Preparation and characterization of nanocrystalline La-doped ZnO powders through a mechanical milling and their optical properties

Structural and optical properties of mechanically milled La-doped ZnO powders are presented in this paper. The Zn_1−xLa_xO phase formed when x varied in a range of 0.02-0.06 and milled at 400 rpm for 20 h. The secondary La₂O₃ phase occurred with an increase of La content. The crystallite and particle size decreased as a function of La content as x = 0-0.14 due to the effect of Zener pinning and solute drag. The absorption edge shifted to a lower wavelength when La content was increased to x = 0.14 because of the size effect. The energy band gap of Zn_1−xLa_xO powders varied in a range of 2.96-3.12 eV depending on the crystallite size. The broad emission bands in a visible region centered at about 640 nm are attributed to oxygen deficiency.     

Chemical reduction of nanocrystalline CeO2

The reduction of commercial and mechanochemically processed CeO₂ powders was studied. Nanostructured CeO₂, with the crystallite size of 21 nm and the lattice distortion of 0.37%, was obtained during 60 min of milling in a high-energetic vibratory mill. X-ray diffraction, scanning electron microscopy and Brunauer-Emmett-Teller method were applied to characterize the milled powders. During the thermal treatment at 1200 and 1400 °C in an argon atmosphere the nonstoichiometric CeO_2−x oxides with the defect fluorite structure were formed. Compositions of CeO_2−x oxides were determined according to its lattice parameter. The results showed that the release of oxygen, as well as the rate of reduction, was more effective in nanocrystalline then in the microcrystalline CeO₂, producing at 1200 °C CeO_1.80 and CeO_1.85 oxides, while at 1400 °C were obtained similarly, CeO_1.77 and CeO_1.78, compositions.     

Dependence of optical properties on doping metal, crystallite size and defect concentration of M-doped ZnO nanopowders (M = Al, Mg, Ti)

ZnO, Al-, Mg- and Ti-doped ZnO nanopowders were synthesized from CTAB-assisted oxalate intermediate by thermal decomposition method at 600 °C in air. All samples presented a hexagonal wurtzite structure. The spherical nanoparticles assembled in a porous octahedron-like shape for all samples. The size of Al-doped ZnO nanopowders increased as a function of Al ion concentration whereas the size of Mg- and Ti-doped ZnO nanopowders decreased when Mg and Ti ion concentrations were increased. The increment and reduction of their sizes can be explained by the Zener pinning effect. The E_g value of Al-doped ZnO nanopowders slightly decreased when Al ions were increased due to the crystallite size and defect concentration increased. In contrast, the E_g value of Mg- and Ti-doped ZnO nanopowders increased as a function of Mg and Ti ion concentration which can be explained by the Moss-Burstein effect.     

Effect of the starting materials on the reaction synthesis of Ti3SiC2

Ternary carbide of titanium and silicon was produced via mechanical milling and following heat treatment. Effects of the starting materials, milling time and heat treatment temperature were studied. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were utilized to evaluate the structural and morphological evolutions of the ball-milled and annealed powders. Results showed that the ball milling of TiO–Si–C as the starting materials failed to synthesize Ti₃SiC₂. Additionally, ball milling the elemental powders for shorter milling times resulted in the activation of the powders. However, after longer milling times, Ti–TiC nanocomposite was obtained. Furthermore, during annealing the milled powders, Ti₃SiC₂–TiC nanocomposite with the mean grain size of 16 nm was synthesized. After 20 h of milling, a very fine microstructure with narrow size of distribution and spheroid particles was achieved.     

On the spinel formation in Co1 − xO/Co2TiO4 composites via reactive sintering, exsolution and oxidation

The formation mechanism and microstructural development of the spinel phases in the Co_1 − xO/Co₂TiO₄ composites upon reactive sintering the Co_1 − xO and TiO₂ powders (9:1 molar ratio) at 1450 °C and during subsequent cooling in air were studied by X-ray diffraction and analytical electron microscopy. The Co₂TiO₄ spinel occurred as inter- and intragranular particles in the matrix of Ti-doped Co_1 − xO grains with a rock salt-type structure during reactive sintering. The submicron sized Co₂TiO₄ particles were able to detach from grain boundaries in order to reach an energetically favorable parallel orientation with respect to the host Co_1 − xO grains via a Brownian-type rotation/coalescence process. Upon cooling in air, secondary Co₂TiO₄ nanoparticles were precipitated and the Ti-doped Co_1 − xO host was partially oxidized as Co_3 − δO₄ spinel by rapid diffusion along the {1 1 1} and {1 0 0}-decorated interphase interface and the free surface of the composites.     

Mechanochemical synthesis and characterisation of BaTa2O6 ceramic powders

Mechanochemical synthesis was used to prepare BaTa₂O₆ powders from BaCO₃ and Ta₂O₅ precursors in a planetary ball mill. Effect of milling time and heat treatment temperature on the formation of BaTa₂O₆ and on the microstructure was investigated. Intensive milling of starting materials resulted in crystallization of BaTa₂O₆ even after 1 h of milling time and single phase BaTa₂O₆ was obtained after 10 h of milling under optimal conditions. The powder derived from 10 h of mechanical activation had crystallite size of 22 nm. But the increase in milling time did not decrease the crystallite size further. High energy milling activated the powders that although 1 h of milling led to formation of single phase BaTa₂O₆ at 1200 °C, this temperature decreased to 900 °C after 5 h of milling. No significant grain growth was observed when the milled powders were heat treated below 900 °C. However, annealing at 1100 and 1200 °C gave an average BaTa₂O₆ grain size of 180 and 650 nm, respectively. An unidentified phase started to form at 1100 °C increasing to high amounts at 1200 °C and they had different shapes and sizes than BaTa₂O₆ grains. These elongated large grains were thought to be due to liquid phase formation caused by iron contamination.     

Preparation and microstructural characterization of (Nd1−xGdx)2(Ce1−xZrx)2O7 solid solutions

(Nd_1−xGd_x)₂(Ce_1−xZr_x)₂O₇ (0 ≤ x ≤ 1.0) powders with an average particle size of 100 nm were synthesized with chemical-coprecipitation and calcination method, and were characterized by X-ray diffractometry and scanning electron microscopy. The sintering behaviour of (Nd_1−xGd_x)₂(Ce_1−xZr_x)₂O₇ powders was studied by pressureless sintering at 1600–1700 °C for 10 h in air. The relative densities of (Nd_1−xGd_x)₂(Ce_1−xZr_x)₂O₇ solid solutions increase with increasing the sintering temperature, and gradually decrease with increasing the content of neodymium and cerium at identical temperature levels. (Nd_1−xGd_x)₂(Ce_1−xZr_x)₂O₇ solid solutions have a single phase of defect fluorite-type structure among all the composition combinations studied. The lattice parameters of (Nd_1−xGd_x)₂(Ce_1−xZr_x)₂O₇ solid solutions agree well with the Vegard's rule.     

Synthesis of MoSi2-TiC nanocomposite powder via mechanical alloying and subsequent annealing

MoSi₂-30 wt.% TiC nanocomposite powder was successfully synthesized by ball milling and following heat treatment. Effect of milling time and annealing temperature were investigated. The products synthesis and reactions progress were characterized by XRD. Morphology and microstructure of milled powders were monitored by SEM and TEM, respectively. Results showed that the synthesis of this composite begins after 10 h of milling and progresses gradually up to 30 h of milling. MoSi₂-TiC composite was completely synthesized after annealing of 30 h milled powder at 900 °C. On the basis of Reitveld refinement method, the mean grain size and microstrain of 13.2 nm and 0.44% were obtained, respectively for 30 h milled powder that is in consistent with TEM image. In the spite of grain growth and strain release, this nanocomposite powder maintained its nanostructure after annealing.     

Mechanochemical synthesis of MgTa2O6 ceramic

MgTa₂O₆ powders were prepared by mechanochemical synthesis from MgO and Ta₂O₅ in a planetary ball mill in air atmosphere using steel vial and steel balls. High-energy ball milling gave nearly single-phase MgTa₂O₆ after 8 h of milling time. Annealing of high-energy milled powder at various temperatures (700–1200 °C) indicated that high-energy milling speed up the formation and crystallization of MgTa₂O₆ from the amorphous mixture. The powder derived from 8 h of mechanical activation gave a particle size of around 28 nm. Although at low-annealing temperatures the grain size was almost the same as-milled powder, the grain size increased with annealing temperature reaching to around 1–2 μm after annealing at 1200 °C for 8 h.     

Effect of the solid precursors on the formation of nanosized TiBx powders in RF thermal plasma

Continuous synthesis of TiB_x (x≈0.5–2) nanoparticles from various low cost solid precursors such as titanium and titanium dioxide admixed with boron and/or carbon in radiofrequency thermal plasma was studied. Feasibility of TiB₂ formation was predicted by thermodynamic equilibrium calculations in the 500–5000 K temperature range. In all the investigated system high temperature reactions resulted in nanometer-sized TiB_x powders with a mean size varying between 13 and 83 nm. The yield of particular runs ranged from 38% to 97%. Among the synthesized products in addition to TiB_x, oxidized precursor residues were also found in smaller quantities. Although addition of carbon to the precursors could not completely prevent surface oxidation of boride particles, it contributed to the reduction of the mean particle size of the formed TiB₂.     

Characterization of Mg1−xNixAl2O4 solid solutions prepared by combustion synthesis

Mg_1−xNi_xAl₂O₄ (x = 0, 0.25, 0.5, 0.75 and 1) solid solutions have been prepared by combustion synthesis. After annealing the combustion synthesized powders at 1000 °C for 3 h single-phase Mg_1−xNi_xAl₂O₄ was obtained over the entire range of compositions. The lattice parameter of Mg_1−xNi_xAl₂O₄ gradually increased from 8.049 Å (NiAl₂O₄) to 8.085 Å (MgAl₂O₄), which certified the formation of the spinel solid solutions. All samples prepared by combustion synthesis had blue color shades, denoting the inclusion of Ni²⁺ in the spinel structure in octahedral and tetrahedral configuration. The crystallite size of Mg_1−xNi_xAl₂O₄ was in the range of 35-39 nm and the specific surface area varied between 5.8 and 7.0 m²/g.     

Influence of ball milling on the sintering behaviour of ZnO powder

A high purity ZnO powder was milled with either YSZ or Al₂O₃ balls. The weight losses of YSZ and Al₂O₃ balls after milling for 4 h are 10 and 40 ppm, respectively. The debris of the milling media acts as sintering aid to the ZnO powder. As a result, the grain size of the sintered ZnO specimens is reduced. The ratio of the grain boundary energy over surface energy is also decreased.     

Development of metal oxide nanoparticles by soft chemical method

An extensive work for the study of SnO₂ samples doped with x-mol% of Sb (x = 0, 6, 10, 14 and 18) is reported. The materials were prepared by the polymeric precursor method (Pechini method), calcined for 4 h between 800 °C and 1200 °C. The Rietveld method with X-ray diffraction data (XRD) was used to analyze the unit cell dimensions, crystallite size and microstrain. It was observed the crystallite size increasing and decrease of the microstrain with the increase of the calcining temperature. The synthesis of tin oxide nanoparticles with high thermal stability against particle growth rate was achieved by doping SnO₂ particles with Sb₂O₃. All the phases tend to have the same dimension when the temperature increases, although its values varies with x and reaches the maximum value when fired at 1100 °C. These variations seem to be an indication that the oxidation state of the antimony changes with the amount of Sb added to the material.     

Synthesis of LaB6 powders from La2O3, B2O3 and Mg blends via a mechanochemical route

This study reports a room temperature mechanochemical route for the synthesis of LaB₆ powders from La₂O₃–B₂O₃–Mg blends. The synthesis reaction was driven by high-energy ball milling and was gradually examined in terms of milling duration and process control agent. Following the mechanochemical synthesis, unwanted MgO phase and Fe contamination worn off from the milling vial/balls were removed with HCl acid leaching under the effect of ultrasonic stirring. Pure LaB₆ powders were obtained after repeated centrifuging, repeated washing and drying. Subsequent annealing was performed in a tube furnace at 800 °C for 5 h under Ar atmosphere in order to reveal residual elements. Phase and microstructural characterizations of the milled, leached and annealed powders were performed using X-ray diffractometry (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques. A novel route for producing fine-grained LaB₆ powders was accomplished with shorter reaction times resulting in higher purity.     

Synthesis and characterization of chlorapatite–ZnO composite nanopowders

The influence of zinc oxide content on the formation of chlorapatite-based composite nanopowders in the mechanically alloyed CaO–CaCl₂–P₂O₅–ZnO system was studied. To mechanosynthesize composite nanopowders, different amounts of hydrothermally synthesized zinc oxide nanoparticles (0–10 wt%) were mixed with ingredients and then were mechanically activated for 5 h. Results showed that in the absence of zinc oxide, high crystalline chlorapatite nanopowder was obtained after 5 h of milling. In the presence of 4 and 7 wt% zinc oxide, the main product of milling for 5 h was chlorapatite–zinc oxide composite nanopowder. On increasing the zinc oxide content to 10 wt%, composite nanopowder was not formed due to improper stoichiometric ratio of the reactants. The crystallite size, lattice strain, volume fraction of grain boundary, and crystallinity degree of the samples fluctuated significantly during the milling process. In the presence of 7 wt% zinc oxide, the crystallite size and crystallinity degree reached 51±2 nm and 79±2%, respectively. During annealing at 900 °C for 1 h, the crystallization of composite nanopowder occurred and as a result the crystallinity degree rose sharply to 96±3%. In addition, the crystallite size increased to 77±2 nm after annealing at 900 °C. According to SEM and TEM images, the composite nanopowder was composed of both ellipse-like and polygonal particles with a mean size of about 98 nm.     

VUV photoluminescence properties of Y1−xGdxVO4:Eu phosphors prepared by ultrasonic spray pyrolysis

The red-emitting (Y_1−xGd_x)_0.94Eu_0.06VO₄ (0 ≤ x ≤ 1.0) phosphors were synthesized by ultrasonic spray pyrolysis. The (Y_1−xGd_x)_0.94Eu_0.06VO₄ (0 ≤ x ≤ 1.0) phosphors had the tetragonal xenotime structure with a space group of I4₁/amd (1 4 1). The calculated crystallite sizes of the annealed phosphors ranged from 58 to 68 nm. In this study, we discussed the photoluminescence properties of the (Y_1−xGd_x)_0.94Eu_0.06VO₄ phosphors under VUV excitation, depending on Gd content. The emission intensity of the (Y_1−xGd_x)_0.94Eu_0.06VO₄ phosphors increased with increasing Gd content up to x = 0.5, and then decreased with a further increase in Gd content. The purest red color was obtained for the (Y_0.5Gd_0.5)_0.94Eu_0.06VO₄ phosphors.     

Cathodic performance of LiMn1−xMxPO4 (M = Ti, Mg and Zr) annealed in an inert atmosphere

To improve the cathodic performance of olivine-type LiMnPO₄, we investigated the optimal annealing conditions for a composite of carbon with cation doping. Nanocrystalline and the cation-doped LiMn_1−xM_xPO₄ (M = Ti, Mg, Zr and x = 0, 0.01, 0.05 and 0.10) was synthesized in aqueous solution using a planetary ball mill. The synthesis was performed at the fairly low temperature of 350 °C to limit particle size. The obtained samples except for the Zr doped one consisted of uniform and nano-sized particles. The performance of LiMnPO₄ was much improved by an annealing treatment between 500 and 550 °C with carbon in an inert atmosphere. A small amount of metal-rich phosphide (Mn₂P) was detected in the sample annealed at 900 °C. In addition, 1 at.% Mg doping for Fe enhanced the rate capability in our doped samples. The discharge capacity of LiMn_0.99Mg_0.01PO₄/C was 146 mAh/g at 0.1 mA/cm² and 125 mAh/g even at 2.0 mA/cm².     

Deposition and characterization of cold sprayed nanocrystalline NiTi

Binary 50Ni-50Ti mixture was prepared by mechanical alloying from elemental powders. After 48 h of milling, the nanocrystalline B2-NiTi powder was produced. Then, this as-milled powder was deposited by cold spraying in order to produce a target which can be used to create thin films by magnetron sputtering technique. The objective is to improve the electrical characterizations of the NiTi/SiO₂/Si M.O.S structures. The morphology evolution of the powder particles, the phase identification and the alloying evolution process as function of milling time were studied using scanning electron microscopy, X-ray diffraction and transmission electron microscopy. In addition, the target was also characterized using X-ray diffraction, Scanning electron microscopy, and microhardness measurements. The milling of powders leads to the formation of disordered nanocrystalline B2-NiTi with a crystallite size of about 12 nm and a microstrain of level 2.10%, after 48 h of milling. The microstructure, the composition and grain size of the milled powders for 24 h and 48 h characterized by TEM are heterogeneous. The as-deposited intermetallic NiTi can be retained in the coating with a lattice parameter of 0.3 nm, crystallite size of 14 nm, microstrain and high microhardness of 2% and 694 Hv_0.25, respectively.     

Mechanosynthesis,crystal structure and magnetic characterization of M-type SrFe12O19

M-type strontium hexaferrite was prepared by mechanosynthesis using high-energy ball milling. The influence of milling parameters, hematite excess and annealing temperature on magnetic properties of SrFe₁₂O₁₉ were investigated. Commercial iron and strontium oxides were used as starting materials. It was found that mechanical milling followed by an annealing treatment at low temperature (700 °C) promotes the complete structural transformation to Sr-hexaferrite phase. For samples annealed at temperatures from 700 to 1000 °C, saturation magnetization values (M_s) are more sensitive to annealing temperature than coercivity values (H_c). The maximum M_s of 60 emu/g and H_c of 5.2 kOe were obtained in mixtures of powders milled for 5 h and subsequently annealed at 700 °C. An increase in the annealing temperature produces negligible changes in magnetic saturation and coercivity. An excess of hematite as a second phase produces a slight decrease in the saturation magnetization but leads to a significant increase in coercive field, reaching 6.6 kOe.     

Synthesis of MnFe2O4 nanocrystals by wet-milling under atmospheric conditions

This work reports an original method for synthesis of well-crystallized manganese ferrite (MnFe₂O₄) nanoparticles via a high energy wet milling technique under atmospheric conditions, starting from metallic Mn and Fe powders in the presence of distilled water. The effects of milling conditions on the formation and magnetic properties of MnFe₂O₄ nanoparticles were investigated in detail. Fully stoichiometric MnFe₂O₄ nanocrystals with an average crystallite size of 14.5 nm were produced after 24 h of milling. As-synthesized MnFe₂O₄ nanocrystals were found to show soft magnetic behavior at room temperature with saturation magnetization of 53 emu/g. Due to reduced thermal effects, the saturation magnetization increased to 68 emu/g at 5 K. Results show that this method is simple and efficient for the mass production of MnFe₂O₄ nanoparticles.