Solid state amorphization transformation in the mechanically alloyed Fe27.9Nb2.2B69.9 powders

Mössbauer spectrometry and Rietveld analysis of X-ray diffraction patterns were used to follow the solid state amorphization transformation during the milling process of the Fe_27.9Nb_2.2B_69.9 powders. The reaction between elemental Fe, Nb and B powders leads to the formation of the Nb(B) and Fe(B) solid solutions after 1 and 10 h of milling, respectively. A mixture of α-Fe, Nb(B) and highly disordered Fe(Nb, B) solid solution is found after 25 h of milling. An amorphous structure is obtained on further milling time (100 h). From the Mössbauer spectrometry results, it is observed that the total mixing of the elemental powders, at the atomic level, is achieved after 50 h of milling and a stationary state corresponding to a full paramagnetic amorphous phase is reached after 100 h of milling. The amorphization process can be described by an Avrami parameter close to n = 1.     

Preparation and characterization of Y3Al5O12 (YAG) nano-powder by co-precipitation method

YAG precursor was synthesized by a co-precipitation method from a mixed solution of aluminum and yttrium nitrates with aqueous ammonia as the precipitator. The structure, phase evolution and morphology of YAG precursor and the sintered powders were studied by means of IR, TG/DTA, XRD, TEM methods. It was found the precursor with approximate composition of Al(OH)₃·0.3[Y₂(OH)₅·(NO₃)₂·2H₂O] directly transformed to pure-YAG phase at 800 °C and no intermediate phases were detected. YAG nanocrystalline powders from sintering the precursor at different temperatures were less-aggregated and the diameters of the grains were about 40-100 nm. BET surface area of the particles decreased with increase of calcination temperature and the powder sintered at 800 °C can be used for fabrication of transparent YAG ceramics.     

Structural and magnetic characterization of LiMn1.825Cr0.175O4 spinel obtained by ultrasonic spray pyrolysis

Quaternary spinel oxide LiMn_1.825Cr_0.175O₄ powder was synthesized by using an ultrasonic spray pyrolysis method, without additional annealing. The crystal structure of the as-prepared powder was revealed by X-ray powder diffraction and identified as a single spinel phase with Fd3m space group. The powders had a spherical morphology with extremely smooth surface appearance and densely congested interior structure. Transmission electron microscopy confirmed that the particle consisted by the cohesion of the primary particles. Magnetic measurements performed in DC field in both zero-field-cooled and field-cooled regimes, as well as AC susceptibility experiments, show that system undergoes spin-glass transition at the freezing temperature T_f = 20 K. The value of the effective magnetic moment μ_eff = 4.34 μ_B obtained from the Curie-Weiss fit in the high temperature region confirms the substitution of Mn³⁺ ions with Cr³⁺ ions.     

Peculiarities of photoluminescence of Al2O3 bulk and nanosize powders at low temperatures

Photoluminescence has been studied in the aluminum oxide (Al₂O₃) bulk and nanosize powders in the 300-8 K temperature range. In both samples luminescence spectrum is characterized by presence of broad blue and red bands caused mainly by emission from the uncontrolled titanium impurity. At low temperatures luminescence intensity increases by several times and the red band obtains fine structure. The nature of the fine structure is discussed suggesting manifestation of splitting of the Ti³⁺ emitting level due to Jahn-Teller effect or overlapping of Ti³⁺ emission band with narrow lines from other emitting ions. The observed differences in low-temperature spectral features of nanopowder compared to its bulk counterpart are explained by lattice structure of nanopowder, which belongs to transition phase of Al₂O₃.     

Neutron powder diffraction and magnetic study of perovskites Pb(Mn1/2Nb1/2)O3 and Pb(Mn1/4Fe1/4Nb1/2)O3

The structural and magnetic properties of the complex metal oxides Pb(Mn_1/2Nb_1/2)O₃ (PMNO) and Pb(Mn_1/4Fe_1/4Nb_1/2)O₃ (PMFNO), which belong to a class of disordered perovskites have been studied. The magnetic susceptibilities of PMNO showed hysteresis between field cooled and zero-field cooled conditions below the transition of 15 K, suggesting that the material has a spin-glass feature. Neutron diffraction patterns of PMNO showed no evidence of a long-range magnetic ordering at 1.5 K, which is consistent with spin-glass behavior. Rietveld refinements of neutron powder diffraction data collected at different temperatures between 1.5 and 700 K have been carried out in order to extract structural information. The crystal structure of this compound is cubic (space group Pmm) within the whole temperature interval. The Mn and Nb ions were found to be disordered over the perovskite B-sites. The main feature of this structure is the positional disorder at the Pb site, the importance of which in connection with the ferroic transitions is briefly discussed. The Pb cations show a positional disorder shifting from their high-symmetry positions along the [1 1 1] direction. The effect of Fe-doping on PMNO has been studied. The substitution of Fe at the Mn site in PMFNO results in a small changes of the magnetic properties without significant differences in the crystal structures. The factors governing the observed structural and magnetic properties of PMNO and PMFNO are discussed and compared with those of other quaternary Mn-containing perovskites. For the PbB³⁺_1/2Nb_1/2O₃ series with the isomorphous substitution B³⁺, graphs of average lattice parameters of the perovskite phase and the temperatures of ferroelectric and magnetic phase transitions as functions of the B³⁺ cation radius were constructed and are discussed. Influence of A-cation sublattice on magnetic properties is also considered.     

UV Raman spectroscopic study on the surface phase of ZrO2 modified with Nd2O3

The Nd₂O₃ modified ZrO₂ was synthesized using two methods of co-precipitation (Nd-ZrO₂) and wet impregnation (Nd/ZrO₂). The surface and bulk crystalline phases of Nd₂O₃ modified ZrO₂ were investigated by using UV Raman spectroscopy, visible Raman spectroscopy, and X-ray diffraction (XRD). It is observed that the tetragonal phase in the surface region of Nd-ZrO₂ was not effectively stabilized by Nd₂O₃, as Nd₂O₃ is mainly present in the bulk of Nd-ZrO₂. However, in Nd/ZrO₂, it is found that with the impregnation of 0.5 mol% Nd₂O₃ on ZrO₂, the surface tetragonal phase of Nd/ZrO₂ can be stabilized even after calcination at 700 °C. The UV Raman results indicate that a disordered structure, or intermediate structure, which is involved in the transition from the tetragonal to the cubic phase, is formed at the surface region of Nd/ZrO₂. The formation of the aforementioned intermediate structure inhibits the phase transition from tetragonal to monoclinic in the surface region of Nd/ZrO₂. Furthermore, it is observed that the mixed tetragonal and monoclinic phases in the surface region of ZrO₂ which has been impregnated with Nd₂O₃ can also be stabilized after calcination at 700 °C. This work provides a simple method for controlling the surface phase of ZrO₂ at high temperatures.     

Synthesis and microwave dielectric properties of CaO-MgO-SiO2 submicron powders doped with Li2O-Bi2O3 by sol-gel method

Using Ca(NO₃)₂·4H₂O, Mg(NO₃)₂·6H₂O, Si(OC₂H₅)₄, LiNO₃ and Bi(NO₃)₃·5H₂O as raw materials, CaO-MgO-SiO₂ submicron powders were prepared at low temperature by sol-gel method. The crystallization temperature was decreased enormously by the introduction of Li-Bi liquid phase sintering aids into Ca-Mg-Si sol, and the powders with average particle sizes of 80-100 nm and 200-400 nm were obtained at the calcining temperature of 750 °C and 800 °C, respectively. The sintering characteristic and dielectric properties of powders calcined at 750 °C with different content of powders calcined at 800 °C were studied. When the content of powders calcined at 800 °C was 10 wt%, the dielectric ceramic sintered at 890 °C had compact structure, and possessed excellent microwave dielectric properties: ?_r = 7.16, Q × f = 25630 GHz, τ_f = −69.26 ppm/°C.     

Structural analysis of mechanically alloyed nanocrystalline Fe75Si15Al10 powders

Nanocrystalline Fe₇₅Si₁₅Al₁₀ powders were synthesized by ball milling elemental powders followed by heat treatment at elevated temperatures. The milling process produced a non-equilibrium solid solution of bcc α-Fe(Si,Al). This solid solution transforms into an ordered DO₃ crystal structure after annealing at 700 °C. Growth of the DO₃ structure with annealing time was studied by comparing the corresponding average crystallite size and long-range order parameter. The milling process was studied by analyzing the X-ray diffraction patterns using the Williamson-Hall and Ungar et al. methods. The applicability of the two methods for the present data is discussed.     

Effect of annealing on microstructure and mechanical properties of bulk nanocrystalline Fe3Al alloy with 5 wt.% Cu prepared by aluminothermic reaction

Microstructure and mechanical properties of bulk nanocrystalline Fe₃Al based alloy with 5 wt.% Cu prepared by aluminothermic reaction before and after annealed at 873, 1073 and 1273 K for 8 h were investigated. Microstructures of the alloy before and after the annealing consisted of a Fe-Al-Cu matrix, a little Al₂O₃ sphere and Fe₃AlC_x fiber phases. The matrix of the alloy before the annealing was composed a nanocrystalline phase with disordered bcc crystal structure and a little amorphous phase. The amorphous phase disappeared after the annealing and Fe₃Al phase with ordered DO₃ structure appeared in the alloy after annealed at 1073 and 1273 K in the matrix of the alloy. Size of the Fe₃AlC_x fiber phase increased with the annealing temperature. The alloy after the annealing had better plasticity, higher yield strength than that of the alloy before the annealing, and the alloy after annealed at 1273 K had the highest yield strength.     

Epitaxial growth and rectification characteristics of double perovskite oxide La2NiMnO6 films on Nb-SrTiO3 single crystal substrates

High-quality thin films of double perovskite La₂NiMnO₆ (LNMO) were epitaxially grown on Nb-doped SrTiO₃ (NSTO) substrates by pulsed laser deposition. The films were found to undergo a ferromagnetic-to-paramagnetic transition at ~ 280 K, which is consistent with the literature report. In the electrical measurements, typical rectifying behavior was observed in the LNMO/NSTO heterojunction. The diffusion voltage (V_D) increases linearly with temperature (T) during cooling until T = 170 K. At T < 170 K, V_D increases at a higher rate and the V_D-T relationship becomes non-linear. A disordered phase related spin polarization was used to understand such behaviors in the heterojunctions.     

The effect of annealing on the photoluminescence of layered perovskite H1.77[Sr0.8Bi0.21Ta2O7] powders

The microstructural and luminescent properties of H_1.77[Sr_0.8Bi_0.21Ta₂O₇] powders under different dehydrating conditions were investigated. The powders were obtained by protonating Bi₂SrTa₂O₉ powders in 3 M aqueous HCl solution, and were dehydrated by a post-annealing in air from 250 to 700 °C. The photoluminescence was enhanced for all dehydrated powders, especially for the sample annealed at 400 °C. The thermogravimetric analysis showed that there is an obvious dehydration temperature range from 200 to 400 °C, which was corresponding to the changing of the microstructure and photoluminescence in the same temperature range. The mechanism behind the experimental results was discussed.     

H2S sensing properties of La-doped nanocrystalline In2O3

The nanocrystalline powders of pure and La³⁺-doped In₂O₃ with cubic structure were prepared by a simple hydrothermal decomposition route. The structure and crystal phase of the powders were characterized by X-ray diffraction (XRD) and microstructure by transmission electron microscopy (TEM). All the compositions exhibited a single phase, suggesting a formation of solid solution in the concentration of doping investigated. Gas-sensing properties of the sensor elements were tested by mixing a gas in air at static state, as a function of concentration of dopant, operating temperature and concentrations of the test gases. The pure In₂O₃ exhibited high response towards H₂S gas at an operating temperature 150 °C. Doping of In₂O₃ with La³⁺ increases its response towards H₂S and La³⁺ (5.0 wt.% La₂O₃)-doped In₂O₃ showed the maximum response at 125 °C. The selectivity of the sensor elements for H₂S against different reducing gases was studied. The results on response and recovery time were also discussed.     

Tantalum influence on physical properties of (K0.5Na0.5)(Nb1−xTax)O3 ceramics

Lead-free (K_0.5Na_0.5)(Nb_1−xTa_x)O₃ ceramics with x = 0.00-0.30 were prepared by the solid-state reaction technique. The effects of Ta on microstructure, crystallographic structure, phase transition and piezoelectric properties have been investigated. It has been shown that the substitution of Ta decreases Curie temperature T_C and orthorhombic-tetragonal phase transition temperature T_O-T, while increasing the rhombohedral-orthorhombic phase transition temperature T_R-O. In addition, piezoelectric activity is enhanced with the increase of Ta content. The ceramics with x = 0.30 have the high value of piezoelectric coefficient d₃₃ = 205 pC/N. Moreover, k_p shows little temperature dependence between −75° C and 75 °C, and d₃₃ exhibits very good thermal stability over the range from −196 °C to 75 °C in the aging test.     

Lowering of L10 phase transition temperature of FePt thin films by single shot H ion exposure using plasma focus device

FePt thin films are exposed to pulsed energetic H⁺ ion beam from plasma focus. In irradiated films, the phase transition from the low K_u disordered face-centered-cubic structure to high K_u ordered face-centered-tetragonal phase was achieved at 400 °C with the order parameter S ranging from 0.73 to 0.83, high coercivity of about 5356 kA/m, high negative nucleation field of about 7700 kA/m and high squareness ratio ranging from 0.73 to 0.79. The advantage of using plasma focus device is that it can lower phase transition temperature and significantly enhance the magnetic properties by a pulsed single shot exposure.     

Temperature dependent model dielectric function of highly disordered Ga0.52In0.48P

We report on the temperature dependence of the dielectric function of Ga_0.52In_0.48P from room temperature to 500°C, and for photon energies from 0.75 eV to 5 eV. The undoped, highly disordered Ga_0.52In_0.48P thin film was grown by metal-organic vapor phase epitaxy lattice matched onto a (001) GaAs substrate. The dielectric function of Ga_0.52In_0.48P was measured by in-situ spectroscopic ellipsometry, and analyzed using Adachi's composite critical point model. We provide a second-order temperature expansion parameter set for calculation of the Ga_0.52In_0.48P dielectric function and its temperature dependence, and which may become useful for in situ growth control or optoelectronic device performance evaluation at elevated temperatures. We discuss the temperature-induced shift of critical point transition energy parameters.     

High-pressure phase transition in Ho2O3

High-pressure X-ray diffraction and Raman studies on holmium sesquioxide (Ho₂O₃) have been carried out up to a pressure of ∼17 GPa in a diamond-anvil cell at room temperature. Holmium oxide, which has a cubic or bixbyite structure under ambient conditions, undergoes an irreversible structural phase transition at around 9.5 GPa. The high-pressure phase has been identified to be low symmetry monoclinic type. The two phases coexist to up to about 16 GPa, above which the parent phase disappears. The high-pressure laser-Raman studies have revealed that the prominent Raman band ∼370 cm⁻¹ disappears around the similar transition pressure. The bulk modulus of the parent phase is reported.     

Crystal structures and phase transitions in Ba2HoTaO6

The structure of the cation-ordered double perovskite Ba₂HoTaO₆ was examined using synchrotron X-ray powder diffraction at fine temperature intervals over the range of 90-300 K. Ba₂HoTaO₆ has a cubic structure in space group at room temperature. A proper ferroelastic phase transition to I4/m tetragonal symmetry occurs near approximately 260 K. Analysis of the spontaneous tetragonal strain versus temperature indicated that the phase transition is second order in nature.     

The study of the electric and magnetic properties of PbZr0.2Ti0.8O3-BiFeO3 multilayers

The results of the electric and magnetic measurements performed on PbZr_0.2Ti_0.8O₃-BiFeO₃ symmetric structures, deposited on Pt/Si wafers, were compared for different number of layers in order to analyse the effect of interfaces over the macroscopic properties. It was found that the shape and magnitude of the capacitance-voltage characteristic, as well as the shape and parameters of the ferroelectric and magnetic hysteresis, depend on the number of interfaces in the intended multilayer structure. A temperature induced gradual transition from a magnetically disordered spin glass like phase of low temperature to an uncompensated antiferromagnetic phase at room temperature takes place in the BiFeO₃ films, under low applied magnetic fields. A partial ferromagnetic like order can be obtained at low temperatures by increasing the field. The observed changes in the electric and magnetic behaviour of the systems were related to an increased degree of disorder for electric dipoles and magnetic moments, due to the increased number of layers and crystallization treatments.     

Crystallite structure,microstructure, dielectric,and piezoelectric properties of (Pb1.06−xBax)(Nb0.94Ti0.06)2O6 piezoelectric ceramics prepared using calcined powders with different phases

In an attempt to obtain dense lead metaniobate-based ceramics with improved dielectric and piezoelectric properties, the (Pb_1.06−xBa_x)(Nb_0.94Ti_0.06)₂O₆ (x = 0, 0.04, 0.08, 0.12) piezoelectric ceramics were prepared separately from the two kinds of calcined powders, i.e., the powders with the rhombohedral phase and orthorhombic phase. For obtaining the calcined powders with the different phases, two different calcination temperatures of 900 °C and 1250 °C were chosen. The calcined powders were characterized using X-ray diffraction, scanning electron microscope, laser particle size analyzer and differential scanning calorimetry. Effects of the phase structures of the calcined powders on crystallite structure, microstructure, dielectric and piezoelectric properties of the ceramics were studied in detail. The lattice parameters and grain size of the ceramics are related to the phase structures of the calcined powders. The doping of Ba²⁺ has an influence on the dielectric and piezoelectric properties of the ceramics. The ceramics with x = 0.08 fabricated from the calcined powders with the orthorhombic phase demonstrate the optimum dielectric and piezoelectric properties.     

Alanine-assisted low-temperature combustion synthesis of nanocrystalline LiMn2O4 for lithium-ion batteries

Nanocrystalline LiMn₂O₄ powders have been synthesized by combustion process in a single step using a novel fuel, l-alanine. Thermogravimetric analysis and differential thermal analysis of the gel indicate a sharp combustion at a temperature as low as 149 °C. Quantitative phase analysis of X-ray diffraction data shows about 97% of phase purity in the as-synthesized powder, which on further calcination at 700 °C becomes single phase LiMn₂O₄. High Brunauer, Emmett, and Teller surface area values obtained for ash (53 m²/g) and calcined powder (23 m²/g) indicate the ultrafine nature of the powder. Average crystallite size is found to be ∼60-70 nm from X-ray diffraction analysis and transmission electron microscopy. Fourier transformed infra-red spectrum shows two strong bands at 615 and 511 cm⁻¹ originating from asymmetrical stretching of MnO₆ octahedra. A nominal composition of Li_0.88 Mn₂O₄ is calculated from the inductive coupled plasma analysis. From UV-vis spectroscopy, an optical band gap of 1.43 eV is estimated which is assigned to a transition between t_2g and e_g bands of Mn 3d. Electrochemical charge-discharge profiles show typical LiMn₂O₄ behavior with a specific capacity of 76 mAh/g.