Reactive sintering cBN-Ti-Al composites by spark plasma sintering

When synthesizing polycrystalline cubic boron nitride (PcBN) at normal pressure, cBN had a trend of hexagonal transformation, which reduces the hardness and strength of PcBN. The cBN-Ti-Al composite was prepared by spark plasma sintering with introducing Ti and Al to absorb hexagonal boron nitride (hBN) transformed from cBN. By the results of X-ray diffraction (XRD), Ti and Al reacted with BN and forming TiN, TiB₂, and AlN, which combined cBN as the binder by chemical bonding. The mechanical properties of the prepared composite increased as the increment of sintering temperature. The threshold temperature for preparing composite without hBN phase was at 1400 °C. The composite with optimal mechanical properties was prepared at 1400 °C, and the relative density, the bending strength, hardness, and fracture toughness were 98.9 ± 0.1%, 390.7 ± 4.4 MPa, 14.1 ± 0.5 GPa, and 7.6 ± 0.1 MPa·m^0.5, respectively.     

Effect of milling type on the microstructural and mechanical properties of W-Ni-ZrC-Y2O3 composites

This study reports the effect of milling type on the microstructural, physical and mechanical properties of the W-Ni-ZrC-Y₂O₃ composites. Powder blends having the composition of W-1 wt% Ni-2 wt% ZrC-1 wt% Y₂O₃ were milled at room temperature for 12 h using a Spex™ 8000D Mixer/Mill or cryomilled in the presence of externally circulated liquid nitrogen for 10 min using a Spex™ 6870 Freezer/Mill or sequentially milled at room temperature and cryogenic condition. Then, powders were compacted in a hydraulic press under a uniaxial pressure of 400 MPa and green bodies were sintered at 1400 °C for 1 h under Ar/H₂ atmosphere. Phase and microstructural characterization of the milled powders and sintered samples were performed using X-ray diffractometer (XRD), TOPAS software, scanning electron microscope/energy dispersive spectrometer (SEM/EDS), X-ray fluorescence (XRF) spectrometer and particle size analyzer (PSA). Archimedes density and Vickers microhardness measurements, and sliding wear tests were also conducted on the sintered samples. The results showed that sequential milling enables the lowest average particle size (214.90 nm) and it is effective in inhibiting W grain coarsening during sintering. The cryomilled and sintered composite yielded a lower hardness value (5.80±0.23 GPa) and higher wear volume loss value (149.42 µm³) than that of the sintered sample after room temperature milling (6.66±0.39 GPa; 102.50 µm³). However, the sequentially milled and sintered sample had the highest relative density and microhardness values of 95.09% and 7.16±0.59 GPa and the lowest wear volume loss value of 66.0 µm³.     

Investigation of the structural and mechanical properties of micro-/nano-sized Al2O3 and cBN composites prepared by spark plasma sintering

Alumina-cubic boron nitride (cBN) composites were prepared using the spark plasma sintering (SPS) technique. Alpha-alumina powders with particle sizes of ∼15 µm and ∼150 nm were used as the matrix while cBN particles with and without nickel coating were used as reinforcement agents. The amount of both coated and uncoated cBN reinforcements for each type of matrix was varied between 10 to 30 wt%. The powder materials were sintered at a temperature of 1400 °C under a constant uniaxial pressure of 50 MPa. We studied the effect of the size of the starting alumina powder particles, as well as the effect of the nickel coating, on the phase transformation from cBN to hBN (hexagonal boron nitride) and on the thermo-mechanical properties of the composites. In contrast to micro-sized alumina, utilization of nano-sized alumina as the starting powder was observed to have played a pivotal role in preventing the cBN-to-hBN transformation. The composites prepared using nano-sized alumina reinforced with nickel-coated 30 wt% cBN showed the highest relative density of 99% along with the highest Vickers hardness (H_v2) value of 29 GPa. Because the compositions made with micro-sized alumina underwent the phase transformation from cBN to hBN, their relative densification as well as hardness values were relatively low (20.9–22.8 GPa). However, the nickel coating on the cBN reinforcement particles hindered the cBN-to-hBN transformation in the micro-sized alumina matrix, resulting in improved hardness values of up to 24.64 GPa.     

The influence of hBN crystallinity and additive Lithium hydride on cBN synthesis in Li3N–hBN system

In this paper, the influence of hBN crystallinity and additive Lithium hydride (LiH) on cBN synthesis with Lithium nitride (Li₃N) as catalyst was investigated under the pressure of 4.5–5 GPa and the temperature of 1500–1700 °C. hBN with different crystallinities was obtained by the same hBN. Some were explored to high pressure and high temperature, and others were subjected to heat treatment with alkali. X-ray diffraction (XRD), Raman spectroscopy and X-ray photoelectronic spectroscopy (XPS) were used to characterize the property of the starting materials. The synthesized samples were observed by optical microscopy (OM). The results indicated that besides the crystallinity of hBN, which is a general parameter for controlling the structural quality of hBN powders, some other factors such as the content of B⁺ at the surface of hBN and additive LiH all strongly influence the synthesis of cBN.     

Processing and properties of polycrystalline cubic boron nitride reinforced by SiC whiskers

Dense polycrystalline cBN (PcBN)–SiCw composites were fabricated by a two-step method: First, SiO₂ was coated on the surface of cubic boron nitride (cBN) particles by the sol-gel method. Then, silicon carbide whisker (SiC_w)- coated cBN powder was prepared by carbon thermal reaction between SiO₂ and carbon powders at 1500°C for 2 hour. Then, cBN–SiC_w complex powders were sintered by high-pressure and high-temperature sintering technology using Al, B, and C as sintering additives. The phase compositions and microstructures of cBN–SiC_w composites were investigated by X-ray diffraction and scanning electron microscopy, respectively. It was found that the SiC_w and Al₃BC₃ had been fabricated by in situ reaction, which cannot only promote densification but also improve mechanical properties. The relative density of PcBN composites increased from 96.3% to 99.4% with increasing SiC_w contents from 5 to 20 wt%. Meanwhile, the Vickers hardness, fracture toughness and flexural strength of as-obtained composites exhibited a similar trend as that of relative density. The composite contained 20 wt% of SiC_w exhibited the highest Vickers hardness and fracture toughness of 42.7 ± 1.9 GPa and 6.52 ± 0.21 MPa•m^1/2, respectively. At the same time, the flexural strength reached 406 ± 21 MPa.     

High pressure synthesis of tungsten carbide–cubic boron nitride (WC–cBN) composites: Effect of thermodynamic condition and cBN volume fraction on their microstructure and properties

Tungsten carbide (WC) with different amounts of Cubic boron nitride (cBN) were synthesized by High Pressure-High Temperature (HPHT) method. The mapping correlation between thermodynamic condition, cBN addition, and microstructure, mechanical properties of WC–cBN composites was established and analyzed by response surface methodology. The main factors affecting the properties of composites were identified by ANOVA. The optimum thermodynamic condition was calculated. It was found that a minor phase transformation of cBN into the low-hardness hBN occurred at a temperature of 1300 °C and intensified at 1500 °C. The homogeneously dispersed cBN particles in the WC matrix promoted an improvement of hardness and fracture toughness, but the phase transition of cBN and its truss effect can dramatically reduce the mechanical properties. The Vickers hardness and fracture toughness of the well-sintered WC-cBN bulks reached a high value of 34 GPa and 13.6 MPa·m^1/2, which are improved by 17% and 52% respectively compared with the pure WC samples sintered under similar high-pressure level.     

Effects of additive LiF on the synthesis of cBN in the system of Li3N–hBN at HPHT

High-quality cBN single crystals were successfully synthesized in the system of Li₃N–hBN with additive LiF at high pressure and high temperature (HPHT). The lowest synthetic conditions of cBN decreased to 4.6 GPa, 1320 °C by employing 3 wt.% LiF, and it didn't change anymore though more than 3 wt.% LiF had been added. The quality of cBN crystals improved markedly. The cBN crystals and other products were examined by X-Ray diffraction and scanning electron microscopy. The X-Ray analysis reveals that the “graphitization index” (GI) of hBN increased by adding 3 wt.% LiF into the system of Li₃N–hBN at HPHT. The SEM photographs show that different growth steps were formed on the cBN crystal surface in systems of Li₃N–hBN and Li₃N–LiF–hBN, respectively.     

First principles calculations and synthesis of multi-phase (HfTiWZr)B2 high entropy diboride ceramics: Microstructural,mechanical and thermal characterization

First principles calculations were conducted on (HfTiWZr)B₂ high entropy diboride (HEB) composition, which indicated a low formation energy and promising mechanical properties. The (HfTiWZr)B₂ HEBs were synthesized from the constituent borides and elemental boron powders via high energy ball milling and spark plasma sintering. X-ray diffraction analyses revealed two main phases for the sintered samples: AlB₂ structured HEB phase and W-rich secondary phase. To investigate the performance of multi-phase microstructures containing a significant percentage of the HEB phase was focused in this study. The highest microhardness, nanohardness, and lowest wear volume loss were obtained for the 10 h milled and 2050 °C sintered sample as 24.34 ± 1.99 GPa, 32.8 ± 1.9 GPa and 1.41 ± 0.07 × 10^?4 mm³, respectively. Thermal conductivity measurements revealed that these multi-phase HEBs have low values varied between 15 and 23 W/mK. Thermal gravimetry measurements showed their mass gains below 2% at 1200 °C.     

cBN-Al2O3 composites in NaCl environment under high pressure and high temperature conditions

A series of experiments of cubic boron nitride (cBN)-Al₂O₃ composites was conducted in NaCl environment under a pressure of 5 GPa at 1200–1650 °C using a Chinese multi-anvil high-pressure apparatus. The oxidation resistance of cBN-Al₂O₃ composites reached 1300 °C, which was 200 °C higher than that of raw cBN powder. The porosity was estimated by the content of NaCl impurities in cBN-Al₂O₃ composites. The content of NaCl impurity increases with increasing temperature and decreases with increasing Al₂O₃ level under high pressure and high temperature conditions. cBN+30 vol% Al₂O₃ sintered at 5 GPa and 1200 °C shows no NaCl impurity, and the Vickers hardness of the sample is 21.6 GPa which is half of cBN+10 vol% Al.     

Microstructure and properties of NiAl/TiC composite synthesized by spark plasma sintering of mechanically activated elemental powders

In this study, NiAl/TiC_0.95 composite was synthesized by reactive spark plasma sintering of mechanically activated elemental powders. The microstructure and properties of activated powders and sintered samples were evaluated. The elemental powders were milled after different milling times and as-mixed and 10 h milled powder mixtures were sintered by the reactive spark plasma sintering method. The phase and the microstructure changes were evaluated by x-ray diffraction and scanning electron microscopy/energy dispersive spectroscopy, respectively. The XRD pattern of 0 h milled powder after sintering showed that Ni₃Al, Ni₂Al₃ beside NiAl and TiC_0.75 formed. While after the sintering of 10 h mechanically activated powder, the Ni₃Al and Ni₂Al₃ were eliminated and NiAl remained with TiC_0.95. The nanoindentation result of the SPSed sample showed a hardness of 12.2 ± 0.1 GPa with an elastic modulus of 25.0 ± 0.5 GPa.     

Preparation of mullite from alumina/aluminum nitrate and kaolin clay through spark plasma sintering process

In the present study, the in-situ synthesized mullite has been prepared successfully by mixing kaolinite with alumina and aluminum nitrate nonahydrate (ANN) powders through high energy milling followed by spark plasma sintering (SPS). Using a high-energy ball-mill, the stoichiometric compositions of the starting powders, considering their final transformation to Al₂O₃ and SiO₂, have been mixed. The SPS process has been performed at 1400 and 1375?°C for the specimens containing Al₂O₃ and ANN, respectively. XRD patterns of the milled powders after 30?h showed the formation of quartz from kaolinite for both starting batches. The displacement-temperature-time (DTT) curves and the corresponded vacuum changes indicated the dehydration and phase transformation of ANN and kaolinite at different stages of the sintering process. The XRD patterns of the sintered samples revealed the formation of mullite alongside un-reacted Al₂O₃ and crystobalite for the batches containing Al₂O₃ and ANN, respectively. The results of the physical and mechanical properties tests showed higher amounts of bending strength (397?±?18?MPa), Vickers hardness (16.32?±?0.21?GPa) and fracture toughness (3.81?±?0.24?MPa?m^?1/2) alongside a lower porosity (0.070?±?0.02%) for the prepared sample containing Al₂O₃, than those of the sample containing ANN.     

Quantitative linear correlations between the cBN synthesis parameters and the structural features of the hBN precursor

Seven selected hBN powders previously characterized by X-ray diffraction were subject to cBN synthesis tests at 1500 °C and 5.2GP using MgB₂ as a solvent-catalyst. Attempts have been made to establish quantitative linear correlations involving the conversion yield and the kinetic parameters (nucleation rate and linear growth rate) obtained in the cBN synthesis and the X-ray revealed features of the hBN precursor to disclose definite hereditary influences in the hBN → cBN conversion. The aspect ratio of the hBN crystallites seems to have an influence on the conversion yield and nucleation rate only if considered jointly with the graphitizing index and special lattice defects such as nanoarches and mid-plane point defects of chemical origin. The model of Sung and Tai for the catalytic synthesis of diamond was used to explain the obtained correlations.     

Micro-sized polycrystalline cubic boron nitride with properties comparable to nanocrystalline counterparts

High-performance polycrystalline cubic boron nitride (PcBN) was sintered without binders at 1500 °C in a pressure range from 11 to 15 GPa using commercial micrometre cubic boron nitride (cBN) with a diameter of approximately 2–4 μm. The results demonstrated that the sample sintered at 12 GPa and 1500 °C had the best mechanical properties and thermal stability. Its average Vickers hardness, fracture toughness, and thermal stability was 63 GPa, 15 MPa m^1/2, and 1315 °C, respectively. The considerable improvement in the mechanical properties was mostly attributed to the high compactness, close bonding between grains, and the sample's internal defect structures. The relatively small specific surface area of the micron grains provides an advantage due to its high thermal stability. The amorphous regions observed in the sample's local areas may provide a new strengthening mechanism under high pressure and temperature.     

Highly Dense Amorphous Si2BC3N Monoliths with Excellent Mechanical Properties Prepared by High Pressure Sintering

The fabrication of dense amorphous Si–B–C–N monoliths is a processing challenge given that it is hard to avoid crystallization at the sintering temperatures needed to attain full density up to 1900°C for conventional hot pressing and SPS methods. We report here successful densification of amorphous Si₂BC₃N monoliths achieved by heating at 1100°C and 5 GPa. The relationships between microstructure, types of chemical bonding, and mechanical properties were investigated. The strong amorphous 3‐D networks of Si–C, C–B, C‐N (sp³), N‐B (sp³), and C–B–N bonds provide high densities at high applied pressure and thus amorphous Si₂BC₃N monoliths show high hardness of 29.4 GPa and elastic modulus of 291 GPa. The amorphous structure is lost with crystallization of β‐SiC and BN(C) reducing contributions from Si–C, C‐N (sp³), and C–B–N bond networks thereby decreasing mechanical properties.     

High pressure sintering of cubic boron nitride compacts with Al and AlN

Cubic boron nitride (cBN) compacts, using 15 wt.% Al and 20 wt.% AlN respectively as additives, were sintered in the temperature range of 1300–1700 °C for 20 min under high pressure of 5.0 GPa. The hardness, microstructure, phase composition and cutting performance of the high pressure sintered samples were investigated. A liquid phase sintering and reaction process was observed in the cBN–Al system, which leads to the formation of AlN and AlB₂ as confirmed by X-ray diffraction (XRD) in the sintered compacts. Scanning electron microscopy (SEM) analysis shows that the samples have a homogeneous microstructure. The hardness decreases with increase of sintering temperature and reaches the highest Vickers hardness of 32.1 GPa at 1350 °C. While in the cBN–AlN system, AlN grains agglomerate heavily at temperature below ~ 1500 °C. As the sintering temperature increasing, Al₂O₃ appeared and the AlN agglomeration disappeared gradually. A highest cBN–AlN composite hardness of 29 GPa was achieved when sintered at 1600 °C. Turning tests showed that cBN compacts with 15 wt.% Al as the additive has a longer tool life as compared to that with 20 wt.% AlN. Our results indicated that cBN–Al system is more favourable to obtain well-sintered cBN compacts comparing with the cBN–AlN system.     

Crystallization processes,compressibility, sinterability and mechanical properties of La-monazite-type ceramics

Lanthanide orthophosphate ceramics with monazite structure gained broad interest for several industrial applications. The crystallization processes, compressibility and sinterability of monazite-type lanthanum orthophosphate powder hydrothermally synthesized at 200 °C as well as mechanical properties of the sintered compacts were investigated. Based on a combination of thermo- and surface area analyses, X-ray diffraction as well as scanning electron microscopy studies it was found that the crystallization process occurs at ∼500 °C and the final crystallization of LaPO₄ monoclinic phase takes place at 1400 °C. The sintered pellets are characterized by a density of 98% of theoretical density, a Vickers hardness of 5.7 ± 0.1 GPa and fracture toughness of 1.4 ± 0.1 MPa m^0.5.     

Highly Transparent Mg0.27Al2.58O3.73N0.27 Ceramic Prepared by Pressureless Sintering

A novel aluminum magnesium oxynitride transparent ceramic with the chemical formula Mg_0.27Al_2.58O_3.73N_0.27 was firstly prepared by pressureless sintering of fine single‐phase powders at 1875°C for 24 h in nitrogen atmosphere. The ceramic was fully dense with the average grain size of 57.5 μm. The sample showed excellent in‐line transmission from the visible to middle‐infrared wavelengths with the maximum transmittance of 84%, which could be attributed to rare pores in the sintering body. The material also exhibited good mechanical properties of Vickers hardness (13.39 ± 0.18 GPa), fracture toughness (2.46 ± 0.3 MPa/m^1/2), and flexural strength (274 ± 6 MPa).     

Influence of dry- and wet-milled LLZTO particles on the sintered pellets

A Ta-doped Li₇La₃Zr₂O₁₂ (LLZTO) solid electrolyte is a promising candidate for all-solid-state lithium battery due to its high ionic conductivity and stability against lithium metal. In this work, physicochemical properties of both dry- and wet-milled LLZTO particles were investigated. Based on X-ray diffraction, Fourier transform–infrared, thermogravimetric analysis, and scanning electron microscopy results, it was confirmed that highly reactive LLZTO powder prepared in dry milling conditions exhibited faster size reduction, rougher surface morphology, fewer surface impurities, and less agglomerated particles, in contrast to those in wet milling conditions. Sintering these dry-milled powders at 1320°C for 10 min in the air via solid-state reaction produced dense ceramic pellets with a relative density of 97.4%. The room-temperature ionic conductivity for LLZTO pellet via the dry milling was determined to be 6.94 × 10⁻⁴ S cm⁻¹. Li–sulfur batteries based on the pellets showed an initial discharge capacity of 1301 mA h g⁻¹ and a coulombic efficiency of 99.82% when cycled at room temperature. The effect of the milled powder on the sintered pellets was discussed in terms of boundary mobility, pore mobility, and morphology.     

Densification and mechanical properties of cBN–TiN–TiB2 composites prepared by spark plasma sintering of SiO2-coated cBN powder

cBN–TiN–TiB₂ composites were fabricated by spark plasma sintering at 1773–1973 K using cubic boron nitride (cBN) and SiO₂-coated cBN (cBN(SiO₂)) powders. The effect of SiO₂ coating, cBN content and sintering temperature on the phase composition, densification and mechanical properties of the composites was investigated. SiO₂ coating on cBN powder retarded the phase transformation of cBN in the composites up to 1873 K and facilitated viscous sintering that promoted the densification of the composites. Sintering at 1873 K, without the SiO₂ coating, caused the relative density and Vickers hardness of the composite to linearly decrease from 96.2% to 79.8% and from 25.3 to 4.4 GPa, respectively, whereas the cBN(SiO₂)–TiN–TiB₂ composites maintained high relative density (91.0–96.2%) and Vickers hardness (17.9–21.0 GPa) up to 50 vol% cBN. The cBN(SiO₂)–TiN–TiB₂ composites had high thermal conductivity (60 W m⁻¹ K⁻¹ at room temperature) comparable to the TiN–TiB₂ binary composite.     

Microstructure and properties of Al2O3–TiC nanocomposites fabricated by spark plasma sintering from high-energy ball milled reactants

In situ synthesis of Al₂O₃–TiC nanocomposite powders from a mixture of titanium, graphite, and Al₂O₃ powders by high-energy ball milling (HEBM) and its consolidation through spark plasma sintering (SPS) were investigated. After being milled for 25 h at ambient temperature, the powder mixtures were mainly composed of homogeneous nanosized Al₂O₃ particle and amorphous TiC solid solution. The relative density of the samples consolidated by SPS technique in vacuum at 1480 °C for 4 min reached 99.2%. The final products exhibited very fine microstructure, and the grain sizes of Al₂O₃ and TiC were about 400 nm and 200 nm, respectively, with a flexure strength of 944 ± 21 MPa, Vickers hardness 21.0 ± 0.3 GPa, fracture toughness 3.87 ± 0.2 MPa m^1/2, and electrical conductivity 1.2787 × 10⁵ S m⁻¹.