Scratch behavior of boron nitride nanotube/boron nitride nanoplatelet hybrid reinforced ZrB2-SiC composites

Spherical instrumented scratch behavior of ZrB₂-SiC composites with and without hybrid boron nitride nanotubes (BNNTs) and boron nitride nanoplatelets (BNNPs) was investigated in this research. Typical brittle fracture such as microcracks both in and beyond the residual groove and grain dislodgement was observed in ZrB₂-SiC composite, while hybrid BN nanofiller reinforced ZrB₂-SiC composite exhibited predominantly ductile deformation. The peculiar three-dimensional hybrid structure in which BNNPs retain their high specific surface area and de-bundled BNNTs extend as tentacles contributes to the improved tolerance to brittle damage. Additionally, easier grain sliding due to BN hybrid nanofillers located at grain boundaries and these BN hybrid nanofillers attached on the scratch surface would provide significant self-lubricating effect to reduce lateral force during scratch and to alleviate contact damage.     

Wear resistant boron carbide compacts produced by pressureless sintering

Boron carbide compacts were produced by pressureless sintering at 2200 °C/2 h and 2250 °C/2 h in Ar atmosphere, using a starting powder with a particle size smaller than 3 µm. Effects of carbon addition (3.5 wt%) and methanol washing of the starting powder were investigated on the densification, Vickers hardness, and micro-abrasive wear resistance of the samples. The removal of oxide phases by methanol washing allowed the production, with no sintering additive, of highly densified (93.6% of theoretical density), hard (25.4 GPa), and highly wear resistant (wear coefficient =2.9×10^–14 m³/N.m) boron carbide compacts sintered at 2250 °C. This optimized combination of properties was a consequence of a reduced grain growth without the deleterious effects associated to the carbon addition. Methanol washing of the starting powder is a simple and general approach to produce, without additives, high quality, wear resistant boron carbide compacts by pressureless sintering.     

On the low-temperature threshold for cubic boron nitride formation in energetic film deposition

The sharp threshold in substrate temperature below which cubic boron nitride (cBN) cannot be formed in energetic film-deposition processes was investigated. We found that cBN could be synthesized below the threshold temperature on top of cBN that had been previously formed above the threshold temperature. That the initial nucleation of cBN is more strongly dependent on temperature than its subsequent growth is suggested. How the structure of the sp²-bonded BN that accompanied cBN growth changed with temperature was also investigated. Lowering the substrate temperature decreased the local ordering within the graphitic planes, and below the threshold temperature the separation of the graphitic planes increased dramatically. How these structural changes may influence the nucleation of cBN is discussed.     

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.     

Cubic boron nitride films for industrial applications

The effects of kinetic energy, chemical nature of substrates and temperature on the synthesis of cBN films are explored to obtain cBN films with industrial quality. Carbon including amorphous carbon, nanocrystalline and polycrystalline diamond enables deposition of stable, thick and adherent cBN films with characteristic Raman signature. Although temperature has been designated as an unimportant parameter, the deposition at higher temperatures yields higher quality of cBN films. The higher temperature (800 °C) was also employed at cBN deposition on diamond coated tungsten carbide (WC) cutting inserts using plasma enhanced chemical vapor deposition (PECVD). The quality of cBN films grown by PECVD significantly overcomes that prepared by physical vapor deposition (PVD) which is affected in large extent by the lower kinetic energies of particles used in PECVD. The low kinetic energy of particles induces surface growth mechanism which differs from the growth models previously proposed.     

Recrystallization behaviour of cubic boron nitride under high pressure

The recrystallization behaviour of micron-sized cubic boron nitride (cBN) was studied by analysing the grain size and morphology of samples treated at 8−16 GPa/1500–2200 °C. The results show that the recrystallization temperature of cBN under a pressure of 8 GPa is approximately 1650 °C and increases by approximately 100 °C with every 2 GPa increase in pressure. Once grain recrystallization starts, the grains grow abnormally quickly as the temperature rises, and the strengthening effects of grain refinement and defect structure are greatly weakened. The recrystallization behaviour of cBN at high pressure is helpful to understand the sintering mechanism and control the microstructure and mechanical properties of sintered polycrystalline cBN compacts. In addition, the melting curve for cBN under high pressure is inferred according to the empirical relationship between recrystallization temperature and melting temperature, and the phase diagram for boron nitride is revised based on this new melting curve.     

Coarsening of boron carbide grains during the infiltration of porous boron carbide preforms by molten silicon

This work investigates the coarsening of boron carbide grains during the infiltration of porous boron carbide preforms by molten silicon with respect to fabrication of reaction-bonded boron carbide ceramics. Experimental results reveal that the shape of boron carbide grains evolve from the irregular shape to faceted shape due to dissolution-precipitation during infiltration. For infiltration temperatures below 1750 °C, the boron carbide grains are irregular and exhibit an unimodal size distribution, which can be ascribed to the normal grain growth. The growth of the irregular grains follow a cubic law of diffusion control. In contrast, for infiltration temperatures above 1750 °C, the boron carbide grains become faceted and exhibit a bimodal size distribution, indicative of the typical abnormal grain growth. The abnormal growth of faceted grains is proposed to be controlled by coalescence-enhanced two-dimensional nucleation.     

Catalytic effect of potassium carbonate on carbothermic production of hexagonal boron nitride

Effect of potassium carbonate addition on the carbothermic formation of hexagonal boron nitride (hBN) was investigated by keeping the K₂CO₃ added B₂O₃+C mixtures in nitrogen atmosphere at 1400 °C for 40–160 min. K₂CO₃ amount was varied in the range of 10–60 wt% of the B₂O₃+C mixture. Products were subjected to XRD and quantitative analyses, SEM and TEM observations, and particle size measurement. Amount of hBN increased considerably with K₂CO₃ addition; also particle size and crystallinity improved. Catalytic role of K₂CO₃ was suggested as forming a potassium borate melt in which hBN particles form, in addition to carbothermic formation reaction. Effect of K₂CO₃ on increasing the hBN amount decreased when it was used over 40%. This was attributed to the rapid evaporation of the formed potassium borate liquid.     

Tribological behaviors of polycrystalline cubic boron nitride sliding against silicon nitride in air and vacuum conditions

In order to evaluate the friction and wear properties of polycrystalline cubic boron nitride (PCBN) based on the drilling tools cutting, the ball-on-disk tribological experiments of PCBN sliding against silicon nitride (Si₃N₄) were carried out in air and vacuum conditions. The tribological behaviors were investigated by Scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDS) and Nanomap-D three-dimensional White Light Interferometer. The results demonstrate that the coefficient of friction (CoF) is closely interrelated with the changing tendency of loads, where the CoFs gradually decrease with the growth of the load whether in air or in vacuum on account of a transfer film in air and a change from sliding friction to rolling friction in vacuum. Moreover, the CoF in vacuum condition is invariably greater than that in air under the similar load owing to friction heat. Furthermore, no observable abrasion appears on Si₃N₄ in air while severe abrasive wear is dominant on Si₃N₄ in vacuum. In addition, there is more intense adhesion on PCBN in vacuum than that in air. The reason is that the friction heat is gathered in vacuum condition with a confined environment.     

The effect of boron nitride nanosheets on the mechanical and thermal properties of aluminum nitride ceramics

The boron nitride nanosheets (BNNSs)/aluminum nitride (AlN) composites were prepared by hot press sintering at 1600°C. The microstructure, mechanical properties, and thermal conductivity of the samples were measured, and the effect of adding BNNSs to AlN ceramics on the properties was studied. It is found that the addition of BNNSs can effectively improve the mechanical properties of AlN. When the additional amount is 1 wt%, the bending strength of the sample reaches the maximum value of 456.6 MPa, which is 23.1% higher than that of the AlN sample without BNNSs. The fracture toughness of the sample is 4.47 MPa m^1/2, a 68.7% improvement over the sample without BNNSs. The composites obtained in the experiment have brilliant mechanical properties.     

Catalyzed synthesis of rhombohedral boron nitride in sodium chloride molten salt

Although a variety of methodologies/techniques have been used to prepare h-BN powders with different sizes and purities, only a few methods are reported to synthesize r-BN. In this work, highly crystalline r-BN with a purity of 94 wt% was successfully synthesized in sodium chloride molten salt using Na₂B₄O₇ and Mg powders as starting materials at 1000 °C in nitrogen atmosphere. The sodium (Na) produced by the reaction of Mg and Na₂B₄O₇ has a positive effect on the formation r-BN in the molten salt. The effect of Na as a crystallization promoter to produce crystallized r-BN was demonstrated by heating a mixture of t-BN and Na at 800–1200 °C. The formation, dissolution and evaporation of Na in the melt was discussed. The influence of synthesis temperature on the phase composition and morphology of the final products in the melt was also investigated. The possible formation mechanism of r-BN is proposed.     

Deposition of cubic boron nitride films on diamond-coated WC:Co inserts

Cubic boron nitride (cBN) thin films were deposited on diamond-coated tungsten carbide (WC) cutting inserts using electron cyclotron resonance (ECR) microwave plasma chemical vapor deposition (MPCVD). The effects of gas flow rate and substrate bias on the phase composition and structure of the BN films deposited on diamond surfaces were studied. It was revealed that both the cubic phase formation and the selective etching of hexagonal phase were controlled by modulating the hydrogen and boron trifluoride flow rate ratio. By the trial and error method the gas flow rate ratio and substrate bias voltage were optimized. Moreover the phase composition of the BN film was found to be affected by the thickness of diamond buffer layer and interrelated to the effective substrate bias. The hardness of the resulting cBN films reached the value of 70 GPa. In the synthesized coatings, the diamond beneath renders the best mechanical supporting capacity while the top cBN provides the superior chemical resistance and extreme hardness. The cBN/diamond bilayers deposited on WC inserts may serve as universal tool coatings for machining steels and other ferrous metals.     

Modification of hexagonal boron nitride nanoparticles with fluorosilane

Surfaces of hexagonal boron nitride (hBN) nanoparticles were modified with perfluorooctyl-triethoxysilane (FTS). Experiments were performed for 40–120 min in 70–150 °C range with FTS/hBN weight ratio in the range of 0.5–1.5. The products were analyzed by FT-IR, TGA, FESEM, HRTEM and EDX. Results of FT-IR analyses indicated that modification takes place in 80 min at 150 °C under reflux with a FTS/hBN ratio of 1.5. Presence of FTS on hBN nanoparticles was confirmed by the weight losses in TGA, and by TEM, TEM-EDX analyses.     

Joining interface and compressive strength of brazed cubic boron nitride grains with Ag-Cu-Ti/TiX composite fillers

Ag-Cu-Ti/TiX (TiX=TiB₂, TiN or TiC) composite filler materials, instead of pure Ag-Cu-Ti alloy, were developed to improve the comprehensive mechanical performance of brazed joints of cubic boron nitride (CBN) grains/bonding layer/steel matrix. This article mainly concerns the effects of TiX addition on the joining interface and compressive strength of brazed CBN grains. The results demonstrate that, due to the variation of chemical activity of Ti atoms induced by TiX addition into the brazing system, the brazing reactions, especially chemical resultants produced at the joining interface between CBN grain and Ag-Cu-Ti alloy, are restrained to some extents. In general, the TiN particles show the greatest suppression effect on the brazing resultants, while the TiC particles have the weakest effect, and TiB₂ particles have the medium effect. The optimum reinforcement of the composite filler is finally determined as the TiB₂ particles with the content of 8 wt%, with which the average compressive strength of brazed CBN grains reaches 15 N, which is nearly the same high as that of original CBN grains.     

Cubic boron nitride film residual compressive stress relaxation by post annealing

The authors demonstrate that the residual compressive stress in cubic boron nitride films could be relaxed by 1500 K post annealing in H₂ atmosphere. According to the IR peak shifting, approximately 4.5 GPa stress was relaxed after 4 hours annealing. Thus film adhesion was improved significantly, cubic boron nitride films with a cubic phase concentration of 90% (vol%) and a thickness of more than 200 nm showed excellent stability and no delaminations were observed even after annealing for over 30 months in the open air, while films without annealing delaminated from substrates within 1 week. Moreover, the relaxation of the compressive stress is accompanied with cubic boron nitride d (111) interplanar distance broadening and corresponding IR peak intensities increasing.     

Hybrid CO2 laser waterjet heat (LWH) treatment of bindered boron nitride composites with hardness improvement

Boron nitride (BN) material is chemically and thermally stable which makes it desirable for high speed machining in demanding chemical and thermal environments. Although the hardness of BN material is well below that of single polycrystalline diamond (PCD), a laser waterjet heat (LWH) treatment process provides a new potential approach to achieve hardness values that are comparable to diamond hardness. This study investigates the hardness change of LWH-treated bindered cBN/TiN and cBN/AlN composites. Results indicate that measured hardness increase is dependent on the laser beam pass and the distance from the beam center.     

Growth of cubic boron nitride films by ibad and triode sputtering: development of intrinsic stress

Two methods are employed to evidenced the stress behavior in c-BN films. On the one hand, in depth stress profile of c-BN film, deposited by ion beam assisted evaporation, was performed by recording infrared spectra and substrate curvature after reactive ion etching (RIE) steps. It shows a peak of stress up to −17 GPa in the h-BN basal layer and a stress relaxation when the cubic phase appears. On the other hand, dynamic stress profiles of c-BN films deposited by a triode sputtering system, are obtained by recording infrared spectra and substrate curvature after various c-BN deposition times, with the same experimental conditions. Likewise, a peak of stress of −12 GPa is unmistakably observed in the h-BN basal layer followed by a stress release during c-BN nucleation, where an average value of −12 GPa is observed in the c-BN film volume. These results provide a support for the stress model proposed by McKenzie even if along with a minimum stress a high level of densification of the layer is needed.     

用于熔盐体系的氮化硼隔膜Ag/AgCl参比电极性能

介绍了熔盐中常使用的参比电极的性质和存在的问题,制得可用于高温氟化物盐中的氮化硼隔膜Ag/AgCl的参比电极,并对它的性能做了重点研究。确定了AgCl的物质的量分数为2%时较好,且需确保AgCl均匀地混合在LiCl-KCl熔盐中;该种参比电极在制备过程中应注意在各接口处严格密封,以减缓盐的蒸发和导线的腐蚀。对参比电极的性能做了评价,发现活化温度对活化时间有影响;温度变化对电位影响较小;参比电极的极化可逆性均良好;稳定性良好,但是受AgCl浓度、温度及光线的影响,长期使用电极的重现性较好。最终发现该参比电极性质稳定可长期连续（至少28 d）用于熔盐电化学实验中。     

A novel route to superhard nanocrystalline cubic boron nitride: Emulsion detonation and high-pressure high-temperature transformation-assisted consolidation

Synthesizing bulk nanocrystalline materials is challenging since grain growth should be suppressed whereas densification promoted. Here, we demonstrate a novel route to synthesize superhard bulk nanocrystalline cubic boron nitride (cBN), which combines the use of emulsion detonation and high-pressure high-temperature transformation-assisted consolidation. The emulsion detonation process activates BN to possess unique structure and chemistry, i.e. wurtzitic BN nanograins in hexagonal BN matrix with enhanced structural disordering and oxygen impurity, a combination that enhances the nucleation rate of cBN and its densification leading to the formation of bulk nanocrystalline cBN at reduced conditions. The cBN, synthesized at 7.5 GPa and 1800 °C, displayed Vickers hardness values of 50?62 GPa for 5?20 N loads. The findings in the study suggest a feasible solution to synthesize bulk nanocrystalline cBN in a more scalable way, while also providing design insights on how to refine grain growth while enhancing densification to synthesize bulk nanocrystalline materials.     

Synthesis of fine boron nitride powders by combining direct boron nitridation with carbothermic boron oxide reduction

Fine boron nitride powders were synthesized by combining direct nitridation of boron with carbothermic reduction of boron oxide. It has been established that the heat released in direct nitridation of boron can be utilized to carry out carbothermic reduction of boron oxide in a mode of self-sustained combustion. Intermediate gaseous products were found to play a key role the SHS reactions under study. The article is published in the original.