Thermal explosion synthesis of ZrC particles and their mechanism of formation from Al–Zr–C elemental powders

ZrC particles were fabricated by thermal explosion (TE) from mixture of Al, Zr and C elemental powders. Without the addition of Al, the synthesized ZrC particles had irregular shape of ~ 4.0 μm in average. Increasing Al content up to 30 wt.%, however, refined significantly them down to < 0.2 μm with regularly square morphology. The Al effect of reaction mechanism promoted the ZrC formation as diluents in the course of TE, which was clarified using differential thermal analysis and X-ray diffraction technique. The melting of Al favored the reaction with Zr to generate ZrAl₃, and then the dissolution of C into the Al–Zr liquid resulted in precipitation of ZrC. Meanwhile, the exothermic effect prompted C atoms dissolving into Zr–Al liquid and eventually led to precipitation of ZrC out of the supersaturated liquid. The Al addition inhibited particle growth, but also promoted the TE reaction.     

Corrosion synthesis of boron carbide with pore and hollow structure

In this study, corrosion synthesis of boron carbide particles with pore size ranging from hundreds of nanometers to several micrometers was reported. Firstly, the pristine boron carbide powders which contain free carbon have been synthesized at 350 °C in a steel autoclave. As the pristine boron carbide was refluxed by HClO₄ at 170 °C for 1–2 h, the boron carbide particles with macropores were produced. Similarly, the boron carbide nanocages can also be obtained. The corrosion of the embedded amorphous and/or low crystallinity carbon/boron carbide using HClO₄ was considered for the formation of boron carbide with macropores and hollow nanocages.     

Nano-sized zirconium carbide powder: Synthesis and densification using a spark plasma sintering apparatus

Nano-sized zirconium carbide powder was synthesized at 1600 °C by the carbothermal reduction of ZrO₂ using a modified spark plasma sintering (SPS) apparatus. The synthesized ZrC powder had a fine particle size of approximately 189 nm and a low oxygen content of 0.88 wt%. The metal basis purity of the synthesized powder was 99.87%. The low synthesis temperature, fast heating/cooling rate and the effect of current during the modified SPS process effectively suppressed the particle growth. Using the synthesized powder, monolithic ZrC ceramics with high relative density (97.14%) were obtained after the densification at 2100 °C for 30 min at a pressure of 80 MPa by SPS. The average grain size of the densified ZrC ceramics was approximately 9.12 μm.     

Synthesis and hydrogen reduction of nano-sized copper tungstate powders produced by a hydrothermal method

The pure nano-sized copper tungstate (CuWO₄) powders were prepared by hydrothermal method and consequent annealing at 500 °C for 120 min. The thermogravimetric analysis was used to study dehydration processes, and the scanning electron microscopy (SEM) indicated that CuWO₄ particles were mostly spherical in the size range from 60 to 90 nm. Hydrogen reduction at 800 °C for 60 min converted the CuWO₄ to W–Cu composite powders. The hydrogen reduction results showed that nano-sized CuWO₄ particles calcining at 500 °C for 120 min indicated finer microstructure than the other calcination temperatures of 0 °C, 400 °C, 620 °C, 650 °C and 700 °C. W–Cu particles were observed finest and homogeneous in the size range from 90 to 150 nm by SEM images. Homogeneous distribution of W and Cu particles was clearly demonstrated by elemental mapping. Encapsulation of Cu phase by the W phase was observed by EDS and TEM. From FFT and HRTEM images, the orientation relationship of (01-1)_Cu ∥(01-1)_W and a semicoherent interface between W and Cu phases could be observed. A good correlation between the HRTEM image and the calculated lattice misfit (δ) was obtained.     

Synthesis and characterization of zirconium carbide nanorods at low temperature

A novel chemical synthetic method at low temperature was developed for the synthesis of ZrC nanorods, using ZrCl₄ and sodium metal in the presence of naphthalene as the carbon source. The results showed that the ZrCl₄, after heat treatment in argon atmosphere at temperatures above 500°C, can be completely converted into ZrC nanorods. However, the initial formation temperature of ZrC was as low as 400 °C whereas ZrO₂ as an intermediate product was also produced from the precursor at 300°C, and the mixture was finally transformed into pure ZrC at 700°C. The synthesized ZrC nanorods exhibited cubic lattice structure.     

Highly sinter-active (Mg–Cu)–Zn ferrite nanoparticles prepared by flame spray synthesis

Nanoscale ZnFe₂O₄, Mg_0.5Zn_0.5Fe₂O₄ and Mg_0.2Cu_0.2Zn_0.62Fe_1.98O_3.99 powders were prepared for the first time by flame spray synthesis (FSS). Solutions of metal β-diketonates in organic solvents were used as precursor. Crystalline particles of spinel structure with 6–13 nm primary particle size resulted from the flame process. Particle and crystallite size depended on the flow rate of the atomizing gas, the precursor and its molarity. Compacts prepared from Mg–Cu–Zn ferrite nanoparticles revealed an extremely high sinter-activity. A sintered density of 5.05 g cm⁻³ was achieved after firing for 2 h at 900 °C without any sintering additives, while a maximum density of 4.91 g cm⁻³ was obtained with particles from the conventional ceramic route. The permeability of the sintered Mg–Cu–Zn ferrite nanopowder compacts reached μ = 600 at 1 MHz and the saturation magnetisation was 80 emu g⁻¹. The outstanding sintering activity of the flame-made ferrite powders is attributed to their small primary particle size.     

Synthesis of V8C7–Cr3C2 nanocomposite via a novel in-situ precursor method

V₈C₇–Cr₃C₂ nanocomposite has been synthesized by a novel in-situ precursor method, and the raw materials are ammonium vanadate (NH₄VO₃), ammonium dichromate ((NH₄)₂Cr₂O₇) and glucose (C₆H₁₂O₆). The products were characterized by thermogravimetric and differential scanning calorimetry (TG-DSC), X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) techniques. The results show that V₈C₇–Cr₃C₂ nanocomposite with an average crystallite size of 31.5 nm can be synthesized at 900 °C for 1 h. The powders show good dispersion and are mainly composed of spherical or nearly spherical particles with a mean diameter of about 100 nm. The weight loss ratio of the precursor throughout the reaction process reaches 70 wt.%, and it changes rapidly before 400 °C (about 35 wt.%). Four endothermic peaks and three exothermic peaks occur during the reaction. The surface of the specimen is mainly composed of V, Cr, C and O four elements. The synthesis temperature of V₈C₇–Cr₃C₂ nanocomposite by the method (900 °C) is 500 °C lower than that of the conventional method (1400 °C).     

Effects of ZrC and SiC addition on the microstructures and mechanical properties of binderless WC

ZrC-added WC ceramics and SiC-added WC–2 mol% ZrC ceramics were sintered at 1800 °C using a resistance-heated hot-pressing machine. Dense WC ceramics containing 0–1 mol% ZrC and WC–2 mol% ZrC ceramics containing 1–6 mol% SiC were obtained. The reaction products W₂C, ZrO₂ and ZrC-based solid solutions were formed in the ZrC-added WC ceramics during sintering. The relative amount of W₂C reached zero at 2 mol% ZrC, increased in the range of 2–6 mol% ZrC, and decreased again above 6 mol% ZrC. The average WC grain size decreased from 0.49 μm for the WC ceramic to 0.24 μm at 4 mol% ZrC. The SiC addition of 1–2 mol% to the WC–2 mol% ZrC ceramics caused abnormal growth of WC grains. The Vickers hardness of the ZrC-added WC ceramics decreased to 17 GPa at 2 mol% ZrC. The hardness of the SiC-added WC–2 mol% ZrC ceramics increased from 12.4 at 2 mol% SiC to 21.5 GPa at 6 mol% SiC. The fracture toughness of the ZrC-added WC ceramics decreased from 6.2 MPa m^0.5 for the WC ceramic to 5.2 MPa m^0.5 at 4 mol% added ZrC. The fracture toughness of the WC–2 mol% ZrC ceramics with 6 mol% SiC were relatively high at 6.7 MPa m^0.5. The addition of SiC to WC-based ceramics thus improved both hardness and fracture toughness.     

Ultra high-pressure spark plasma sintered ZrC-Mo and ZrC-TiC composites

Ultra-high-pressure spark plasma sintering was applied to ZrC-20 wt%Mo and ZrC-20 wt%TiC composites with a pressure up to 7.8 GPa and temperatures of 1550 °C and 1950 °C. Mechanical performance of the composites was benchmarked against a plain ZrC produced by the same method. Both composites outperformed the pure ZrC with superior hardness and indentation fracture toughness of 2239 HV1 and 5.4 MPa m^1/2, and 1896 HV1 and 5.9 MPa m^1/2, respectively, for ZrC-Mo and ZrC-TiC composites. It was shown that ultra-high compaction pressure affected the ZrC-20 wt%TiC miscibility gap by lowering the temperature threshold from the usually applied 1800 °C down to 1550 °C resulting in formation of the solid state solution of (Zr,Ti)C. In contrast, the high pressure does not inhibit the carburisation of Mo with ZrC to form MoC, even when experiments were performed in a graphite free environment. The equiaxed morphology of ZrC grains along with a right-shift in XRD peaks for ZrC indicates dissolution of Mo in ZrC resulting in formation of the solid solution of (Zr,Mo)C. High-temperature X-ray diffraction analysis under oxidation conditions was performed on the samples showing degradation of ZrC-20 wt%Mo due to the oxidation of Mo at high-temperature leading to MoO₃ vaporisation. Conversely, the oxidation of ZrC-20 wt%TiC composites was characterised by formation of ZrO₂ and TiO₂ remaining stable up to 1500 °C.     

Effect of ball-milling time on structural characteristics and densification behavior of W-Cu composite powder produced from WO3-CuO powder mixtures

Understanding the microstructure of W–Cu nanocomposite powder is essential for elucidating its sintering mechanism. In this study, the effect of milling time on the structural characteristics and densification behavior of W-Cu composite powders synthesized from WO₃-CuO powder mixtures was investigated. The mixture of WO₃ and CuO powders was ball-milled in a bead mill for 1 h and 10 h followed by reduction by heat-treating the mixture at 800 °C in H₂ atmosphere with a heating rate of 2 °C/min to produce W-Cu composite powder. The microstructure analysis of the reduced powder obtained by milling for 1 h revealed the formation of W–Cu powder consisting of W nanoparticle-attached Cu microparticles. However, Cu-coated W nanocomposite powder consisting of W nanoparticles coated with a Cu layer was formed when the mixture was milled for 10 h. Cu-coated W nanopowder exhibited an excellent sinterability not only in the solid-phase sintering stage (SPS) but also in the liquid-phase sintering stage (LPS). A high relative sintered density of 96.0% was obtained at 1050 °C with a full densification occurring on sintering the sample at 1100 °C. The 1 h-milled W-Cu powder exhibited a high sinterability only in the LPS stage to achieve a nearly full densification at 1200 °C.     

Precipitation of Cr-rich phases in rapidly solidified Ni–20Al–8Cr (at.%) powders

The evolution of the microstructure in rapidly solidified Ni–20.9Al–8Cr–0.49B (at.%) powders after different continuous and isothermal heat treatments at temperatures up to 1100 °C has been studied by electron microscopy and microanalysis. Powders in the rapidly solidified condition have a dendritic microstructure consisting of Ni₃Al dendrites and a NiAl phase in the interdendritic regions. Chromium is in solid solution in both phases. This microstructure is stable when heating at 10 K min⁻¹ up to 750 °C. When the powders are heated up to 950 °C, partial dissolution of the NiAl phase and the precipitation of very small chromium-rich particles take place.The microstructure of the powders after annealing at temperatures between 750 and 1100 °C for different times is characterised by the dissolution of the β-NiAl phase and the simultaneous precipitation of various Cr-rich phases. α-Chromium, the metastable X-phase, and dark polygonal Cr₅B₃ precipitates have been identified.The segregation of chromium and boron in the form of borides removes these elements from the intermetallic matrix, so the content of both elements should be optimised to preserve their beneficial influence on the ductility of the γ′-Ni₃Al phase.     

Direct synthesis of varistor-grade doped nanocrystalline ZnO and its densification through a step-sintering technique

A direct synthesis of varistor-grade doped ZnO powder was attempted by simple hydrolysis followed by low-temperature refluxing (80 °C) in aqueous and alcoholic media. Rod like, one-dimensional nanocrystalline doped ZnO powders with crystallite size 24 nm and Brunauer–Emmett–Teller (BET) bulk surface area 22 m² g⁻¹ were synthesized. Sintering characteristics of these powders were analyzed under step-sintering coupled with rapid heating up to 1050 °C. The microstructural features and I–V characteristics of the step-sintered doped ZnO were compared with composite varistors. The study shows the advantage of the addition of nanosize doped varistor-grade ZnO as well as step-sintering for controlling grain size and improving varistor performance.     

Kinetics of synthesis olivine LiFePO4 by using a precipitated-sintering method

The LiFePO₄ precursor was synthesized using a precipitation with raw materials LiOH·H₂O, (NH₄)₂HPO₄ and FeSO₄·7H₂O. The kinetics of synthesis olivine LiFePO₄ was studied by using a differential thermal analysis (DTA) at different heating rates. The average activation energy of the reaction where the precursor form olivine LiFePO₄ was 239.39 kJ mol^?1, calculated by Doyle–Ozawa and Kissinger methods. The reaction order, frequency factor, rate equation and kinetic equation of the reaction were determined by the Kissinger method. The samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and Fourier transform infrared spectrometer (FTIR). The sample synthesized by the precursor sintered for 6 h at 550 °C shows a single-phase, regular morphology, well-distributed particle sizes and good electrochemical properties.     

In situ synthesis and sintering of ZrB2 porous ceramics by the spark plasma sintering–reactive synthesis (SPS–RS) method

Zirconium diborides (ZrB₂) porous ceramics were synthesized by the Spark Plasma Sintering-Reactive Synthesis (SPS–RS) technique using ZrO₂ and B₄C as precursors which undergo solid state reaction that lead to pore formation. Phase analysis of the products indicated that the reaction started between 1200 °C and 1300 °C and was carried out at 1600 °C within 10 min under SPS conditions, which was consistent with the thermodynamic calculations. The as-prepared ZrB₂ porous ceramics had a relatively smaller crystallite size (~ 1 μm), a lower oxygen content (~ 1.04 wt.%) and a relative density of 29.9%. The oxygen impurities decreased with the sintering temperature and holding time. In addition, the measured results showed that the reaction was carried out within 10 min holding time at the temperature of 1600 °C and the synthesized ZrB₂ products had high purity in comparison to commercial ZrB₂ powder product.     

Giant dielectric response in (Li,Ti)-doped NiO ceramics synthesized by the polymerized complex method

This paper reports on the synthesis of nanocrystalline (Li, Ti)-doped NiO powders (i.e., Li_0.3Ti_0.02Ni_0.68O, abbreviated as LTNO) by the polymerized complex (PC) method. The synthesized LTNO powders were characterized by thermogravimetric–differential thermal analysis (TG–DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The powders, with particle sizes of 39, 65 and 72 nm as estimated from XRD, were sintered in air at 1280 °C for 4 h to obtain bulk LTNO ceramics. A giant dielectric constant of 10⁴–10⁵ at low frequency with weak temperature dependence over the measured temperature range (−30 to 160 °C) was observed in the sintered LTNO ceramics. The origin of the high permittivity observed in these LTNO ceramics is attributed to the Maxwell–Wagner polarization mechanism and a thermally activated mechanism.     

Synthesis of NiCrAl/MgO–ZrO2 cermet powders by chemical method for functionally graded coatings

Functionally graded materials (FGMs) are receiving great attention as they provide optimum thermal and mechanical properties without a discrete interface between two materials. In order to control the chemical composition and microstructure of FGMs, NiCrAl/MgO–ZrO₂ cermet powders were successfully developed in the present work. The NiCrAl/MgO–ZrO₂ powders were synthesized from a solution of NiCrAl, ZrO₂ and Mg hydroxide carbonate precursors using chemical synthesis. The powders were dried at 125 °C for 3 h and then pellet samples were sintered at 1381 °C for 30 min under N₂–5%H₂ atmosphere. The powders were characterized by scanning electron microscope, energy dispersive spectroscopy, X-ray mapping and X-ray diffraction. The obtained results showed that the optimum particle sizes of NiCrAl/MgO–ZrO₂ powders were between 45 and 90 μm. Microstructural studies have shown a uniform mixing in the cermet powders. It was also found that ZrO₂, MgO, MgZr₇O₁₄, Ni, Cr and Ni₅Al₃ phases were present in the cermet powder.     

Preparation of Eu-activated strontium orthosilicate (Sr1.95SiO4:Eu0.05) phosphor by a sol–gel method and its luminescent properties

Eu²⁺-activated Sr₂SiO₄ phosphor was successfully synthesized by a sol–gel method using sodium silicate and SrO as the starting materials. The wavelength of the emission peak and the emission intensity of the phosphor powders were influenced by the pre-treating temperature. The maximum emission intensity of the phosphor was found as pre-treated at 1200 °C in air and then heated at 1300 °C in the reducing atmosphere (10% H₂ + 90% He). As the pre-treating temperature was <1200 °C, the composition of the phosphor powder was not uniform, which leads to decrease of the emission intensity, whereas >1200 °C, the decrease of the emission intensity may be caused from the reversible phase transformation of Sr₃SiO₅ → Sr₂SiO₄ at 1300 °C, which also shows the red-shift behavior.     

Oxidation behavior of micro-sized Al2O3–TiC–Co composites prepared from cobalt-coated powders

The oxidation behavior of hot-pressed Al₂O₃–TiC–Co composites prepared from cobalt-coated powders has been studied in air in the temperature range from 200 °C to 1000 °C for 25 h. The oxidation resistance of Al₂O₃–TiC–Co composites increases with the increase of sintering temperature at 800 °C and 1000 °C. The oxidation surfaces were studied by XRD and SEM. The oxidation kinetics of Al₂O₃–TiC–Co composites follows a rate that is faster than the parabolic-rate law at 800 °C and 1000 °C. The mechanism of oxidation has been analyzed using thermodynamic and kinetic considerations.     

In situ X-ray synchrotron diffraction study of MgB2 synthesis from elemental powders

The kinetics of MgB₂ synthesis is studied in situ by synchrotron X-ray diffraction, using pressed compacts of 200–400 μm magnesium powders mixed with three types of submicrometer, amorphous, high-purity boron powders. Reaction times for commercially available and plasma-synthesized boron powders decreases from 100 to 2 min as temperature increases from 670 to 900 °C. They can be described by diffusion-controlled models of a reacting sphere with kinetics characterized by diffusion coefficients increasing with temperature from 2 × 10⁻¹⁷ to 3 × 10⁻¹⁶ m² s⁻¹, with activation energies of 123–143 kJ mol⁻¹. Plasma-synthesized boron powders doped with 7.4 at.% carbon show no significant differences in reaction kinetics as compared to undoped powders.     

B4C/TiB2 composite powders prepared by carbothermal reduction method

B₄C–(10–20 vol%)TiB₂ composite powders have been synthesized with the temperature of 1650–1800 °C by carbothermal reduction process using boron acid, carbon black and TiO₂ powder as the starting materials. B/C mole ratio of the starting materials is ascertained, thermodynamics temperature of the reactions is calculated and the effect of ball milling on the composite powders is discussed. The experimental results indicate that B/C mole ratio of the starting materials and composite powders are 4.4 and 3.98–4.03, respectively. The purity of the gained powders is more than 99 wt%. Wet ball milling eliminates the size of the B₄C/TiB₂ composite powders from 30–40 to 3–5 μm by decreasing the conglomeration of the composite powders. XRD and EDS results show that the composite powders are composed of B₄C and TiB₂.