stirred 0.05 M Na₂SiO₃.5H₂O/0.1 M KOH electrolyte. The findings revealed thick, dense oxide coatings, with an average hardness of 3.4 GPa, formed at an average rate of ∼1 μm min⁻¹ for treatment times up to 100 min and ∼0.2 μm min⁻¹ for later times. The coatings are composed mainly of MgO and Mg₂SiO₄, with an increased silicon content in the outer regions, constituting <10% of the coating thickness. SiC particles are incorporated into the coating, with formation of a silicon-rich layer at the particle/coating interface due to exposure to high temperatures during coating formation. The distribution of the particles in the coating indicated growth of new oxide at the metal/coating interface. The corrosion rate of the MMC in 3.5% NaCl is reduced by approximately two orders of magnitude by the PEO treatment.     

Superconductivity in porous MgB2

Porous magnesium diboride samples have been prepared by the heat treatment of a pressed mixture of Mg and MgB₂ powders. It was found that linked superconducting structure is formed down to the minimum normalized density γ_c=d/d₀≅0.16 (percolation threshold), where d is the density of MgB₂ averaged over the sample, d₀=2.62 g/cm³ is the X-ray density. Lattice parameters and critical temperature of the porous sample decrease with increasing porosity (decreasing γ) and T_c2≅32 K is minimal at γ_c. The grain boundaries in the porous samples are transparent for the current and J_c∼3×10⁵ A/cm² in self field at T=20 K in the samples with γ∼0.24.     

Van der Pauw resistivity measurements on evaporated thin films of cadmium arsenide, Cd3As2

Cadmium arsenide is a II-V semiconductor, exhibiting n-type intrinsic conductivity with high mobility and narrow bandgap. It is deposited by thermal evaporation, and has shown the Schottky and Poole-Frenkel effects at high electric fields, but requires further electrical characterisation. This has now been extended to low-field van der Pauw lateral resistivity measurements on films of thickness up to 1.5 μm. Resistivity was observed to decrease with increasing film thickness up to 0.5 μm from about 3 × 10⁻³ Ω m to 10⁻⁵ Ω m, where the crystalline granular size increases with film thickness. This decrease in resistivity was attributed to a decrease in grain boundary scattering and increased mobility. Substrate temperature during deposition also influenced the resistivity, which decreased from around 10⁻⁴ Ω m to (10⁻⁵ to 10⁻⁶) Ω m for an increase in substrate deposition temperature from 300 K to 423 K. This behaviour appears to result from varying grain sizes and ratios of crystalline to amorphous material. Resistivity decreased with deposition rate, reaching a minimum value at about 1.5 nm s⁻¹, before slowly increasing again at higher rates. It was concluded that this resulted from a dependence of the film stoichiometry on deposition rate. The dependence of resistivity on temperature indicates that intercrystalline barriers dominate the conductivity at higher temperatures, with a hopping conduction process at low temperatures.     

The synthesis and kinetic growth of anisotropic silver particles loaded on TiO2 surface by photoelectrochemical reduction method

Silver nanorods with average diameters of 120-230 nm and aspect ratio of 1.7-5.0 were deposited on the surface of TiO₂ films by photoelectrochemical reduction of Ag⁺ to Ag under UV light. The composite films prepared on soda-lime glass substrates were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and atomic force microscopy (AFM). The results show that the TiO₂ film after UV irradiation in AgNO₃ solution is composed of anatase phase TiO₂ and metallic silver with face centered cubic structure. Other compounds cannot be found in the final films. The maximum deposition content of silver particles on the surface of TiO₂ film was obtained with the AgNO₃ concentration of 0.1 M. The kinetic growth rates of silver particles can be controlled by photocatalytic activity of TiO₂ films. The studies suggest that the growth rates of silver particles increase with the enhancement of photocatalytic activity of TiO₂ films. The maximum growth rate of silver particles loaded on TiO₂ films can be up to 0.353 nm min⁻¹ among samples 1#, 2# and 3#, while the corresponding apparent rate constant of TiO₂ is 1.751 × 10⁻³ min⁻¹.     

A kinetic study of the thermal decomposition process of potassium metabisulfite: Estimation of distributed reactivity model

The thermal decomposition kinetics of potassium metabisulfite was studied by thermogravimetric (TG) and differential thermogravimetric (DTG) techniques using non-isothermal experiments. The apparent activation energy (E_a) is determined using the differential (Friedman) isoconversional method. The results of the Friedman's isoconversional analysis of the TG data suggests that the investigated decomposition process follows a single-step reaction and the observed apparent activation energy was determined as 122.4±2.1 kJ mol⁻¹. A kinetic rate equation was derived for the decomposition process of potassium metabisulfite with contracting area model, f(α)=2(1−α)^1/2, which is established using the Malek's kinetic procedure. The value of pre-exponential factor (A) is also evaluated and was found to be A=1.37×10¹² min⁻¹. By applying the Miura's procedure the distributed reactivity model (DRM) for investigated decomposition process was established. From the dependence α versus E_a, the experimental distribution curve of apparent activation energies, f(E_a), was estimated. By applying the non-linear least-squares analysis, it was found that the Gaussian distribution model (with distribution parameters E₀=121.3 kJ mol⁻¹ and σ=1.5 kJ mol⁻¹) represents the best reactivity model for describing the investigated process. Using the Miura's method, the A values were estimated at five different heating rates and the average A values are plotted against E_a. The linear relationship between the A and E_a values was established (compensation effect). Also, it was concluded that the E_a values calculated by the Friedman's method and estimated distribution curve, f(E_a), are correct even in the case when the investigated decomposition process occurs through the single-step reaction mechanism.     

Influence of heating rate on the crystalline properties of 0.7BiFeO3-0.3PbTiO3 thin films prepared by sol-gel process

0.7BiFeO₃-0.3PbTiO₃ (BFPT7030) thin films were deposited on SiO₂/Si substrates by sol-gel process. The influence of heating rate on the crystalline properties of BFPT7030 thin films were studied by X-ray diffraction (XRD), scanning electron microscope (SEM), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). XRD patterns of the films showed that a pure perovskite phase exists in BFPT7030 films annealed by rapid thermal annealing (RTA) technique. SEM and AFM observations demonstrated that the BFPT7030 films annealed by RTA at 700 °C for 90 s with the heating rate of 1 °C s⁻¹ could show a dense, crack-free surface morphology, and the films’ grains grow better than those of the films annealed by RTA at the same temperature with other heating rates. XPS results of the films indicated that the ratio of Fe³⁺:Fe²⁺ is about 21:10 and 9:5 for the films annealed by RTA at 700 °C for 90 s with the heating rate of 1 and 20 °C s⁻¹, respectively. That means the higher the heating rate, the higher the concentration of Fe²⁺ in the BFPT7030 thin films.     

Stable cycle-life properties of Ti-doped LiFePO4 compounds synthesized by co-precipitation and normal temperature reduction method

Submicron-sized LiFePO₄ and Ti-doped LiFePO₄ cathode materials were synthesized by a reformative co-precipitation and normal temperature reduction method, for which Ti ions were added in the process of preparing precursors to pursue a kind of sufficient and homogenous doping way. ICP and XRD analyses indicate that Ti ions were sufficiently doped in LiFePO₄ and did not alter its crystal structure. It is noted that higher Ti ions doping levels are conducive to electrochemical performance of LiFePO₄, especially on the aspect of stable cycle-life at higher C rates. The sample doped with 3 at% Ti shows the most impressive cycling performance, even after 100 cycles, discharge capacity of 133 mAh g⁻¹ was obtained (102.3% of its initial value) at 1C rate, and the discharge decreased little from 124 to 120 mAh g⁻¹ (96.8% of its initial value) at 2C rate.     

Chitin-humic acid hybrid as adsorbent for Cr(III) in effluent of tannery wastewater treatment

Adsorption of Cr(III) from both synthetic and real samples of tannery wastewater treatment's effluent on chitin-humic acid (chitin-HA) hybrid has been carried out. Rate constant and capacity of adsorption of Cr(III) from the synthetic sample were investigated and removal of Cr(III) from the real sample was tested at optimum medium acidity equivalent to pH 3.5. Characterization using Fourier transform infra red (FT-IR) spectroscopy revealed that both COO⁻ and N-acetyl originated from respectively humic acid (HA) and chitin were involved on the adsorption of Cr(III), and hence the Freundlich's multilayer and multi-energy adsorption model was more applicable to treat the adsorption data than the Langmuir's monolayer and mono-energy model. The quantification of adsorption capacity and rate constant using Freundlich isotherm model and first order adsorption reaching equilibrium yielded values of 6.84 × 10⁻⁴ mol g⁻¹ (35.57 mg g⁻¹) and 1.70 × 10⁻² min⁻¹, respectively. Removal test for the real wastewater treatment's effluent showed that the maximum amount of Cr(III) could be removed by 1 g of chitin-HA hybrid was 2.08 × 10⁻⁴ mol or equivalent to 10.82 mg.     

Low-temperature synthesis of nanocrystalline Ca1−xHoxMnO3−δ (0?x?0.3) powders

Nanocrystalline Ca_1−xHo_xMnO_3−δ (0?x?0.3) manganites were synthesized as phase-pure by a simple and instantaneous solution autogel combustion method, which is a low temperature initiated synthetic route to obtain fine grain size. All the samples, heated at 800 °C for 18 h, can be produced as phase-pure; the polycrystalline powders are homogeneous and possess ultrafine particle size. The holmium-doped calcium manganites retain the orthorhombic phase of the undoped sample. The scanning electron microscope (SEM) images revealed that the combustion-derived compounds exhibit particle size that decreases with holmium content from 300 to 80 nm. All manganites show two active IR vibrational modes near 400 and 600 cm⁻¹. The high temperature dependence of resistivity was measured using a standard four-probe method in the range 25-600 °C. All the samples exhibit semiconductor behaviour and holmium induces a marked decrease in the electrical resistivity when compared with the parent CaMnO₃. The results can be well attributed to the Mn⁴⁺/Mn³⁺ ratio and to the particle grain size.     

Synthesis of spherical LiFePO4/C via Ni doping

Spherical LiFePO₄/C powders were synthesized by the conventional solid-state reaction method via Ni doping. Low-cost asphalt was used as both the reduction agent and the carbon source. An Ni-doped spherical LiFePO₄/C composite exhibited better electrochemical performances compared to an un-doped one. It presented an initial discharge capacity of 161 mAhg⁻¹ at 0.1 C rate (the theoretical capacity of LiFePO₄ with 5 wt% carbon is about 161 mAhg⁻¹). After 50 cycles at 0.5 C rate, its capacity remained 137 mAhg⁻¹ (100% of the initial capacity) compared to 115 mAhg⁻¹ (92% of the initial capacity) for an un-doped one. The electrochemical impedance spectroscopy analysis and cyclic voltammograms results revealed that Ni doping could decrease the resistance of LiFePO₄/C composite electrode drastically and improve its reversibility.     

Effects of peak current density on the mechanical properties of nanocrystalline Ni-Co alloys produced by pulse electrodeposition

Cobalt content, grain size, microhardness and tensile strength of nanocrystalline Ni-Co deposits produced from a solution containing saccharin and cobalt sulfate at constant electrodeposition conditions (pulse on-time T_on at 1 ms and pulse off-time T_off at 15 ms) but varying the peak current density J_p were investigated. It is found that an increase in J_p makes the deposit Co content lower, colony-like morphology more obvious, grain size smaller, and hardness and tensile strength higher. All of the facts are believed to result from the higher overpotential and nucleation rates caused by the J_p increase. But its further increase could lead to reduction in the hardness and tensile strength. Peak current densities in the range of 100-120 A dm⁻² are recommended for the preparation of nanostructured Ni-Co alloy deposits with grain sizes in the range of 15-20 nm, containing 7-8% Co, possessing hardness of 590-600 kg mm⁻² and tensile strength of 1180-1200 MPa—significantly higher than the strength of pure nickel deposit which is produced by the similar method and gets similar grain size.     

Annealing temperature influence on electrical properties of ion beam sputtered Bi2Te3 thin films

Ion beam sputtering process was used to deposit n-type fine-grained Bi₂Te₃ thin films on BK7 glass substrates at room temperature. In order to enhance the thermoelectric properties, thin films are annealed at the temperatures ranging from 100 to 400 °C. X-ray diffraction (XRD) shows that the films have preferred orientations in the c-axis direction. It is confirmed that grain growth and crystallization along the c-axis are enhanced as the annealing temperature increased. However, broad impurity peaks related to some oxygen traces increase when the annealing temperature reached 400 °C. Thermoelectric properties of Bi₂Te₃ thin films were investigated at room temperature. The Bi₂Te₃ thin films, including as-deposited, exhibit the Seebeck coefficients of −90 to −168 μV K⁻¹ and the electrical conductivities of 3.92×10²-7.20×10² S cm⁻¹ after annealing. The Bi₂Te₃ film with a maximum power factor of 1.10×10⁻³ Wm⁻¹ K⁻² is achieved when annealed at 300 °C. As a result, both structural and transport properties have been found to be strongly affected by annealing treatment. It was considered that the annealing conditions reduce the number of potential scattering sites at grain boundaries and defects, thus improving the thermoelectric properties.     

Preparation of five-layered Si/SixGe1−x nano-films by RF helicon magnetron sputtering

Five-layered Si/Si_xGe_1−x films on Si(1 0 0) substrate with single-layer thickness of 30 nm, 10 nm and 5 nm, respectively were prepared by RF helicon magnetron sputtering with dual targets of Si and Ge to investigate the feasibility of an industrial fabrication method on multi-stacked superlattice structure for thin-film thermoelectric applications. The fine periodic structure is confirmed in the samples except for the case of 5 nm in single-layer thickness. Fine crystalline Si_xGe_1−x layer is obtained from 700 °C in substrate temperature, while higher than 700 °C is required for Si good layer. The composition ratio (x) in Si_xGe_1−x is varied depending on the applied power to Si and Ge targets. Typical power ratio to obtain x = 0.83 was 7:3, Hall coefficient, p-type carrier concentration, sheet carrier concentration and mobility measured for the sample composed of five layers of Si (10 nm)/Si_0.82Ge_0.18 (10 nm) are 2.55 × 10⁶ /°C, 2.56 × 10¹² cm⁻³, 1.28 × 10⁷ cm⁻², and 15.8 cm⁻²/(V s), respectively.     

Properties of highly oriented spray-deposited fluorine-doped tin oxide thin films on glass substrates of different thickness

Transparent conducting thin films of fluorine-doped tin oxide (FTO) have been deposited onto the preheated glass substrates of different thickness by spray pyrolysis process using SnCl₄·5H₂O and NH₄F precursors. Substrate thickness is varied from 1 to 6 mm. The films are grown using mixed solvent with propane-2-ol as organic solvent and distilled water at optimized substrate temperature of 475 °C. Films of thickness up to 1525 nm are grown by a fine spray of the source solution using compressed air as a carrier gas. The films have been characterized by the techniques such as X-ray diffraction, optical absorption, van der Pauw technique, and Hall effect. The as-deposited films are preferentially oriented along the (2 0 0) plane and are of polycrystalline SnO₂ with a tetragonal crystal structure having the texture coefficient of 6.19 for the films deposited on 4 mm thick substrate. The lattice parameter values remain unchanged with the substrate thickness. The grain size varies between 38 and 48 nm. The films exhibit moderate optical transmission up to 70% at 550 nm. The figure of merit (φ) varies from 1.36×10⁻⁴ to 1.93×10⁻³ Ω⁻¹. The films are heavily doped, therefore degenerate and exhibit n-type electrical conductivity. The lowest sheet resistance (R_s) of 7.5 Ω is obtained for a typical sample deposited on 4 mm thick substrate. The resistivity (ρ) and carrier concentration (n_D) vary over 8.38×10⁻⁴ to 2.95×10⁻³ Ω cm and 4.03×10²⁰ to 2.69×10²¹ cm⁻³, respectively.     

Influence of Al2O3 additions on crystallization mechanism and conductivity of Li2O-Ge2O-P2O5 glass-ceramics

The crystallization mechanism and conductivity of lithium aluminum germanium phosphate [LAGP] glass-ceramics fabricated from Li_1+xAl_xGe_2−x(PO₄)₃ (x=0.0-0.7) glass system were investigated as a function of Al₂O₃ additions. A non-isothermal analysis was performed to study the crystallization behavior of LAGP glass-ceramics at various heating rates (5-25K min⁻¹) by the Kissinger equation and the Augis-Bennett equation, illustrating volume crystallization for the glass-ceramics. The crystal identification and microstructure in glass-ceramics containing various Al₂O₃ contents were analyzed by means of XRD and FESEM. The main phase of the glass-ceramics was found to be LiGe₂(PO₄)₃, with AlPO₄ as the impurity phase. Additionally the highest total ionic conductivity (5.8×10⁻⁴ S/cm) at room temperature was obtained when x=0.5 for Li_1+xAl_xGe_2−x(PO₄)₃ (x=0.0-0.7) glass-ceramics, suggesting that it was a promising electrolyte for practical application in all-solid-state lithium batteries.     

Hierarchically porous nanoflowers from TiO2–B nanosheets with ultrahigh surface area for advanced lithium-ion batteries

In this work, hierarchically porous TiO₂–B nanoflowers have been successfully synthesized via a facile solvothermal method followed by calcination treatment. The TiO₂–B nanoflowers are constructed by thin nanosheets, presenting ultrahigh specific surface area, up to 214.6 m² g⁻¹. As anode materials for Li-ion batteries, the TiO₂–B sample shows high reversible capacity, excellent cycling performance and superior rate capability. The specific capacity of TiO₂–B could remain over 285 mA h g⁻¹ at 1 C and 181 mA h g⁻¹ at 10 C rate after 100 cycles. We believe that the pseudocapacitive mechanism, ultrahigh surface area and scrupulous nanoarchitecture of the TiO₂–B are responsible for the enhancement of electrochemical properties.     

Li-intercalation into hexagonal boron nitride

A Li hexagonal boron nitride (hBN) intercalation compound (Li-hBNIC) was successfully synthesized by the annealing of powder or bulk hBN and Li at 1523 K. By an XRD analysis, a strong peak indicating the expansion of BN interlayer distance due to Li-intercalation was observed at an angle lower than that of hBN (0 0 2). In the sample, the interlayer distance and its expansion ratio were 3.76 Å and 12.6%, respectively, and these values were similar to those of a first stage Li-graphite intercalation compound (Li-GIC), LiC₆. The electrical conductivity of the sample was increased by several orders of magnitude, from 10⁻¹⁵ to 10⁻⁷ Ω⁻¹ cm⁻¹ at room temperature. Li de-intercalation was confirmed by the dispersion of the sample in purified water.     

Experimental determination of solid-liquid interfacial energy for solid Sn in the Sn-Mg system

The equilibrated grain boundary groove shapes for solid Sn in equilibrium with the Sn-9 at.% Mg eutectic liquid were directly observed annealing a sample at the eutectic temperature for about 5 days with a radial heat flow apparatus. The thermal conductivities of the solid phase, κ_S, and the liquid phase, κ_L, for the groove shapes were measured. From the observed grain boundary groove shapes, the Gibbs-Thomson coefficient, the solid-liquid interfacial energy and grain boundary energy for solid Sn in equilibrium with the Sn-9 at.% Mg eutectic liquid have been determined to be (7.35 ± 0.36) × 10⁻⁸ Km, (136.41 ± 13.64) × 10⁻³ J m⁻² and (230.95 ± 25.40) × 10⁻³ J m⁻², respectively.