Effect of Al addition on SiC–B4C cermet prepared by pressureless sintering and spark plasma sintering methods

SiC–B₄C–Al cermets containing 5, 10 and 20 wt.% of Al were fabricated by high-energy planetary milling followed by conventional sintering and spark plasma sintering (SPS) techniques separately. The average particle size reduced to ~ 3 μm from an initial size of 45 μm after 10 h of milling. The as-milled powders were conventionally sintered at 1950 °C for 30 min under argon atmosphere and SPS was carried out at 1300 °C for 5 min under 50 MPa applied pressure. The formation of Al₈B₄C₇ and AlB₁₂ phases during conventional sintering and SPS were confirmed by X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses. The formation of Al₈B₄C₇ at 700 °C and AlB₁₂ at 1000 °C was well supported by XRD and differential scanning calorimetry (DSC). The maximum relative density, microhardness and indentation fracture resistance of SiC–B₄C–10Al consolidated by SPS are 97%, 23.80 GPa and 3.28 MPa·m^1/2, respectively.     

Influence of glass additives on the sintering behavior and dielectric properties of BaO·(Nd0.8Bi0.2)2O3·4TiO2 ceramics

Effects of various glasses (Bi₂O₃–B₂O₃–ZnO–SiO₂ (BBXSZ, where X = the mole fraction of Bi₂O₃ in the glass) glasses with different Bi₂O₃ content) on both the sintering behavior and microwave dielectric properties of BaO·(Nd_1?xBi_x)₂O₃·4TiO₂ (BNBT) ceramics were investigated in developing low-temperature-fired dielectric ceramics for microwave devices. Glass wetting characteristics on the BNBT surface, X-ray diffractometer (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and a dilatometer were used to examine the effect of various glasses on BNBT densification and the chemical reaction between the glass and BNBT. The results indicate that BB25SZ glass can be used as a sintering aid to reduce the densification temperature of BNBT from 1300 to 900 °C without secondary phase formation. BNBT ceramics with 20 wt.% BB25SZ glass sintered at 900 °C show a relative density of 92%, a high-dielectric-constant of 84, a quality factor (Qxf) of 2999, and a temperature coefficient of resonant frequency of 23.7 ppm/°C.     

Spark plasma sintering of TiC particle-reinforced molybdenum composites

In order to improve the recrystallization resistance and the mechanical properties of molybdenum, TiC particle-reinforcement composites were sintered by SPS. Powders with TiC contents between 6 and 25 vol.% were prepared by high energy ball milling. All powders were sintered both at 1600 and 1800 °C, some of sintered composites were annealed in hydrogen for 10 h at 1100 up to 1500 °C. The powders and the composites were investigated by scanning electron microscopy and XRD. The microhardness and the density of composites were measured, and the densification behavior was investigated. It turns out that SPS produces Mo–TiC composites, with relative densities higher than 97%.The densification behavior and the microhardness of all bulk specimens depend on both the ball milling conditions of powder preparation and the TiC content. The highest microhardness was obtained in composites containing 25 vol.% TiC sintered from the strongest milled powders. The TiC particles prevent recrystallization and grain growth of molybdenum during sintering and also during annealing up to 10 h at 1300 °C. Interdiffusion between molybdenum and carbide particles leads to a solid solution transition zone consisting of (Ti_1 −x Mo_x)C_y carbide. This diffusion zone improves the bonding between molybdenum matrix and TiC particles. A new phase, the hexagonal Mo₂C carbide, was detected by XRD measurements after sintering. Obviously, this phase precipitates during cooling from sintering temperature, if (Ti_1 −x Mo_x)C_y or molybdenum, are supersaturated with carbon.     

Synthesis and characterization of bismuth alkaline titanate powders

In this work, samples of bismuth alkaline titanate, (K_0.5Na_0.5)_(2?x/2)Bi_(x/6)TiO₃, (x = 0.05–0.75) have been prepared by conventional ceramic technique and molten salts. Metal oxides or carbonates powders were used as starting raw materials. The crystalline phase of the synthesized powders was identified by the X-ray diffraction (XRD) and particle morphology was characterized by scanning electron microscopy (SEM). Solid state reaction method was unsuccessful to obtain pellets. From XRD results, a rhombohedral structure was detected and the parameter lattice were estimated to be a = 5.5478 Å and α = 59.48°. These parameters were used to refine the structure by Rietveld analysis. SEM results showed several morphologies. Apparently, bismuth is promoting the grain growth whose sizes vary from 30 nm to 180 nm It is expected that these materials can be utilized in practical applications as substitutes for lead zirconatetitanate (PZT)-based ceramics.     

A study of the densification mechanisms during spark plasma sintering of zirconium (oxy-)carbide powders

Zirconium oxycarbide powders with controlled composition ZrC_0.94O_0.05 were synthesized using the carboreduction of zirconia. They were further subjected to spark plasma sintering (SPS) under several applied loads (25, 50, 100 MPa). The densification mechanism of zirconium oxycarbide powders during the SPS was studied. An analytical model derived from creep deformation studies of ceramics was successfully applied to determine the mechanisms involved during the final stage of densification. These mechanisms were elucidated by evaluating the stress exponent (n) and the apparent activation energy (E_a) from the densification rate law. It was concluded that at low macroscopic applied stress (25 MPa), an intergranular glide mechanism (n ? 2) governs the densification process, while a dislocation motion mechanism (n ? 3) operates at higher applied load (100 MPa). Transmission electron microscopy observations confirm theses results. The samples treated at low applied stress appear almost free of dislocations, whereas samples sintered at high applied stress present a high dislocation density, forming sub-grain boundaries. High values of apparent activation energy (e.g. 687–774 kJ mol^?1) are reached irrespective of the applied load, indicating that both mechanisms mentioned above are assisted by the zirconium lattice diffusion which thus appears to be the rate-limiting step for densification.     

Combined effect of Ni and nano-Y2O3 addition on microstructure,mechanical and high temperature behavior of mechanically alloyed W-Mo

Nanostructured tungsten (W) based alloys with the nominal compositions of W₇₀Mo₃₀ (alloy A), W₅₀Mo₅₀ (alloy B), and 1.0 wt.% nano-Y₂O₃ dispersed W₇₉Ni₁₀Mo₁₀ (alloy C) (all in wt.%) have been synthesized by mechanical alloying followed by compaction at 0.50, 0.75 and 1 GPa pressure for 5 mins and conventional sintering at 1500 °C for 2 h in Ar atmosphere. The microstructure, evolution of phases and thermal behavior of milled powders and consolidated products has been investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), High resolution transmission electron microscopy (TEM), Energy dispersive spectroscopy (EDS) and differential scanning calorimetry (DSC). Minimum crystallite size of 29.4 nm and maximum lattice strain and dislocation density of 0.51% and 18.93 (10¹⁶/m²) respectively has been achieved in alloy C at 20 h of milling. Addition of nano-Y₂O₃ reduces the activation energy for recrystallization of W based alloys. Alloy C compacted at 1 GPa pressure shows enhanced sintered density, hardness, compressive strength and elongation of 95.2%, 9.12 GPa, 1.51 GPa, 19.5% respectively as well as superior wear resistance and oxidation resistance (at 1000 °C) as compared to other W-Mo alloys.     

Sub-micron binderless tungsten carbide sintering behavior under high pressure and high temperature

Pure tungsten carbide (WC) compacts of about 200 nm grain size were prepared by high pressure and high temperature (HPHT) method. The best property sample with high relative density (99.2%), high Vickers hardness (2925 kg·mm^− 2) and high fracture toughness (8.9 MPa·m^1/2) was obtained in the condition of 1500 °C temperature and 5 GPa pressure. By means of scanning electron microscopy (SEM) and transmission electron microscope (TEM) observations, a large number of twins and stacking faults appeared in sintered samples, and the grain size of sintered samples maintained in the initial range. The XRD patterns of bulk samples reveal that there is a phase transition from WC to W₂C with the increasing of temperature. Moreover, the effect of HPHT condition for sintering kinetics, microstructure evolutions, and mechanical properties of the sintered samples were also discussed.     

Preparation of Si3N4-TaC and Si3N4-ZrC composite ceramics and their mechanical properties

Si₃N₄-TaC and Si₃N₄-ZrC composite ceramics with sintering additives were consolidated in the sintering temperature range of 1500–1600 °C using a resistance-heated hot-pressing technique. The addition of 20–40 mol% carbide improved the sinterability of the ceramics. The ceramics were densely sintered under 0–40 mol% TaC or ZrC at 1500 °C, 0–80 mol% TaC at 1600 °C, and 0–60 mol% ZrC at 1600 °C. In ceramics sintered at 1500 °C, the proportion of α-Si₃N₄ was larger than that of β-SiAlON; α-Si₃N₄ transformed mostly to β-SiAlON at 1600 °C. Carbide addition was effective in inhibiting α-Si₃N₄-to-β-SiAlON phase transformation. Young's modulus for the dense Si₃N₄-TaC and Si₃N₄-ZrC ceramics increased with the carbide amount, and the hardness of dense Si₃N₄-ZrC and Si₃N₄-TaC ceramics increased from 14 GPa to 17 GPa with increasing α-Si₃N₄ content. Dense Si₃N₄-TaC and Si₃N₄-ZrC ceramics, with larger quantities of α-Si₃N₄ sintered at 1500 °C, exhibited high hardness; the fracture toughness of these ceramics decreased with increasing α-Si₃N₄ proportion. Both the hardness and fracture toughness of the dense Si₃N₄-TaC and Si₃N₄-ZrC ceramics were strongly related to the proportion of α-Si₃N₄ in the sintered body.     

Microstructure and mechanical properties of bulk nanocrystalline Al–Fe alloy processed by mechanical alloying and spark plasma sintering

Nanocrystalline Al–5 at.% Fe alloy powders produced by mechanical alloying were consolidated by spark plasma sintering. The sintered sample showed high strength >1000 MPa with a large plastic strain of 15% at room temperature and 500 MPa at 350 °C. Microstructure characterizations by transmission electron microscopy and atom probe tomography revealed that the sintered samples are composed of α-Al and Al₆Fe nanocrystalline regions with 90 nm in diameter and a minor fraction of Al₁₃Fe₄ phase and coarsened 0.5–1 μm α-Al grains. This bimodally grained feature is attributed to the relatively large plastic strain for the strength level of 1000 MPa at room temperature.     

Synthesis of (Mo1−x–Crx)Si2 nanostructured powders via mechanical alloying and following heat treatment

MoSi₂–CrSi₂ nanocomposite powder was successfully synthesized by ball milling of Mo, Si and Cr elemental powders. Effects of the Cr content, milling time and annealing temperature were studied. X-ray diffraction (XRD) was used to characterize the milled and annealed powders. The morphological and microstructural evolutions were studied by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). High temperature polymorph (HTP) of MoSi₂ begins to form after 50 h of milling and completes after 70 h of milling. MoSi₂–CrSi₂ composite powder was also prepared with a combination of short milling time (50 h) and low temperature annealing (850 °C). Annealing led to the HTP to low temperature polymorph (LTP) transformation of MoSi₂. MoSi₂–CrSi₂ nanocomposite powder with the mean grain size less than 50 nm was obtained at the end of milling. This composite maintained its nanocrystalline nature after annealing. A spherical morphology was procured for 50 h milled powder with 0.25 mole Cr.     

Effect of short carbon fiber addition on pressureless densification and mechanical properties of ZrB2–SiC–Csf nanocomposite

In the present paper, ZrB₂–SiC–C_sf composites were produced by pressureless sintering method. Carbon fiber and SiC nanoparticles with different weight percentages were added to the milled ZrB₂ powder. The mixed powders were formed by hot pressing and cold isostatic press (CIP) and after the pyrolysis, were sintered at 2100 °C and 2150 °C. In order to compare the microstructure and mechanical properties of samples scanning electron microscopy (SEM) equipped with EDS spectroscopy, XRD analysis, hardness and toughness tests were used. The results show that with the increase in weight percentage of carbon fiber, the porosity increases but the hardness, fracture toughness and density decrease. On the other hand, with the increase in weight percentage of SiC nano-particles, the porosity decreases and fracture toughness, hardness and density increase. The results indicate that in an optimal percentage of both additives, the hardness and toughness increase. Additionally, with the increase in sintering temperature, the values of hardness and fracture toughness increase and porosity decreases.     

Synthesis of chromium carbide nanopowders via a microwave heating method

Chromium carbide nanopowders were firstly synthesized via a simple microwave heating technique using nanometer chromic oxide (Cr₂O₃) and nanometer carbon black as raw materials in argon gas atmosphere. The samples were characterized by X-ray diffractometry (XRD), thermogravimetric and differential scanning calorimetry (TG–DSC), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) techniques. The results show that chromium carbide nanopowders with an average crystallite size of 24 nm can be synthesized at 1000 °C for 1 h. The synthesis temperature required by the method is 400 °C lower than those required by the conventional approaches for preparing chromium carbide. SEM and TEM results show that the powders show good dispersion and are mainly composed of spherical or nearly spherical particles with a mean diameter of about 30 nm. The phase transformation sequence during the heat treatment is: Cr₂O₃ → CrO → Cr₇C₃ → Cr₂C → Cr₃C₂.     

Spark plasma sintering of a commercially available granulated zirconia powder: Comparison with hot-pressing

A commercially available granulated TZ3Y powder has been sintered by hot-pressing (HP). The “grain size/relative density” relationship, referred to here as the “sintering path”, has been established for a constant value of the heating rate (25 °C min^?1) and a constant value of the macroscopic applied pressure (100 MPa). It has then been compared to that obtained previously on the same powder but sintered by spark plasma sintering (SPS, heating rate of 50 °C min^?1, same applied macroscopic pressure). By coupling the analysis of a sintering law (derived from creep rate equations) and comparative observations of sintered samples using transmission electron microscopy, a hypothesis about the densification mechanism(s) involved in SPS and HP has been proposed. Slight differences in the densification mechanisms lead to scars in the microstructure that explain the higher total ionic conductivity measured, in the temperature range 300–550 °C, when SPS is used for sintering.     

Synthesis and properties of nanostructured dense LaB6 cathodes by arc plasma and reactive spark plasma sintering

Nanostructured polycrystalline LaB₆ ceramics were prepared by the reactive spark plasma sintering method, using boron nanopowders and LaH₂ powders with a particle size of about 30 nm synthesized by hydrogen dc arc plasma. The reaction mechanism of sintering, crystal structure, microstructure, grain orientations and properties of the materials were investigated using differential scanning calorimetry, X-ray diffraction, Neutron powder diffraction, Raman spectroscopy, transmission electron microscopy and electron backscattered diffraction. It is shown that nanostructured dense LaB₆ with a fibrous texture can be fabricated by SPS at a pressure of 80 MPa and temperature of 1300 °C for 5 min. Compared with the coarse polycrystalline LaB₆ prepared by traditional methods, the nanostructured LaB₆ bulk possesses both higher mechanical and higher thermionic emission properties. The Vickers hardness was 22.3 GPa, the flexural strength was 271.2 MPa and the maximum emission current density was 56.81 A cm^?2 at a cathode temperature of 1600 °C.     

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.     

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.     

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.     

Synthesis of nanocrystalline Bi2Te3 via mechanical alloying

Bi₄₀Te₆₀ thermoelectric compound was fabricated via mechanical milling of bismuth and tellurium as starting materials. Effect of the milling time and heat treatment temperatures were investigated. In order to characterize the ball milled powders, the X-ray diffraction (XRD) was used. Thermal behavior of the mechanically alloyed powders was studied by differential thermal analysis (DTA). The morphological evolutions were studied by scanning electron microscopy (SEM). Results showed that the nanocrystalline Bi₂Te₃ compound was formed after 5 h of milling. Further milling (25 h) and heating to 500 °C showed that the synthesized phase was stable during these conditions. Nanocrystalline Bi₂Te₃ with 9–10 nm mean grain size and flaky morphology (lamellar structure) was obtained at the end of milling.     

Effect of sintering temperature on the structure and magnetic properties of SmCo5/Fe nanocomposite magnets prepared by spark plasma sintering

Highly dense SmCo₅/Fe nanocomposite bulk magnets were prepared by spark plasma sintering of magnetic field-milled SmCo₅/Fe nanocrsytalline powders. The sintering experiments were conducted with varying temperatures of 973–1123 K. The resultant bulk materials had densities of 85–98% and mean grain sizes of 17–30 nm. The SEM analysis showed that the bulk samples prepared at higher sintering temperature exhibited dense and uniform microstructure. The XRD studies in complement with energy dispersive X-ray analysis revealed that the bulk magnets sintered at or above 1073 K exhibited Sm(Co,Fe)₅ as main phase, along with other secondary phases such as Sm₂(Co,Fe)₁₇ and α-Fe(Co). A single-phase behavior with high remanence ratios (0.67–0.77) for the nanocomposite magnets was demonstrated by the magnetic measurements. In the present study, the sintering temperature of 1073 K was found to be optimum in achieving relatively high coercivity (8.2 kOe), magnetization (97.5 emu/g) and energy product (278.7 kJ/m³) for the SmCo₅/Fe nanocomposite bulk magnets.     

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.