Hydrothermal Synthesis and Low-Temperature Sintering of Zinc Gallate Spinel Fine Particles

Nanosized powders of single-phase zinc gallate (ZnGa₂O₄) spinel were hydrothermally synthesized from solutions in the presence of NaOH over the pH range of 1.9 to 7.0 and from solutions above pH 7.0, i.e., the very basic medium (pH of 13.85), by removing the residual ZnO phase by washing with aqueous H₂SO₄ from the precipitate mixtures of zinc gallate spinel particles and ZnO. A very wide compositional range (Zn/2Ga = 0.705–1.157) of zinc gallate spinel solid solutions could be hydrothermally synthesized in the form of nanosized particles from acid and very basic mediums (pH of 2.4–13.85) in the presence of NaOH. These hydrothermally synthesized spinel powders showed good sinterability and almost full densification at 1100°C for 1 h. Dense sintered bodies consisting of single-phase zinc gallate spinel were fabricated at 1100°C using zinc gallate spinel powders having almost stoichiometric composition formed from the solution at pH 9.95 in the presence of aqueous ammonia.     

Photocatalytic performance of Fe-substituted ZnAl2O4 powders under sunlight irradiation on degradation of industrial dyes

Using the sol–gel auto combustion method with diethanolamine (DEA) as fuel, a sequence of iron-substituted zinc aluminates, ZnFe_xAl_2-xO₄ powders, including variable Fe³⁺ ion concentrations (0 ≤ x ≤ 2) were effectively prepared. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), the Brunauer–Emmett–Teller (BET) method, UV–visible diffuse reflectance spectroscopy (UV-DRS), and vibrating sample magnetometer (VSM) were employed to examine the structures, chemical bonds, morphologies, composition, surface area, and optical properties as well as the magnetic behavior of the obtained samples. A single-phase spinel structure was obtained for the calcined aluminate powders with different interplanar spacing and crystallite sizes, as revealed by the classification results. The bandgap energy (E_g) of adapted aluminates was in the range of 2.04-3.14 eV, identified as being much lower compared to the pure sample (5.60 eV). Thus, Fe³⁺-substituted ZnAl₂O₄ samples could be successfully photoexcited using both ultraviolet and visible light, as suggested by the results. Examination of how the four main pollutant types decay when irradiated by sunlight was carried out to assess the samples and establish photocatalytic activity. These contaminants included rhodamine B (RhB), methylene blue (MB), methyl orange (MO), and methyl red (MR). The performance of photocatalytic degradation reached 98% after 150 min for all optimal samples of organic dyes. Besides, each of the altered photocatalysts could be recycled and displayed high stability. The S-shaped curve of ferrimagnetism can result in those samples as found by the magnetic measurements, though pure ZnAl₂O₄ displays diamagnetic characteristics. The adapted samples show intense improvement in the remanent magnetization (M_r) when compared to pure ZnAl₂O₄, signifying that magnetic photocatalyst recovery by applying an external magnetic field is easy. Thus, these results offer a convincing sign that ZnAl₂O₄ powders replaced by Fe³⁺ could provide the ability to aid in the ecologically friendly collection of solar energy.     

Formation of Zinc–Antimony-Based Spinel Phases

Formation of spinel phases in ZnO–Sb₂O₃and ZnO–Sb₂O₃–Bi₂O₃systems is studied by the use of X-ray diffraction. The formation of nonstoichiometric Zn_2.33Sb_0.67O₄phase is observed in both the systems at ∼900°C. However, in these systems, at higher temperatures ( T ≥ 1100°C), formation of the inverse spinel phase Zn₇Sb₂O₁₂is observed. The study has been extended to understand the effect of CrO₃doping on the stability of the different spinel phases in the previously mentioned systems. Interestingly, in both the systems, samples doped with CrO₃, displayed the presence of Zn_2.33Sb_0.67O₄phase <1200°C, indicating the stabilization of the spinel phase by CrO₃.     

Studies of structure and cycleability of LiMn2O4 and LiNd0.01Mn1.99O4 as cathode for Li-ion batteries

Lithium manganese oxides LiMn₂O₄ and rare earth elements doped LiNd_0.01Mn_1.99O₄ were synthesized by microwave method. The structure and the electrochemical performances of the samples were characterized. XRD data shows both samples exhibit the same pure spinel phase. But due to the introduction of Nd³⁺ ion into the unit cell, the lattice parameter of the Nd-doped spinel was larger than that of the undoped one. The two samples had a similar morphology including small particle size and homogeneous particle distribution as tested by SEM. The cyclic voltammmetry and constant-current charge-discharge tested that Nd-doped spinel displayed a better reversibility and cycleability.     

The air oxidation of an austenitic Fe-Mn-Cr stainless steel for fusion-reactor applications

The oxidation in air of an austenitic Fe-Mn-Cr steel containing 17.8 Mn, 9.5 Cr, 1.0 Ni, 0.27 C, and 0.03 N was studied over the range 700–1000°C. Oxidation of surface-abraded samples at low temperatures, 700–750°C, resulted in only Mn ₂O₃ containing dissolved chromium, except at corners, where large nodules containing spinel and manganowustite formed. The Mn₂O₃ layer grew into the substrate forming a globular-type film. This growth mode was the result of slow interdiffusion in the alloy after the cold-worked surface layer had been recrystallized and/or consumed, as evidenced by the formation of a ferrite layer subjacent to the scale and by the instability of the planar interface. No internal oxidation was observed beneath the Mn₂O₃ film at either 700 or 750°C. Samples oxidized in thehigh-temperature region, 800–1000°C, exhibited vastly different behavior, forming thick stratified scales at long times (24 hr), the scales consisting of a very thin outer layer of Mn₂O₃ (with appreciable iron in solution), Fe-Mn spinel beneath the outer layer, and a thick inner layer of manganowustite and a chromium-containing spinel. No chromium was found in the outer two layers. A thin layer of nearly pure Fe₂O₃ formed between Mn₂O₃ and the outer spinel. Quasiparabolic kinetics were observed. The high-temperature rates were about 10³ to 10⁴ times greater than at low temperatures at the transition temperature. The rapid rates at high temperatures were attributed to manganowustite growth. However, oxidation of an electropolished sample at 750°C, from which the superficial cold-worked layer had been removed, formed scales similar to those observed at high temperatures at comparable rates. A difference by a factor of over 10⁴ existed between the oxidation rate of the electropolished sample and the surface-abraded sample at 750°C. The much slower oxidation rate of the latter is attributed to greatly enchanced manganese diffusion through the high dislocation-density, cold-worked layer. Short-time tests at 800°C revealed an incubation period during which a thin protective layer of Mn²O₃ formed. The incubation period corresponded to the recrystallization time of the cold-worked layer. Subsequently, nodular growth occurred which was associated with internal oxidation. The nodules, consisting of spinel and manganowustite, eventually linked up to form a thick, stratified scale. Comparison of the scale structures with calculated phase diagrams of composition versus oxygen activity (at constant temperature), showed that the protective films formed at low temperatures were due to kinetics factors, involving enhanced manganese diffusion through the cold-worked layer, rather than to thermodynamics. A model for the breakdown of protective films is proposed which involves internal oxidation.     

The oxidation of Fe-19.6Cr-15.1Mn stainless steel

The oxidation behavior in air of Fe-19.6Cr-15.1Mn was studied from 700 to 1000°C. Pseudoparabolic kinetics were followed, giving an activation energy of 80 kcal/mole. The scale structure varied with temperature, although spinel formation occurred at all temperatures. At both 700 and 800°C, a thin outer layer of -Mn₂O₃ formed. The inner layer at 700°C was (Fe,Cr,Mn)₃O₄, but at 800°C there was an intermediate layer of Fe₂O₃ and an inner layer of Cr₂O₃ + (Fe, Cr,Mn)₃O₄. Oxidation at 900°C produced an outer layer of Fe₃O₄ and an inner layer of Cr₂O₃+(Fe,Cr,Mn)₃O₄. Oxidation at 1000°C caused some internal oxidation of chromium. In addition, a thin layer of Cr₂O₃ formed in some regions with an intermediate layer of Fe₃O₄ and an outer layer of (Fe,Mn)₃O₄. A comparison of rates for Fe₃O₄ formation during oxidation of FeO as well as for the oxidation of various stainless steels, which form spinels, gave good agreement and strongly suggests that spinel growth was rate controlling. The oxidation rate of this alloy (high-Cr) was compared with that of an alloy previously studied, Fe-9.5Cr-17.8Mn (low-Cr) and was less by about a factor of 12 at 1000°C and by about a factor of 100 at 800°C. The marked differences can be ascribed to the destabilization of wustite by the higher chromium alloy. No wustite formation occurred in the high-Cr alloy, whereas, extensive wustite formed in the low-Cr alloy. Scale structures are explained by the use of calculated stability diagrams. The mechanism of oxidation is discussed and compared with that of the low-Cr alloy.     

Spray pyrolysis synthesis of nanostructured LiFexMn2−xO4 cathode materials for lithium-ion batteries

A series of partially Fe-substituted lithium manganese oxides LiFe_xMn_2−xO₄ (0 ≦ x ≦ 0.3) was successfully synthesized by an ultrasonic spray pyrolysis technique. The resulting powders were spherical nanostructured particles which comprised the primary particles with a few tens of nanometer in size, while the morphology changed from spherical and porous to spherical and dense with increasing Fe substitution. The densification of particles progressed with the amount of Fe substitution. All the samples exhibited a pure cubic spinel structure without any impurities in the XRD patterns.The as-prepared powders were then sintered at 750 °C for 4 h in air. However, the particles morphology and pure spinel phase of LiFe_xMn_2−xO₄ powders did not change after sintering. The as-sintered powders were used as cathode active materials for lithium-ion batteries, and cycle performance of the materials was investigated using half-cells Li/LiFe_xMn_2−xO₄. The first discharge capacity of Li/LiFe_xMn_2−xO₄ cell in a voltage 3.5-4.4 V decreased as the value x increased, however these cells exhibited stable cycling performance at wide ranges of charge-discharge rates.     

SYNTHESIS OF NANOSTRUCTURED LiM0.15Mn1.85O4 (M = Mn,Co, Al,AND Fe) PARTICLES BY SPRAY PYROLYSIS IN A FLUIDIZED BED REACTOR

A novel technique has been developed to directly produce fine ceramic powders from liquid solution via spray pyrolysis in a fluidized bed reactor (SPFBR). Using this technique the preparation of LiM_0.15Mn_1.85O₄ (M = Mn, Co, Al, and Fe), which are the most promising cathode materials for lithium-ion batteries, has been carried out at a superficial velocity U₀ of 0.71 m/s, a reactor temperature T of 800°C, and a static bed height L_s of 100 mm. The as-prepared powders were spherical nanostructured particles that comprised primary particles of a few tens of nanometers in size, and they exhibited a pure cubic spinel structure without any impurities in the XRD patterns. The chemical composition of as-prepared samples showed good agreement with the theoretical values that proved stoichiometric formulae of the compounds. The specific surface area of as-prepared LiM_0.15Mn_1.85O₄ (M = Mn, Co, Al, and Fe) powders decreases with increasing the static bed height in each doping metal, while the crystallite size increases with the static bed height. As a result, the as-prepared powders showed larger crystallite size and smaller specific surface area than those prepared by conventional spray pyrolysis.     

Mechanochemical Synthesis of Magnesium Aluminate Spinel Powder at Room Temperature

MgAl₂O₄ spinel was successfully synthesized using a mechanochemical route that avoided the formation and calcination of its precursors at high temperatures. The method involved a single step in which γ-Al₂O₃–MgO, AlO(OH)–MgO, and α-Al₂O₃–MgO mixtures were milled at room temperature under air atmosphere. The formation of MgAl₂O₄ occurred faster with γ-Al₂O₃ than with AlO(OH) or α-Al₂O₃. After 140 h, the mechanochemical treatment of the γ-Al₂O₃–MgO mixture yielded 99% of MgAl₂O₄.     

Analysis of optoelectronic and trasnport properties of magnesium based MgSc2X4 (X=S,Se) spinels for solar cell and energy storage device applications

Intense research work is underway for identifying materials with potential applications in energy storage and energy harvesting systems. The magnesium based scandium chalcogenides have recently emerged as potential candidates for Mg batteries owing to their high Mg ionic conductivity and low electron conduction. At the same time, their band gaps are capable of absorbing electromagnetic radiations in visible to UV range; making them suitable for solar cell applications. In order to analyze the application of MgSc₂X₄(X = S, Se) compounds in energy devices, in this work we employ density functional theory calculations using the full potential linear augmented plane-wave method for examining their optoelectronic and thermoelectric properties. For the structural properties, the generalized gradient approximation functional designed for solids (PBEsol-GGA) has been used, while modified Becke and Johnson (mBJ) potential functional is used for computing the optoelectronic and transport properties. Our calculated optical properties indicate that these materials can find applications in solar cells. Moreover, the electronic transport properties computed using Boltzmann transport equation suggest carrier concentrations in MgSc₂S₄ to MgSc₂Se₄ spinels can be tuned for making them suitable for metal ion batteries.