Formation of TiB2 by volume combustion and mechanochemical process

Titanium diboride was produced both by volume combustion synthesis (VCS) and by mechanochemical synthesis (MCP) through the reaction of TiO₂, B₂O₃ and Mg. VCS products, expected to be composed of TiB₂ and MgO, were found to contain also side products such as Mg₂TiO₄, Mg₃B₂O₆, MgB₂ and TiN. HCl leaching was applied to the reaction products with the objective of removing MgO and the side products. Formation of TiN could be prevented by conducting the VCS under an argon atmosphere. Mg₂TiO₄ did not form when 40% excess Mg was used. Wet ball milling of the products before leaching was found to be effective in removal of Mg₃B₂O₆ during leaching in 1 M HCl. When stoichiometric starting mixtures were used, all of the side products could be removed after wet ball milling in ethanol and leaching in 5 M HCl when pure TiB₂ was obtained with a molar yield of 30%. Pure TiB₂ could also be obtained at a molar yield of 45.6% by hot leaching of VCS products at 75 °C in 5 M HCl, omitting the wet ball milling step. By MCP, products containing only TiB₂ and MgO were obtained after 15 h of ball milling. Leaching in 0.5 M HCl for 3 min was found to be sufficient for elimination of MgO. Molar yield of TiB₂ was 89.6%, much higher than that of VCS. According to scanning electron microscope analyses, the TiB₂ produced had average grain size of 0.27 ± 0.08 μm.     

Phase structure, morphology, and Raman characteristics of NaNbO3 particles synthesized by different methods

NaNbO₃ (NN) particles were synthesized by using conventional mixed-oxide (CMO), molten salt synthesis (MSS) and topochemical micro-crystal conversion methods (TMC), respectively. The effects of preparation methods on the phase structure, morphology and Raman characteristics of the NaNbO₃ particles were investigated. The results show that the NN particles prepared by conventional mixed-oxide and molten salt synthesis methods are all of orthorhombic structure in Pbma space group. Furthermore, those particles have equiaxial morphology. The single-crystal NaNbO₃ particles synthesized by the topochemical micro-crystal conversion method are of pseudocubic structure. Moreover, they are of plate-like shape with a high aspect ratio and a high (h 0 0) degree of orientation, which is very promising as template for texturing (K, Na)NbO₃ (KNN) based ceramics. Besides, all the spectra lines in the Raman spectra can be attributed to the internal modes of NbO₆ octahedron, and they prove that the particles synthesized by the different methods have different structure types.     

Structure study of Bi4Ti3O12 produced via mechanochemically assisted synthesis

Nanosized bismuth titanate was prepared via high-energy ball milling process through mechanically assisted synthesis directly from their oxide mixture of Bi₂O₃ and TiO₂. Only Bi₄Ti₃O₁₂ phase was formed after 3 h of milling time. The excess of 3 wt% Bi₂O₃ added in the initial mixture before milling does not improve significantly the formation of Bi₄Ti₃O₁₂ phase comparing to stoichiometric mixture. The formed phase was amorphized independently of the milling time. The Rietveld analysis was adopted to determine the crystal structure symmetry, amount of amorphous phase, crystallite size and microstrains. With increasing the milling time from 3 to 12 h, the particle size of formed Bi₄Ti₃O₁₂ did not reduced significantly. That was confirmed by SEM and TEM analysis. The particle size was less than 20 nm and show strong tendency to agglomeration. The electron diffraction pattern indicates that Bi₄Ti₃O₁₂ crystalline powder is embedded in an amorphous phase of bismuth titanate. Phase composition and atom ratio in BIT ceramics were determined by X-ray diffraction and EDS analysis.     

Mechanosynthesis and magnetic properties of nanocrystalline LaFeO3 using different iron oxides

The synthesis of the orthoferrite LaFeO₃ using high-energy ball-milling of La₂O₃ and Fe₃O₄ or α-Fe₂O₃ oxides and subsequent thermal treatments of resulting powders was studied. The phase evolution during the mechanical treatment was analyzed by X-ray diffraction (XRD), differential thermal analysis (DTA) and scanning electron microscopy (SEM). Also, magnetic properties of the obtained materials were measured at room temperature by vibrating sample magnetometry (VSM). From 30 min of mechanochemical activation the gradual disappearance of reactants and the formation of LaFeO₃ were observed. For both reactive mixtures the reaction was completed after 3 h of milling. Magnetic hysteresis loops of these mechanoactivated samples showed a significant ferromagnetic component in LaFeO₃. This behavior was interpreted on the basis of a spin-canting effect induced by the mechanochemical treatment. Thermal treatments allowed the relaxation of the distorted structure, resulting in the formation of the conventional antiferromagnetic LaFeO₃ phase.     

Microstructure and martensitic transformation in Si-coated TiNi powders prepared by ball milling

Si was coated on the surface of Ti–49Ni (at%) alloy powders by ball milling in order to improve the electrochemical properties of the Si electrodes of secondary Li ion batteries and then the microstructure and martensitic transformation behavior were investigated by means of scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and differential scanning calorimetry (DSC). Ti–Ni powders coated with Si were fabricated successfully by ball milling. As-milled powders consisted of highly deformed Ti–Ni powders with the B2 phase and amorphous Si layers. The thickness of the Si layer coated on the surface of the Ti–Ni powders increased from 3–5 μm to 10–15 μm by extending the milling time from 3 h to 48 h. However, severe contamination from the grinding media, ZrO₂ occurred when the ball milling time was as long as 48 h. By heating as-milled powders to various temperatures in the range of 673–873 K, the highly deformed Ti–Ni powders were recovered and Ti₄Ni₄Si₇ was formed. Two-stage B2–R–B19′ transformation occurred when as-milled Si-coated Ti–49Ni alloy powders were heated to temperatures below 873 K, above this temperature one-stage B2–B19′ transformation occurred.     

Fast amorphization and crystallization in Al-Fe binary system by high-energy ball milling

Large amount of amorphous phase of Al-Fe binary system was obtained by MA of elemental powders using a high-energy ball mill at milling intensity of 150G (G is the gravitational acceleration). XRD, HRTEM and DSC were used to analyze the process of amorphization and crystallization. The time required achieving almost complete amorphous state is only 4.2 ks for Al-25 at.%Fe system and 3 ks for Al-30 at.%Fe system, respectively. The time of amorphous formation is very shorter than that of previous reports on Al-Fe binary system. Further milling causes rapid crystallization of the amorphous phase. By analysis of S(Q), the presence of a strong Al-Fe chemical short-range order in the amorphous matrix is suggested. Moreover, the superstructure of these Al-Fe clusters in the amorphous matrix is similar to the solid structure of Al₅Fe₂, and the clusters transform into the nucleus of Al₅Fe₂ intermetallic compound under the action of milling energy.     

Mechanochemical-molten salt synthesis of Na2Ti6O13 nanobelts

A novel route for the preparation of Na₂Ti₆O₁₃ nanobelts by mechanochemical treatment of the TiCl₄-Na₂SO₄·10H₂O-Na₂CO₃ mixture for 5 min followed by molten salt synthesis is described. The mixture of the amorphous TiO₂ and NaCl-Na₂SO₄·xH₂O-Na₂CO₃ salt matrix was generated during milling. The molten salt synthesis of the Na₂Ti₆O₁₃ nanobelts with lengths up to 0.5-2 μm and with a width in the range of 20-250 nm was carried out in the temperature range of 700-800 °C for 1 h. The partial formation of titanate nanotubes was observed after annealing at 600 °C and washing procedure. X-ray diffraction (XRD), transmission electron microscopy (TEM) and differential thermal analysis (DTA) were used to characterize the formation and structure of Na₂Ti₆O₁₃ nanobelts.     

Structural and spectroscopic studies of mechanochemically activated nanosized apatite from Syria

Phosphorite sample from Syria is subjected to mechanochemical treatment in planetary mill equipped with 20 mm steel milling bodies. A complex of chemical and physical methods was applied, namely chemical analysis, powder XRD, IR spectroscopy, and SEM in order to prove changes in the structure of the minerals in the modified samples. These changes are manifested mainly in transformations of a considerable part of apatite into a nanosized phase, breakage of the coordination complex CaO₆F, and localization of OH⁻ groups in the position of F⁻ and CO₃²⁻ in the position of PO₄³⁻ of the apatite structure. As a result of these transformations the assimilable content of in the activated samples is increased and this gives opportunity to suppose that the activated phosphorite could be used as a phosphorous fertilizer.     

Lead-free piezoelectric thin films of Mn-doped NaNbO3-BaTiO3 fabricated by chemical solution deposition

Lead-free piezoelectric thin films of NaNbO₃-BaTiO₃ were fabricated on Pt/TiO_x/SiO₂/Si substrates by chemical solution deposition. Perovskite NaNbO₃-BaTiO₃ single-phase thin films with improved leakage-current and ferroelectric properties were prepared at 650 °C by doping with a small amount of Mn. The 1.0 and 3.0 mol% Mn-doped 0.95NaNbO₃-0.05BaTiO₃ thin films showed slim ferroelectric P-E hysteresis and field-induced strain loops at room temperature. The 1.0 and 3.0 mol% Mn-doped 0.95NaNbO₃-0.05BaTiO₃ films showed remanent polarization values of 6.3 and 6.2 μC/cm², and coercive field of 41 and 55 kV/cm, respectively. From the slope of the field-induced strain loop, the effective piezoelectric coefficient (d₃₃) was found to be 40-60 pm/V.     

Formation of NiFe2O4 nanoparticles by mechanochemical reaction

Preparation of nanosized NiFe₂O₄ particles by mechanochemical reaction(NiO+α-Fe₂O₃) and subsequent thermal treatment was investigated using X-ray diffraction (XRD). Thermal treatment of the as-milled powder at 700 °C for 1 h led to the formation of NiFe₂O₄ nanoparticles with an average crystal size of about 23 nm. Effect of thermal treatment temperature on the crystal size of the nanoparticles was studied. The mechanism of nanoparticles growth was primarily discussed. The activation energy of NiFe₂O₄ nanoparticle formation during calcination was calculated to be 16.6 kJ/mol.     

Effect of Ni addition on formation of amorphous and nanocrystalline phase during mechanical alloying of Al-25 at.%Fe-(5,10) at.%Ni powders

Al-Fe-Ni ternary powder mixtures containing 25 at.%Fe-5 at.%Ni and 25 at.%Fe-10 at.%Ni were mechanically alloyed by a high-energy planetary ball mill. Structural evolution of these powders during milling was investigated by X-ray diffraction technique and transmission electron microscopy. Almost complete amorphous phase in Al₇₀Fe₂₅Ni₅ system is observed at the early milling stage. The amorphous phase transforms into metallic compound Al₅(Fe,Ni)₂ and then the compound changes to ordered Al(Fe,Ni) phase. The last milling products in Al₇₀Fe₂₅Ni₅ system are amorphous phase plus nanocrystalline of the disordered Al(Fe,Ni) phase changed from the ordered Al(Fe,Ni) phase. During milling of Al₆₅Fe₂₅Ni₁₀ system, α-Al and α-Fe solid solutions formed at the early stage change to the ordered Al(Fe,Ni) compound and at last the ordered phase changes to the disordered Al(Fe,Ni) phase. Ten percent of Ni addition promotes retardation of the formation of the amorphous phase.     

Synthesis and high-pressure sintering of (W0.5Al0.5)C

A new solid solution of Al in WC, which can be expressed by the chemical formula (W_0.5Al_0.5)C, has been synthesized directly by reaction milling (RM) of a W_0.5Al_0.5 alloy and the proper amount of carbon. The total reaction time is about 50 h. The ESEM photograph shows that the prepared (W_0.5Al_0.5)C powders are spherical, and the average particle size is about 40 nm. (W_0.5Al_0.5)C has been identified to crystallize in the hexagonal space group P-6m2 (No.187) and belongs to the WC structure type. The lattice parameter of (W_0.5Al_0.5)C is calculated to be a = 2.908(1) Å, c = 2.836(1) Å. This nanocrystalline powder can be well sintered at the high temperature (1600 °C) under the high pressure (4.5 GPa), and the relative density reaches 99.1%. The hardness of the sintered (W_0.5Al_0.5)C is tested to be 1500 ± 50 kg mm⁻², while the density is about 9.417 ± 0.003 g cm⁻³, which is far lower than that of WC.     

Microstructural characterization of amorphous and nanocrystalline boron nitride prepared by high-energy ball milling

Microstructural parameters like crystallite size, lattice strain, stacking faults and dislocation density were evaluated from the X-ray diffraction data of boron nitride (BN) powder milled in a high-energy vibrational ball mill for different length of time (2-120 h), using different model based approaches like Scherrer analysis, integral breadth method, Williamson-Hall technique and modified Rietveld technique. From diffraction line-broadening analysis of the successive patterns of BN with varying milling time, it was observed that overall line broadening was an operative cause for crystallite size reduction at lower milling time (∼5 h), whereas lattice strains were the prominent cause of line broadening at higher milling times (>19 h). For intermediate milling time (7-19 h), both crystallite size and lattice strain influence the profile broadening although their relative contribution vary with milling time. Microstructural information showed that after long time milling (>19 h) BN becomes mixture of nanocrystalline and amorphous BN. The accumulations of defects cause this crystalline to amorphous transition. It has been found that twin fault (β′) and deformation fault (α) significantly contributed to BN powder as synthesized by a high-energy ball-milling technique. Present study consider only three ball-milled (0, 2 and 3 h) BN powder for faults calculation because fault effected reflections (1 0 1, 1 0 2, 1 0 3) disappear with milling time (>3 h). The morphology and particle size of the BN powders before and after ball milling were also observed in a field emission scanning electron microscope (FESEM).     

Fabrication of Sr- and Co-doped lanthanum chromite interconnectors for SOFC

Many studies have been performed dealing with the processing conditions of electrodes and electrolytes in solid oxide fuel cells (SOFCs). However, the processing of the interconnector material has received less attention. Lanthanum chromite (LaCrO₃) is probably the most studied material as SOFCs interconnector. This paper deals with the rheology and casting behaviour of lanthanum chromite based materials to produce interconnectors for SOFCs. A powder with the composition La_0.80Sr_0.20Cr_0.92Co_0.08O₃ was obtained by combustion synthesis. Aqueous suspensions were prepared to solids loading ranging from 8 to 17.5 vol.%, using ammonium polyacrylate (PAA) as dispersant and tetramethylammonium hydroxide (TMAH) to assure a basic pH and providing stabilization. The influence of the additives concentrations and suspension ball milling time were studied. Suspensions prepared with 24 h ball milling, with 3 wt.% and 1 wt.% of PAA and TMAH, respectively, yielded the best conditions for successful slip casting. Sintering of the green discs was performed in air at 1600 °C for 4 h leading to relatively dense materials.     

Synthesis of CuCr and CuCrAg alloy with nano-ceramic dispersion by mechanical alloying and consolidation by laser assisted sintering

Cu-4.5Cr and Cu-4.5Cr-3Ag (in wt%) alloys without or with 10 wt% nanocrystalline Al₂O₃ and ZrO₂ dispersion have been synthesized by mechanical alloying or milling and consolidated by laser assisted sintering in Ar atmosphere. Microstructural characterization by scanning and transmission electron microscopy and phase analysis by X-ray diffraction suggest that the alloyed matrix undergoes significant grain growth after sintering while the dispersoids retain their ultrafine size and uniform distribution in the matrix. The dispersion of nano-Al₂O₃ is more effective than that of nano-ZrO₂ in enhancing the mechanical properties due to the smaller initial particle size of Al₂O₃ than that of ZrO₂. In general, laser sintering of mechanically alloyed Cu-4.5Cr and Cu-4.5Cr-3Ag alloys with 10 wt% nanocrystalline Al₂O₃ at 100 W laser power and 1-2 mm s⁻¹ scan speed yields the optimum combination of high density (7.1-7.5 mg m⁻³), hardness (165-225 VHN), wear resistance and electrical conductivity (13-20% IACS).     

Tribological properties of Al6061–Al2O3 nanocomposite prepared by milling and hot pressing

Tribological properties of bulk Al6061–Al₂O₃ nanocomposite prepared by mechanical milling and hot pressing were investigated. Al6061 chips were milled for 30 h to achieve a homogenous nanostructured powder. A 3 vol.% Al₂O₃ nanoparticles (∼30 nm) were added to the Al6061 after 15 and 30 h from the beginning of milling. The milling times with Al₂O₃ in these two samples were then 15 h and 30 min, respectively. Additionally, 3 vol.% Al₂O₃ (1 μm and 60 μm) was added to the Al6061 after 15 h of milling; where, the micron size Al₂O₃ in these two samples, was milled 15 h with the matrix. Hot pressing of milled samples was executed at 400 °C under 128 MPa pressure in a uniaxial die. The hot pressed samples were characterized by micro-hardness test, bulk density measurements, pin on disc wear test, and finally scanning electron microscopy observations. Fifteen hour-milled nanocomposite with nanoscale Al₂O₃, showed improvement in wear resistance and bulk density compared with that of 30 min-milled nanocomposites due to better dispersion of Al₂O₃ nanoparticles, improved surface quality of nanocomposite particles before pressing and more grain refinement of Al matrix. Moreover, increasing the reinforcement size increased the wear rate because of reduction in relative density, hardness and inter-particle spacing.     

Synthesis and characterization of a new monophosphate (5-Cl-2,4-(OCH3)2C6H2NH3)H2PO4

Chemical preparation, crystal structure and NMR spectroscopy of a new organic cation 5-chloro(2,4-dimethoxy)anilinium monophosphate H₂PO₄ are given. This new compound crystallizes in the monoclinic system, with the space group P2₁/c and the following parameters: a = 5.524(2) Å, b = 9.303(2) Å, c = 23.388(2) Å, β = 90.66(4), V = 1201.8(2) Å³, Z = 4 and D_x = 1.573 g cm⁻³. Crystal structure has been determined and refined to R = 0.031 and R_w = 0.080 using 1702 independent reflections. Structure can be described as an infinite (H₂PO₄)_nⁿ⁻ corrugated chains in the a-direction. The organic groups (5-Cl-2,4-(OCH₃)₂C₆H₂NH₃)⁺ are anchored between adjacent polyanions through multiple hydrogen bonds. This compound is also investigated by IR, thermal, and solid-state, ¹³C, ³¹P MAS NMR spectroscopies.     

Rapid formation of lead magnesium niobate-based ferroelectric ceramics via a high-energy ball milling process

Pyrochlore-free nano-sized 0.90Pb(Mg_1/3Nb_2/3)O₃(PMN)-0.10PbTiO₃(PT) and 0.65PMN-0.35PT powders were synthesized from oxides via a high-energy ball milling process. Single perovskite phase PMN-PT were readily formed from the oxide mixture after milling for only 2 h. The grain size calculated from X-ray diffraction (XRD) patterns of all samples is about 20 nm, which is in agreement with the observation from scanning electron microscopy (SEM) (20-50 nm). PMN-PT ceramics were obtained by sintering the milled powders at temperature from 1000 to 1100°C for 2 h. The dielectric, ferroelectric properties of the PMN-PT ceramics derived from the synthesized powders were comparable with the reported results in the literature.     

Preparation of ultra-fine cobalt-nickel manganite powders and ceramics derived from mixed oxalate

Co_0.30Ni_0.66Mn_2.04O₄ negative temperature coefficient ceramics were derived from mixed oxalate Co_0.30Ni_0.66Mn_2.04(C₂O₄)₃·nH₂O. The mixed oxalate was synthesized by milling a mixture of cobalt acetate, nickel acetate, manganese acetate, and oxalic acid at room temperature. An ultra-fine Co_0.30Ni_0.66Mn_2.04O₄ powder was obtained by calcining the mixed oxalate in air at 800 °C for 3 h. The oxide powder compact was sintered at a relatively low temperature of 1100 °C for 5 h, achieving a relative density of ∼98%. The specific resistivity ρ_25 °C and the thermal constant B_25/85 °C were 765.2 Ω cm and 3604 K, respectively. The resistance drift after aging at 150 °C for 500 h was 1.5%.     

Thermal and mechanically activated decomposition of LiAlH4

Thermal stability of as-received LiAlH₄ and milled LiAlH₄ has been investigated. The thermal decomposition mechanism of as-received LiAlH₄ depends on the temperature-time history. Apparent activation energies and enthalpies of the reactions have been obtained. During milling treatment, the high temperature and pressures locally induced by shocks lead to LiAlH₄ mechanically decomposition. The decomposition temperatures of LiAlH₄ and Li₃AlH₆ are both reduced by ∼60 °C due to particle size reduction produced by mechanical milling. Besides, the activation energy of the decomposition reaction of LiAlH₄ decreases as compared to as-received LiAlH₄. Moreover, a layer of oxide (∼5 nm) at the surface of the milled alanate Li₃AlH₆ is observed. This layer could have a drastic influence on decomposition H-kinetics.