Preparation of CeB6 nano-powders by self-propagating high-temperature synthesis （SHS）

CeB6 powders were prepared by high-temperature self-propagating synthesis(SHS) in which CeO2,B2O3 and Mg were taken asreactants.The adiabatic temperature and dynamics of SHS reactions were investigated.The SHS reaction products and leached products werecharacterized by X-ray diffraction(XRD) and scanning electron microscopy(SEM).The results indicated that the adiabatic temperature ofMg-B2O3-CeO2 reaction system was rather higher than 1800 K to make the reaction propagate by itself,and the apparent activation energy(Ea)and reaction order(n) of exothermic peak on Mg-B2O3-CeO2 differential scanning calorimetry(DSC) curve were 23.03 kJ/mol and 1.31,respectively.The apparent activation energy was lower,so the reaction occurred easily.The SHS products consisted of MgO,CeB6 and littleMg3B2O6.The leached products consisted of single CeB6 phase and its purity was higher than 99.0%,and the average particle sizes of CeB6were smaller than 150 nm.     

A two-stage approach of manufacturing FeAl40 iron aluminides by self-propagating synthesis and pressureless sintering

A two-stage sintering process was successfully used to sinter FeAl to densification levels of just above 95% at a temperature of 1300°C. In the first stage, mixed iron and aluminium powders were synthesised at 750°C via self-propagating high-temperature synthesis (SHS) to form brittle and porous Fe₂Al₅. Then the pellets were crushed and milled to various sizes and mixed with iron powders in the nominal composition of FeAl40 and pressurelessly sintered at a higher temperature to obtain a higher densification by taking advantage of the less violent exothermic reaction of Fe₂Al₅ and Fe. The intermediate and end products in SHS and sintering were characterised by SEM/EDX and XRD. The porosity level of the final FeAl40 product was controlled by the heating rate and powder size, which was also strongly influenced by the temperature, holding time and the ratio of the two powders.     

Submicron LaB6 powders with high purity prepared in large scale by salt-assisted combustion synthesis

LaB₆ powders were synthesized in large scale by salt-assisted combustion synthesis (CS) with different NaCl diluent contents. The variety of phases, particle size and purity of the powders were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometer (EDS), and transmission electron microscope (TEM). With increase of NaCl content, the adiabatic combustion temperature of the reaction system linearly declines, the average particle size of leached products decreases, the impurity phases are easier to remove, and the products purity enhances obviously. When NaCl content is 40 wt%, the purity of the superfine powders of LaB₆ is more than 98 wt%, and the average particle size is 380 nm.     

Combustion characteristics of the Ni3Ti-TiB2 intermetallic matrix composites

Combustion synthesis (SHS) of Ni₃Ti-TiB₂ metal matrix composites (MMCs) was selected to investigate the effect of gravity in a reaction system that produced a light, solid ceramic particle (TiB₂) synthesized in situ in a large volume (>50 pct) of the liquid metallic matrix (Ni₃Ti). The effects of composition, green density of pellets, and nickel particle size on the combustion characteristics are presented. Combustion reaction temperature, wave velocity, and combustion behavior changed drastically with change in reaction parameters. Two types of density effects were observed when different nickel particle sizes were used. The structures of the combustion zones were characterized using temperature profile analysis. The combustion zone can be divided into preflame, reaction, and after-burning zones. The combustion mechanism was studied by quenching the combustion front. It was found that the combustion reactions proceeded in the following sequence: formation of liquid Ni-Ti eutectic at 940 °C → Ni₃Ti+NiTi phases → reduction of NiTi with B→TiB₂+Ni₃Ti.     

Synthesis of zirconium diboride-alumina composite by the self-propagating,high-temperature synthesis process

Synthesis of a ZrB₂-Al₂O₃ in-situ composite powder by the self-propagating, high-temperature synthesis (SHS) process using oxides as raw materials has been investigated. The combustion velocity was found to be about 5 mm/s. The combustion temperature varied in the range of 2173 to 2223 K, respectively. The SHS reaction was found to be mediated through melting of aluminum and, thereby, the SHS reaction. The ignition temperature is estimated to be about 1503 K by thermal analysis. Dendrite structures were also observed during SHS processing of the composite.     

UV-light-assisted synthesis of CeB6@Ag nano-trees for SERS application

The conventional methods of using surfactants to synthesize noble metal nanoparticles usually introduce residues on the surface,which inevitably decreases nanoparticles’ surface enhanced Raman scattering(SERS) performance.Herein,we propose a surfactant-free and feasible approach of preparing cerium hexaboride-Ag nano-trees hybrids(CeB₆@Ag nano-trees) as the SERS substrate.First,the CeB₆ was synthesized by a one-pot ionothermal method.Secondly,the CeB₆ powder and ...     

Calciothermic co-reduction of TiO2-Cr2O3 oxides in molten CaCl2: Effect of particle size of starting materials

In this research, the effect of particle size of starting materials (TiO₂ and Cr₂O₃) was investigated on calciothermic co-reduction of oxides and in-situ dissolution of the CaO by-product in molten CaCl₂. The particle size of starting oxides, molar ratio of molten salt and holding time of reaction at elevated temperature affected the progress of reduction reactions and the remaining oxygen. In the best optimized condition, the remaining oxygen in the obtained TiCr₂ was 1020 and 802 ppm using 388 and 120 nm particle sizes of starting oxides, respectively. The formation of TiCr₂ in calciothermic co-reduction process was considered to be mutual diffusion phenomena. Also, the kinetics of hydrogen adsorption for the co-reduced sample was better than that of the arc-melted sample. Particle sizes of the obtained products decreased with-the decrease of the particle sizes of the starting oxides.     

Fabrication of Ni-Ti Alloy by Self-Propagating High-Temperature Synthesis and Spark Plasma Sintering Technique

This work is focused on the possibilities of preparing Ni-Ti46 wt pct alloy by powder metallurgy methods. The self-propagating high-temperature synthesis (SHS) and combination of SHS reaction, milling, and spark plasma sintering consolidation (SPS) are explored. The aim of this work is the development of preparation method with the lowest amount of undesirable phases (mainly Ti₂Ni phase). The SHS with high heating rate (approx. 200 and 300 K min^?1) was applied. Because the SHS product is very porous, it was milled in vibratory disk milling and consolidated by SPS technique at temperatures of 1173 K, 1273 K, and 1373 K (900 °C, 1000 °C, and 1100 °C). The microstructures of samples prepared by SHS reaction and combination of SHS reaction, milling, and SPS consolidation are compared. The changes in microstructure with increasing temperature of SPS consolidation are observed. Mechanical properties are tested by hardness measurement. The way to reduce the amount of Ti₂Ni phase in structure is leaching of powder in 35 pct hydrochloric acid before SPS consolidation.     

Effects of Si and Ni powder refining on the formation mechanism of nickel silicides induced by mechanical alloying

The synthesis of the Ni₂Si, Ni₅Si₂, and NiSi phases has been investigated by mechanical alloying (MA) of Ni-33.3 at. pct Si, Ni-28.6 at. pct Si, and Ni-50 at. pct Si powder mixtures. As-received and 60-minute premilled elemental powders were subjected to MA. The average surface area of the premilled Ni powder particles, which had a flaky shape, was 3.5 times larger than that of the as-received Ni powder particles, which had a spherical shape. The as-received Si powder was angular in shape and the mean particle size was 19.1 μm, whereas the mean particle size of the premilled Si powder was 10 μm. A self-propagating high-temperature synthesis (SHS) reaction, followed by a slow solid-state diffusion reaction, was observed to produce Ni silicide phases during MA of the elemental powders. The reactants and the product, however, coexisted for a long period of MA time. On the other hand, only the SHS reaction was observed to produce Ni silicides during MA of the premilled elemental powders, indicating that Ni silicides formed rather abruptly in a short period of MA time. The mechanisms and reaction rates for the formation of Ni silicides via MA appeared to be influenced by the elemental powder particle size and shape as well as the heat of formation of the products.     

Features of Production and High-Temperature Oxidation of SHS Ceramics Based on Zirconium Boride and Zirconium Silicide

This article is devoted to the investigation into the combustion kinetics and mechanism of reaction mixtures in Zr–Si–B and Zr–B systems formed according to the forced SHS-pressing of compact ceramic materials, as well as to studying their heat resistance. It is shown that dependences of the combustion temperature and rate on the initial temperature (T₀) for compositions in the Zr–Si–B system are linear; i.e., staging of chemical reactions of formation of zirconium diboride and disilicide remains invariable with an increase in T₀. The values of effective activation energy of SHS process, which evidence the leading role of the reaction interaction of zirconium with boron and silicon in the melt, are calculated. Staging of chemical transformations in the combustion wave of the Zr–Si–B system is investigated: initially the ZrB₂ phase is formed by crystallization from the melt, and then the ZrSi₂ phase appears with a delay of 0.5 s; unreacted Si crystallizes after 1 s. The phase composition of synthesis products, in which the main component is ZrB₂ diboride, and zirconium disilicide, Si, and ZrB₁₂ boride are contained depending on the composition of the reaction charge, is investigated. Compact samples having high hardness and low residual porosity are fabricated according to forced SHS-pressing technology. High-temperature oxidation of SHS samples results in the formation of SiO₂–ZrO₂–B2O₃ oxide films and ZrSiO₄ complex oxide on their surface depending on the composition, which serve the effective diffusion barrier and lower the oxidation rate.     

Production of silicon nitride by the acid enrichment of products of combustion of ferrosilicon in nitrogen

Production of silicon nitride by acid enrichment of products of interaction between ferrosilicon and gaseous nitrogen under conditions of self-propagating high-temperature synthesis (SHS) is studied. The effect of the nature of acid, its concentration, agitation of solution, and process temperature is determined. The reaction of the Si₃N₄ + Fe composite powder and the hydrochloric acid solution is found to have a stage behavior. The apparent activation energy of iron passing into the solution is determined. The purity of the produced Si₃N₄ powder is demonstrated to depend on a degree of nitration of SHS products. The chemical and phase composition of the powder and its specific surface are determined.     

Effects of Si and Ni powder refining on the formation mechanism of nickel silicides induced by mechanical alloying

The synthesis of the Ni₂Si, Ni₅Si₂, and NiSi phases has been investigated by mechanical alloying (MA) of Ni-33.3 at. pct Si, Ni-28.6 at. pct Si, and Ni-50 at pct Si powder mixtures. As-received and 60-minute premilled elemental powders were subjected to MA. The average surface area of the premilled Ni powder particles, which had a flaky shape, was 3.5 times larger than that of the asreceived Ni powder particles, which had a spherical shape. The as-received Si powder was angular in shape and the mean particle size was 19.1 μm, whereas the mean particle size of the premilled Si powder was 10 μm. A self-propagating high-temperature synthesis (SHS) reaction, followed by a slow solid-state diffusion reaction, was observed to produce Ni silicide phases during MA of the elemental powders. The reactants and the product, however, coexisted for a long period of MA time. On the other hand only the SHS reaction was observed to produce Ni silicides during MA of the premilled elemental powders, indicating that Ni silicides formed rather abruptly in a short period of MA time. The mechanisms and reaction rates for the formation of Ni silicidesvia MA appeared to be influenced by the elemental powder particle size and shape as well as the heat of formation of the products. W.H. LEE, Professor, formerly with the School of Metallurgical and Materials Engineering, Kookmin University, Seoul 133-791, Korea     

Leaching of sulfide copper ore in a NaCl–H2SO4–O2 media with acid pre-treatment

A study was made of the leaching of a sulfide copper ore in a NaCl–H₂SO₄–O₂ media after pre-treatment by agglomeration with H₂SO_4(conc) and NaCl. The leaching variables evaluated included the amount of NaCl to be employed, the percentage of solids in the leaching solution, particle size of the raw mineral to be leached, and the preferable method of agitation in the leaching system. Mineralogical characterization of the material to be leached included analysis of the raw ore and of the leached ore residue using reflected-light microscopy, X-ray diffraction, and scanning electron microscopy. The soluble species included djurleite and digenite. The most important parameters in the leaching process proved to be particle size and type of agitation. A total percentage of copper extraction of 70% was achieved using mechanical stirring, which increased to 78% when using compressed air agitation. The best extraction of the copper was achieved when leaching with 3 g/L of chloride, room temperature of 20 °C, and when all particles were < 1.65 mm in diameter.     

Wetting of Polycrystalline α-Al2O3 by Molten Mg in Ar Atmosphere

The characteristic wetting behavior and modes of the evaporating Mg drops on the α-Al₂O₃ surfaces were evaluated by a combination of the variations in contact angle and drop geometry using both improved and modified sessile drop methods. The system is essentially partial wetting at 973 to 1173 K with initial contact angles of 94 to 67 deg, decreasing with increasing temperature. The wettability improves with interfacial reaction but deteriorates with Mg surface oxidation. The presence of the oxide film at the Mg drop surface strongly inhibits the movement of the triple line and thus makes the constant contact diameter mode dominate the entire wetting process. Removal of the oxide film greatly facilitates the depinning of the triple line. On the other hand, the interfacial reaction leads to the prior formation of MgO and later MgAl₂O₄ as a result of consumption of Mg, while it increases the amount of displaced Al. Nevertheless, the role of the interfacial reaction on the wetting is difficult to quantitatively evaluate because of concurrent diminishing in the drop volume under evaporation.     

Oxidation of pyrrhotite particles falling through a vertical tube

The oxidation of pyrrhotite particles of 51 and 88 Μm size was studied during falling in a downward stream of O₂-N₂ gas mixture. At the temperature of reaction tube lower than 825 K, the oxidation rate of particles of 51 Μm size was higher than that of 88 Μm. At higher temperature, on the other hand, the oxidation rate was virtually unvaried with the particle size, and the fractional reaction of oxidized particles increased in proportion to the oxygen partial pressure. Progress of oxidation and fusion of the particles was calculated based on a mathematical model. According to the calculation, when the particle temperature was attained at about 1100 K, it increased instantaneously and the particles were melted, because the rate of heat loss from the particles was overbalanced by the rate of heat generation due to oxidation.     

Reaction products of Al/TiC composites fabricated by the pressureless infiltration technique

The interfacial reaction products of the Al-Mg/TiC _p composite fabricated by the pressureless infiltration method were analyzed using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and transmission electron microscopy (TEM). During the fabrication of composites, reaction products with various morphologies and sizes were formed in the A1 matrix as well as in the vicinity of the TiC particles by the interfacial reaction between the Al alloy and the TiC particles. From the EDS and selected-area diffraction pattern (SADP) analysis, Al₄C₃, Al₁₈Ti₂Mg₃, Ti₂AlC, Al₃Ti, and TiAl could be identified to form as interfacial reaction products. Both the size and the amount of the reaction products were increased with increasing fabrication temperature as well as fabrication time. Coarse Al₃Ti was barely observed in water-quenched composites, while it was observed at all fabrication temperatures (700 °C to 1000 °C) in furnace-cooled conditions. An erratum to this article is available at .     

Influence of the synthesis conditions of boron carbide on its structural parameters

Boron carbide is prepared by self-propagating high-temperature synthesis (SHS) in a composition range from 5 to 30 at % carbon. The introduction of an inert (MgO) and active (Mg(ClO₄)₂) additives into the reaction mixture leads to a variation in process parameters such as the temperature and combustion rate. It is established that the unit cell metrics of boron carbide substantially vary depending on the synthesis conditions. The degree of the effect of the SHS mode on the crystal structure rises with an increase in the carbon fraction in the boron carbide structure. This regularity is associated with the ordering diversity of carbon atoms in nonstoichiometric boron carbide. No influence of the synthesis conditions on the unit cell parameters is observed for stoichiometric boron carbide, which is associated with the structure saturation with carbon. It is shown that the variation in the combustion temperature during SHS of boron carbide of the same composition leads to the variability of the structural parameters, thus reflecting the influence of the synthesis conditions on the material crystal structure.     

Structure and phase formation of combustion products during the synthesis of γ-AlON in self-propagating high-temperature synthesis

Synthesis of aluminum oxynitride (γ-AlON) in conditions of self-propagating high-temperature synthesis (SHS) gas-statting under high pressures (10–100 MPa) of gaseous nitrogen, including the mode of so-called coupled combustion reactions (chemical furnaces) is investigated. It is shown that chemical and phase compositions of combustion products, as well as their structure and morphology of powder particles, depend on the reagent ratio in Al–Al₂O₃ initial mixture, as well as on nitrogen pressure, combustion temperature of highly exothermic components of chemical furnaces, and grade of initial reagents. The structure of γ-AlON powder particles are determind and its relation with operation conditions of SHS. Optimal SHS parameters for Al₅O₆N (γ-AlON) formation are established.