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.     

Electrochemical formation of AlN in molten LiCl-KCl-Li3N systems

Electrochemical formation of aluminum nitride was investigated in molten LiCl-KCl-Li₃N systems at 723 K. When Al was anodically polarized at 1.0 V (versus Li⁺/Li), oxidation of nitride ions proceeded to form adsorbed nitrogen atoms, which reacted with the surface to form AlN film. The obtained nitrided film had a thickness of sub-micron order. The obtained nitrided layer consisted of two regions; the outer layer involving AlN and aluminum oxynitride and the inner layer involving metallic Al and AlN. When Al electrode was anodically polarized at 2.0 V, anodic dissolution of Al electrode occurred to give aluminum ions, which reacted with nitride ions in the melt to produce AlN particles (1-5 μm of diameter) of wurtzite structure.     

Effects of cubic BN addition and phase transformation on hardness of Al2O3-cubic BN composites

The Vickers hardness of dense Al₂O₃-cubic BN (cBN) composites prepared by spark plasma sintering under a moderate pressure of 100 MPa at 1200-1600 °C was investigated at indentation loads of 0.098-19.6 N. The BN grains in the Al₂O₃-BN composite prepared at 1300 °C showed no transformation from the cBN to hBN phase, and the hardness was 59 GPa at 0.098 N. The hardness of the Al₂O₃ matrix in the Al₂O₃-BN composites containing 10-30 vol% cBN prepared at 1300-1400 °C was around 25 GPa at 0.098 N, which was higher than monolithic Al₂O₃ bodies prepared at the same temperatures. The hardness of the Al₂O₃ matrix in the Al₂O₃-BN composites decreased with increasing sintering temperature. The increase in the hardness of the Al₂O₃ matrix may be due to the decrease in the size of Al₂O₃ grains in the Al₂O₃-BN composites owing to the addition of cBN particles and the decrease in sintering temperature. The Meyer exponents of the monolithic Al₂O₃ bodies and Al₂O₃-BN composites were 1.90-1.94 independent of cBN content.     

Kinetics and mechanism of cubic boron nitride formation in the AlN–BN system at 6 GPa

The kinetics of hBN-into-cBN transformation at 6 GPa and 1770, 1880 and 1990 K in the presence of AlN have been studied. The transformation proceeds without liquid phase. It has been established that a limiting stage of the transformation is diffusion of boron and nitrogen atoms in wurtzitic aluminum nitride. Activation energy of the transformation is 170±40 kJ/mol. On the basis of our results we conclude that hexagonal BN dissolves in aluminum nitride solid solution and supersaturates it with respect to cBN, and then cubic boron nitride precipitates from the supersaturated solution of BN in AlN. An AlN–BN system phase diagram is proposed.     

Densification and Phase Transformation of β-SiAlON–Cubic Boron Nitride Composites Prepared by Spark Plasma Sintering

β-SiAlON–cubic boron nitride (cBN) composites were prepared from β-SiAlON and cBN powders at 1600°–1900°C under a pressure of 100 MPa by spark plasma sintering. The effects of cBN content and sintering temperature on densification and phase transformation of the β-SiAlON–cBN composites were studied. When 10–30 vol% cBN was added to β-SiAlON, the shrinkage rate of the compacts increased. The compacts of β-SiAlON–BN composites originally containing 10–30 vol% cBN ceased to shrink at a temperature lower than that of β-SiAlON and the density of the composites increased. The densification of β-SiAlON–BN composites originally containing >40 vol% cBN was suppressed. The phase transformation of cBN to hexagonal BN in the β-SiAlON–BN composite was inhibited to a greater degree than that in the cBN body.     

Tribological study of boron nitride films

Boron nitride (BN) films with different cubic and hexagonal phase compositions were deposited on silicon substrates via diamond interlayers by magnetron sputtering and electron cyclotron resonance microwave plasma chemical vapor deposition. The tribological behaviors of the BN films were investigated systematically using a ball-on-disc tribometer with silicon nitride as the counterpart. Comparison studies were also performed on sintered cubic and hexagonal BN compacts. The influence of phase compositions and surface roughness of BN coatings on their tribological characteristics was studied. The cubic BN (cBN) films showed excellent wear resistance against silicon nitride. The wear rate of the cBN films was estimated to be about 1.0 × 10^?7 mm³/N m by measuring the cross-sectional area of the wear track after the sliding test over a distance of 12 km.     

Investigation on mechanochemical synthesis of Al2O3/BN nanocomposite by aluminothermic reaction

Alpha-alumina–boron nitride (α-Al₂O₃–BN) nanocomposite was synthesized using mixtures of aluminum nitride, boron oxide and pure aluminum as raw materials via mechanochemical process under a low pressure of nitrogen gas (0.5 MPa). The phase transformation and structural evaluation during mechanochemical process were investigated by X-ray diffractometry (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and differential thermal analysis (DTA) techniques. The results indicated that high exothermic reaction of Al–B₂O₃ systems under the nitrogen pressure produced alumina, aluminum nitride (AlN), and aluminum oxynitride (Al₅O₆N) depending on the Al value and milling time, but no trace of boron nitride (BN) phases could be identified. On the other hand, AlN addition as a solid nitrogen source was effective in fabricating in-situ BN phase after 4 h milling process. In Al–B₂O₃–AlN system, the aluminothermic reaction provided sufficient heat for activating reaction between B₂O₃ and AlN to form BN compound. DTA analysis results showed that by increasing the activation time to 3 h, the temperature of both thermite and synthesis reactions significantly decreased and occurred as a one-step reaction. SEM and TEM observations confirmed that the range of particle size was within 100 nm.     

Effects of titanium and aluminum incorporations on the structure of boron nitride thin films

Boron nitride (BN)-based composite thin films have been prepared by ion-beam-assisted deposition (IBAD) employing two electron-beam evaporators. Approximately 3–5 at.% of either Ti or Al was incorporated into the BN composite films. Fourier-transform infra-red (FTIR) spectroscopy was used for phase identification of the BN composite films. The influences of the Ti and Al additions on the cubic phase formation in the BN films are reported. It has been found that Al incorporation has a strong negative effect on cubic BN (cBN) formation. No cubic phase can be obtained under the presently chosen ion-bombardment parameters. However, the disturbance of 3∼5 at.% Ti addition, depending on the preparation conditions for the BN thin films, only shifts the threshold of the ion/atom ratio of the IBAD process, which is required for cBN formation to a higher value. In order to understand the different behaviors of the Ti and Al incorporations, the chemical states of the Ti and Al additions in the BN composite films were examined by X-ray photoelectron spectroscopy (XPS), indicating preferential formation of TiB₂ and AlN, respectively.     

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.     

The effect of SrSO4 and BaSO4 on the corrosion and wetting by molten aluminum alloys of mullite ceramics

In order to improve the corrosion resistance of aluminosilicate refractories by molten aluminum, SrSO₄ and BaSO₄ powders were used. Mullite substrates with and without addition of 20 wt.% SrSO₄ or BaSO₄ were sintered at 1400 °C for 6 h. Corrosion and wetting experiments with molten pure Al and Al–7.5Si were carried out at 900 °C for 24 h and 900 °C for 2 h, respectively. The corrosion layer was thicker in the mullite sample (≥2 mm) than that of the SrSO₄- or BaSO₄-containing mullite samples (<50 μm). The contact angles for mullite samples containing SrSO₄ or BaSO₄ were higher (≈118° and 149°) than those of the mullite sample (≈109° and 127°), with both pure aluminum and Al–7Si alloy. This increase in the contact angle improves the corrosion resistance in mullite samples by means of non-wetting effect.     

High-pressure synthesis of cubic BN using Fe–Mo–Al and Co–Mo–Al alloy solvents

The pressure and temperature regions of cubic BN formation were determined using Fe–Mo–Al and Co–Mo–Al ternary alloys as synthetic solvents of cubic BN. The alloy compositions employed in the present study were (in weight percent) Fe60.14–Mo36.86–Al3 and Co57.6–Mo38.4–Al4. The cubic BN was successfully synthesized at minimum pressure of about 4.4 GPa and temperature of about 1250 °C. Pressure and temperature of cubic BN synthesis were decreased drastically by small amount of Al addition into Fe–Mo or Co–Mo alloy solvents. The growth of cubic BN was started at the interface between the molten alloy and the source hexagonal BN. In the present study, we proposed that Fe–Mo and Co–Mo work as solvent of B and N atoms and Al acts as a nucleation agent of cubic BN.     

Processing of dense nanostructured HAP ceramics by sintering and hot pressing

A nanosized HAP powder was sintered and hot pressed, in order to obtain dense HAP ceramics. In a first series of experiments, the powder was isostatically pressed into uniform green compacts and sintered at temperatures ranging from 1000 °C to 1200 °C in air atmosphere for different times. In a second series, the isostatically pressed green compacts were hot pressed in argon atmosphere at 900 °C, 950 °C and 1000 °C. The SEM micrograph of the sample sintered at 1200 °C for 2 h showed a uniform 3 μm mean grain size dense microstructure. In the case of hot pressed HAP compacts, full dense, translucent nanostructures were obtained having mean grain size below 100 nm and improved mechanical properties. With the grain size decreasing from 3 μm to 50 nm, the fracture toughness of pure HAP ceramics increased from 0.28 MPa m^1/2 to 1.52 MPa m^1/2.     

Mechanical properties of cBN-Al composite materials

The relationship between microstructure and mechanical properties for a wide range of composite materials based on polycrystalline cubic boron nitride and aluminium as a binder phase (PcBN-Al) has been examined. The PcBN-Al composites were made using high-pressure, high-temperature (HPHT) sintering methods, yielding materials with grain sizes of cBN between 2 and 20 μm and an initial amount of Al binder between 15 and 25 vol.%. Hardness ranged between 15 and 40 GPa, while fracture toughness and strength were between 6.4-8.0 MPa m^1/2 and 355-454 MPa, respectively. Fractography was employed to investigate the large scatter in fracture strengths and correlate fracture strength with fracture toughness through the size of the fracture origins.     

PECVD of h-BN and c-BN films from boranedimethylamine as a single source precursor

Boron nitride (BN) thin films have been successfully synthesised via low pressure plasma enhanced chemical vapour deposition (PECVD) by using boranedimethylamine, BH₃NH(CH₃)₂, as a single source precursor in the temperature range 280-550 °C in a nitrogen-argon atmosphere. The plasma power was optimised with the aim of obtaining suitable cubic/hexagonal phase ratios. The annealing of the h-BN films at temperatures up to 1000 °C in a nitrogen atmosphere, at normal pressure, gave rise to a complete transformation into the cubic phase. FTIR measurements provided a suitable method for identifying the structure of BN films. UV-vis spectroscopy was carried out in order to investigate the optical behaviour of the films.     

Effect of time on microstructure and hardness of βSiAlON-cubic boron nitride composites during spark plasma sintering

βSiAlON-cubic boron nitride (cBN) composites were consolidated by spark plasma sintering, and the effects of holding time and heating rate on the phase transformation of cBN and Vickers hardness were investigated. The cBN phase transformed into hexagonal BN (hBN) and the hardness decreased with increasing holding time. The phase transformation from cBN to hBN was retarded by increasing the heating rate, resulting in increased hardness.     

Growth of nitride crystals,BN, AlN and GaN by using a Na flux

Bulk crystals of BN, AlN and GaN were grown by means of Na flux. All these crystals were grown at a temperature of 800°C and a nitrogen pressure of 100 atm, relatively lower than that required by many flux and melt growth methods. High-quality GaN single crystals as large as 0.5 mm were obtained. Furthermore, the oriented GaN crystals were obtained by means of the seeded Na flux method with the addition of oriented AlN (0001) film in the growth ambient. The nucleation of bulk GaN was spatially confined on top of the AlN film and grown with the GaN [0001] axis parallel to the AlN [0001] axis. In addition, the h-BN polycrystals were confirmed by the h-BN (0002) peak of X-ray diffraction (XRD) at 2θ=26.700. A hexagonal grain with a size as large as 2 μm was observed by scanning electron microscopy (SEM). Likewise, AlN crystals were also obtained from Al wires.     

Densification and properties of AlN ceramic bonded carbon

To obtain light and tough materials with high thermal conductivity, AlN ceramic bonded carbon (AlN/CBC) composites were fabricated at temperatures from 1600 to 1900 °C in a short period of 5 min by the spark plasma sintering technique. All AlN/CBCs (20 vol% AlN) have unique microstructures containing carbon particles of 15 μm in average size and continuous AlN boundary layers of 0.5-3 μm in thickness. With an increase in sintering temperature, AlN grains grow and anchor into carbon particles, resulting in the formation of a tight bonding layer. The AlN/CBC sintered at 1900 °C exhibited a light weight (2.34 g/cm³), high bending strength (100 MPa), and high thermal conductivity (170 W/mK).     

Hydrolysis Control of AlN Powders for the Aqueous Processing of Spherical AlN Granules

Spherical granules of aluminum nitride (AlN) with an average particle size of about 50 μm were produced from aqueous suspensions using an AlN powder surface treated against hydrolysis with aluminum dihydrogenphosphate [Al(H₂PO₄)₃]. Two different amounts of Al(H₂PO₄)₃ were tested and the effects of surface treatment and aging time were evaluated by various techniques (XRD, TG‐DTA, zeta potential and pH measurements). The treated powder exhibited antihydrolytic property and good dispersing behavior, enabling the preparation of low‐viscosity and high‐concentration aqueous AlN slurries for freeze granulation. The spherical AlN granules were sintered in a boron nitride (BN) powder bed followed by ultrasonic washing of the AlN granulates/BN mixture to remove BN. The sintered spherical AlN granules present excellent crystallinity and high sphericity as observed from SEM micrographs.     

Correlation of compaction pressure, green density, pore size distribution and sintering temperature of a nano-crystalline 2Y-TZP-Al2O3 composite

Highly sinter-active nano crystalline composite powder of 2 mol% yttria doped tetragonal zirconia polycrystal (2Y-TZP) with 2 wt% alumina was synthesized by co-precipitation method. Crystallization temperature of the amorphous precursor powder, measured from simultaneous thermogravimetric (TG) and differential thermal analysis (DTA) techniques was found to be ∼470 °C. The powder was calcined at different temperatures in the range of 700-1000 °C. XRD patterns of the calcined powders revealed the presence of a single tetragonal phase. Particle size of the calcined powder measured by different techniques (X-ray line broadening, BET surface area and laser scattering technique) indicated an increase in the average particle size with calcination temperature. The study of compaction behaviour revealed the presence of soft agglomerates in the calcined powder. Pore size distribution of the green compacts obtained from a mercury porosimeter was found to be monomodal above a critical pressure. The onset temperature of sintering was found to increase with calcination temperature. Powders calcined at 800 °C and 900 °C had shown better sinterability at 1200 °C owing to the presence of finer pores with a narrow size distribution in the green compacts. Sintering behaviour of the powder calcined at 700 °C was found to be marginally poorer in comparison to the other samples, whereas the powder calcined at 800 °C had demonstrated best densification behaviour, especially when compacted at 300 MPa.     

Reactive synthesis for porous Ti3AlC2 ceramics through TiH2, Al and graphite powders

Porous Ti₃AlC₂ ceramics were fabricated by reactive synthesis. The process of fabrication involved five steps: (i) the pyrolysis of stearic acid at 450 °C; (ii) the decomposition of TiH₂ at 700 °C, which leads to the conversion of TiH₂ to Ti; (iii) the solid–liquid chemical reaction of solid Ti and molten Al at 800–1000 °C, which converts the mixture to Ti–Al compounds; (iv) the newly synthesized Ti–Al compounds that react with surplus Ti and graphite to form ternary carbides and TiC at 1100–1200 °C; and (v) reactive synthesized ternary carbides and TiC that yield porous Ti₃AlC₂ at 1300 °C.