Effect of sintering temperature on the structure and properties of polycrystalline cubic boron nitride prepared by SPS

The polycrystalline cubic boron nitride (PcBN) with Si₃N₄–AlN–Al₂O₃–Y₂O₃ ceramic system as binding agents was prepared by spark plasma sintering (SPS). The starting materials Si₃N₄, AlN, Al₂O₃, Y₂O₃, and cBN in the ratio of 22:14:10:4:50 were heated to a sintering temperature between 1250 °C and 1450 °C at a heating rate of 300 °C/min, with a holding time of 5 min in nitrogen atmosphere. The microstructure, phase constitution, microhardness and fracture toughness of the prepared PcBN were then studied. It was shown that the Si₃N₄–AlN–Al₂O₃–Y₂O₃–cBN polycrystalline materials were densified in a very short sintering time resulting in materials with relative densities of more than 95%. When the sintering temperature increased, the microhardness and fracture toughness of prepared PcBN were also increased. The microhardness of PcBN prepared at 1250–1450 °C was between 28.0 ± 0.5 GPa and 48.0 ± 0.9 GPa, and its fracture toughness K_IC was from 7.5 ± 0.2 MPa m^1/2 to 11.5 ± 0.3 MPa m^1/2. Microstructure study showed that the ceramic-binding agents bonded with cubic boron nitride particles firmly. Our work demonstrated that spark plasma sintering technology could become a novel method for the preparation of PcBN cutting materials.     

Ti (C,N)-based cermets sintered under high pressure

In this study, high pressure and high temperature sintering (HPHT) is adopted in the cermet fabrication process, and the microstructure and mechanical properties of cermets with TiC_0.5N_0.5–15WC–10Mo₂C–5TaC–10Ni–10Co (wt%) sintered under 5 GPa and different temperatures (900–1600 °C) using 6 × 14 MN cubic press are investigated. Results show that the densities of samples can reach up to 7.00 g/cm³. Vickers hardness and fracture toughness of the products are over 1727 HV30 and 7.2 MPa m^1/2 respectively. In addition, the sintering results are compared with the data that obtained from commercial samples which produced via conventional sintering technique. The conclusion is that high density and high hardness cermets can be obtained through HPHT sintering.     

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.     

Self-bonding mechanism of pure polycrystalline cubic boron nitride under high pressure and temperature

Cubic boron nitride (cBN) powders with different grain size were used as a starting material, and the pure polycrystalline cubic boron nitride (PcBN) samples were sintered under the same conditions at 7GPa, 1700 °C, 270 s. Abrasion resistance and compressive strength of sintered pure PcBN samples were tested, and the microstructure was observed and analyzed by SEM, HRTEM, XRD and Raman spectrum. The results show that the particle size of cBN has not only a great influence on microstructure and property of the sintered pure PcBN un-der the same conditions but also influence on the bonding mechanism of the cBN particles. The inner stress of the pure PcBN sintered with the cBN particle size of 10 μm during the high pressure sintering process is about 199–222% higher than that of the sample with the cBN size of 1 μm. The wear ratio and the compressive strength of PcBN samples sintered with 10 μm cBN was increased by 47.7% and 39.7% than that of the sintered sample with 1 μm cBN respectively. The coarser-grained PcBN contains serious deformation and crushing, which can be attributed to the twin boundary and the stacking faults in the samples. As a consequence, the abrasion ratio and compressive strength of the pure PcBN are dramatically increased. It is assumed that self-bonding mechanism generated from plasticity deformation, which is a main bonding mechanism for the high pressure sintering of pure cubic boron nitride.     

新型组装方式烧结纯PcBN材料

为降低合成纯PcBN的温度和压力条件,改进合成腔体内的组装方式:使用横截面积更小的高导电型石墨管,采用双加热管设计和填充大尺寸的白云石.采用新型组装方式,在高温超高压条件下用粒度尺寸为10μm的cBN的微粉合成出纯聚晶立方氮化硼(PcBN)烧结体.利用扫描电子显微镜(SEM)、X射线衍射仪(XRD)对烧结体的微观形貌和...     

Effect of Mo2C additions on the properties of SPS manufactured WC–TiC–Ni cemented carbides

The effect of spark plasma sintering (SPS) on the microstructure and mechanical properties of WC–Co and WC–Ni cemented carbides was studied, and compared to WC–Co produced by liquid phase sintering (LPS). There were finer WC grains with larger Co pools in the spark plasma sintered WC–Co, resulting in higher hardness and slightly lower fracture toughness than the liquid phase sintered WC–Co. The influence of the addition of 0.5–5 wt.%Mo₂C to WC-based cemented carbide containing 6.25 wt.%TiC and 9.3 wt.%Ni prepared by SPS was also studied. This addition improved the wettability between WC and Ni and lead to the improvements of microstructures, resulting in good combinations of hardness, fracture toughness and modulus of elasticity that were comparable to WC–Co based cemented carbides.     

Al添加量对PcBN复合片显微结构和性能的影响

将cBN微粉添加体积分数为5%、10%、15%、20%的Al粉进行高温高压烧结制备出PcBN复合片。利用X射线衍射仪、扫描电子显微镜分析PcBN复合片的物相组成和显微结构,并研究其磨耗比和抗冲击性能。结果表明,PcBN层主要由cBN晶粒和AlN组成。随着Al粉添加量的增加,AlN的体积分数逐步增加,PcBN复合片的性能也发生相应变化。Al粉添加量为体积分数10%时,PcBN复合片的磨耗比为21 842,冲击次数超过100次,综合性能最好。     

Development of ultra-fine-grain binderless cBN tool for precision cutting of ferrous materials

A new cutting tool was developed from ultra-fine-grain (<100 nm), binderless cubic boron nitride (cBN) material fabricated by transforming hexagonal boron nitride to cBN by means of sintering under an ultra-high pressure of 10 GPa at 1800 °C. The cutting edges of the newly developed cBN tool can be made as sharp as those of single-crystal diamond tools. In this experiment, cBN and single-crystal diamond tools of the same shape were compared by precision cutting tests using stainless steel specimens and steel specimens coated with an electroless Ni-P layer. The surface roughness (R_z) of specimen surfaces cut with the cBN tool by means of planing was approximately 100 nm for both the Ni-P-coated steel and stainless steel specimens. Though similar R_z values were obtained for Ni-P layers cut by the cBN and diamond tools, an R_z value exceeding 2000 nm was obtained for stainless steel cut by the diamond tool. High-precision surfaces with R_z values of 50–100 nm were obtained for stainless steel specimens cut with the cBN tool under high-speed milling (942 m/min) conditions. These results indicate that the newly developed cBN tool is useful for the ultra-precision or precision cutting of ferrous materials.     

Microstructure of the cBN/WC6Co composite produced by the pulse plasma sintering (PPS) method

The cBN/WC6Co composite with the relative density of 99.8% and hardness of 2130 HV5 was produced by sintering at a temperature of 1150 °C under a pressure of 100 MPa for 5 min. The composite was sintered using electric pulses generated periodically by discharging a capacitor battery. The constituent phases of the composite, as identified by the NBED method, were the cBN, WC, and Co phases. The HR STEM observations have shown that the interfaces between the individual phases are continuous and no pores or precipitates of other phases can be seen there. Thanks to the specific heating realized by electric pulses, the composite is heated during each current pulse to a temperature of 1950 °C at a rate of 10⁵ °C/s. As a result of these quick changes of the temperature, transient thermal compressive stresses of about 3 GPa are induced in the composite, which results in the grains of the WC composite matrix being refined and defected.     

Effect of tungsten content on microstructure and mechanical properties of PCBN synthesized in cBN-Ti-Al-W system

Polycrystalline cubic boron nitride (PCBN) compacts were prepared using the mixture of cubic BN and Ti-Al-W powders at 5.5 GPa and 1550 °C for 10 min. The influence of different Tungsten (W) content on composition, microstructure, porosity, mechanical property and cutting performance of the PCBN is investigated. The results show that, with the addition of tungsten, the cubic boron nitride (cBN) crystals are connected with each other by the new product phases TiB_2, TiN, Al₃Ti and W₂B under the pressure of 5.5 GPa and the temperature of 1550 °C. The rod-shaped crystals in the PCBN are expanded from the surface portion of the cBN. As the W content increases, the amount of rod-shaped crystals and the length-diameter ratios decrease in the system. When the tungsten content is 6 wt%, PCBN presents the best comprehensive performance and cutting performance, the porosity, the hardness, the flexural strength and the flank wear are 0.55%, 30.71 GPa, 972.3 MPa and 292 μm, respectively.     

Mechanical properties and rapid sintering of nanostructured WC and WC–TiAl3 hard materials by the pulsed current activated heating

Tungsten carbides are primarily used as cutting tools and abrasive materials in the form of composites with a binder metal, such as Co or Ni. However, these binder phases have inferior chemical characteristics compared to the carbide phase and the high cost of Ni or Co. Therefore, low corrosion resistance of the WC–Ni and WC–Co cermets has generated interest in recent years for alternative binder phases. In this study, TiAl₃ was used as a novel binder and consolidated by the pulsed current activated sintering (PCAS) method. Highly dense WC–TiAl₃ with a relative density of up to 99% was obtained within 2 min by PCAS under a pressure of 80 MPa. The method was found to enable not only the rapid densification but also the inhibition of grain growth preserving the nano-scale microstructure. The average grain sizes of the sintered WC and WC–TiAl₃ were lower than 100 nm. The addition of TiAl₃ to WC enhanced the toughness without great decrease of hardness due to crack deflection and decrease of grain size.     

Fragmentation and stress response characteristics of cubic boron nitride under high pressure

Exploring the fragmentation behavior and stress response of cubic boron nitride (cBN) particles under high pressure offers insights into preparing polycrystalline cubic boron nitride (PcBN) with excellent properties. In this study, the distribution characteristics and micro-morphology of cBN particles with different sizes (2 μm, 15 μm and 40 μm) with and without aluminum (Al) binder are investigated using scanning electron microscopy (SEM) and laser particle size distribution instrument after cold compression at pressures up to 10.0 GPa. The results demonstrate that the fragmentation of the cBN particles without Al is more evident than that with Al. Moreover, the stress distribution among cBN grains is obtained via in-situ high-pressure synchrotron radiation X-ray diffraction experiments with diamond anvil cell (DAC). The results indicate that the stress difference in the cBN grains between the high-pressure and low-pressure zones is approximately 6.0 GPa under 4.2 GPa loading, while the stress difference reached to 40.0 GPa when compressed to 62.0 GPa. The main reason for the cBN particle breakage is the stress difference caused by mutual extrusion among particles under cold compression. These findings may provide a practical guide for preparing PcBN with excellent performance using high pressure sintering methods.     

Self-compacting high density tungsten–bronze composites

Green compacts of W–bronze were encapsulated in shells of bronze powder, placed in a ceramic mold and sintered in alumina tube furnace at 1150 °C. Throughout the sintering cooling stage the differential coefficient of thermal expansion ΔCTE of W–bronze was employed to induce an external compressive densification action. The process included simultaneous sintering, hot isostatic pressing (HIP) and infiltration act to enhance densification. By this technique, pilot sintered compacts of different W50–80 wt.%–pre-mix bronze of 97–99% theoretical density were produced. This process resulted in compacts of higher hardness, higher sintered density and better structure homogeneity as opposed to similar compacts densified by the conventional sintering process. The results showed a gain in hardness by 10–20% and in density by 5–15%. The impact of different cooling rates of 3, 4, 8 and 30 °C min^?1 on sintered density, microstructure and densification mechanisms was examined and evaluated. Low cooling rates of 3 and 4 °C min^?1 gave the best results.     

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.     

Titanium diboride composite with improved sintering characteristics

Titanium diboride (TiB₂) and its ceramic composites were prepared by hot pressing process. The sintering process, phase evolution, microstructure and mechanical properties of TiB₂ ceramics prepared by using different milling media materials: tungsten carbide (WC/Co) or SiAlON was studied. It was found that the inclusion of WC/Co significantly improved the sinterability of the TiB₂ ceramics. A core/rim structure with pure TiB₂ as the core and W-rich TiB₂, i.e. (Ti,W)B₂ as the rim was identified. Microstructure analysis revealed that this core/rim structure was formed through a dissolution and re-precipitation process. In addition, silicon carbide (SiC) was also introduced to form TiB₂–SiC composites. The addition of SiC as the secondary phase not only improved the sinterability but also led to greatly enhanced fracture toughness. The optimum mechanical properties with Vickers hardness ~ 22 GPa, and fracture toughness ~ 6 MPa m^1/2 were obtained on TiB₂–SiC composites milled with WC/Co.     

Effects of Ni addition and cyclic sintering on microstructure and mechanical properties of coarse grained WC–10Co cemented carbides

Coarse grained WC–10(Co, Ni) cemented carbides with different Ni contents were fabricated by sintering-HIP and cyclic sintering at 1450 °C. The effects of Ni addition and cyclic sintering on the microstructures, magnetic behavior and mechanical properties of coarse grained WC–10(Co, Ni) cemented carbides have been investigated using scanning electron microscope (SEM), magnetic performances tests and mechanical properties tests, respectively. The results showed that the mean grain size of hardmetals increases from 3.8 μm to 5.78 μm, and the shape factor Pwc decreases from 0.72 to 0.54, with the Ni content increases from 0 to 6 wt.%. Moreover, the W solubility reaches the highest value of 10.33 wt.% when the Ni content is 2 wt.%. The hardness and transverse rupture strength of WC–8Co–2Ni are 1105 HV₃₀ and 2778 MPa, respectively. The cyclic sintering is conducive to increase the WC grain size of WC–10(Co, Ni) and improves the transverse rupture strength of WC–10Co without compromising the hardness of alloys.     

Effects of sintering processes on the mechanical properties and microstructure of Ti(C,N)-based cermet cutting tool materials

In this study, two types of Ti(C_0.7,N_0.3)-based cermet cutting tool materials (Ti(C,N)–Mo–Ni–Co, named as TMNC, and Ti(C,N)–WC–Mo–Ni–Co–TaC–HfC, named as TWMNCTH) were fabricated by the hot pressed sintering process at different temperatures (from 1380 °C to 1500 °C) for different holding times (from 30 min to 60 min) in a vacuum atmosphere and at a compressive stress of 32 MPa. The polished surface and the fracture surface of the two types of cermets were observed by a scanning electron microscope (BSE/SEM) and energy dispersive spectrometry (EDS), and the relationships among sintering processes, mechanical properties and microstructure were discussed. The experimental results showed that the sintering temperature and holding time both had a great influence on the flexural strength and a small effect on the hardness and the fracture toughness of the two types of cermets. The two cermets both had the optimal comprehensive mechanical properties when they were sintered at 1400 °C for 30 min. The sintering temperature and holding time also had a great influence on the microstructure of the two cermets, and the grain sizes increased when the sintering temperature varied from 1400 °C to 1500 °C and the holding time varied from 30 min to 60 min. The properties and microstructure of the two cermets were also compared. The results indicated that the cermet TWMNCTH had a lower flexural strength, a similar value of fracture toughness, a higher hardness and a thicker rim in the microstructure.     

Structural and mechanical properties of Cr–Al–O–N thin films grown by cathodic arc deposition

Coatings of (Cr_xAl_1?x)_δ(O_1?yN_y)_ξ with 0.33 ? x ? 0.96, 0 ? y ? 1 and 0.63 ? δ/ξ ? 1.30 were deposited using cathodic arc evaporation in N₂/O₂ reactive gas mixtures on 50 V negatively biased WC–10 wt.% Co substrates from different Cr and Al alloys with three different Cr/Al compositional ratios. For N₂ < 63% of the total gas, ternary (Cr,Al)₂O₃ films containing <1 at.% of N forms; as determined by elastic recoil detection analysis. Increasing the N₂ fraction to 75% and above results in formation of quaternary oxynitride films. Phase analyses of the films by X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy show the predominance of cubic Cr–Al–N and cubic-(Cr,Al)₂O₃ solid solutions and secondary hexagonal α-(Cr,Al)₂O₃ solid solution. High Cr and Al contents result in films with higher roughness, while high N and O contents result in smoother surfaces. Nanoindentation hardness measurements showed that Al-rich oxide or nitride films have hardness values of 24–28 GPa, whereas the oxynitride films have a hardness of ～30 GPa, regardless of the Cr and Al contents. Metal cutting performance tests showed that the good wear properties are mainly correlated to the oxygen-rich coatings, regardless of the cubic or corundum fractions.     

Reduced-temperature processing and consolidation of ultra-refractory Ta4HfC5

TaC, HfC, and WC powders were subjected to high-energy milling and hot pressing to produce Ta₄HfC₅, a composite of Ta₄HfC₅ + 30 vol.% WC, and a composite of Ta₄HfC₅ + 50 vol.% WC. Sub-micron powders were examined after four different milling intervals prior to hot pressing. XRD was used to verify proper phase formation. SEM, relative density, and hardness measurements were used to examine the resulting phases. Hot pressed compacts of Ta₄HfC₅ showed densification as high as 98.6% along with Vickers hardness values of 21.4 GPa. Similarly, Ta₄HfC₅ + 30 vol.% WC exhibited 99% densification with a Vickers hardness of 22.5 GPa. These levels of densification were achieved at 1500 °C, which is lower than any previously reported sintering temperature for Ta₄HfC₅. Microhardness values measured in this study were higher than those previously reported for Ta₄HfC₅. The WC additions to Ta₄HfC₅ were found to improve densification and increase microhardness.     

Mechanical behavior of diamond matrix composites with ceramic Ti3(Si,Ge)C2 bonding phase

Polycrystalline diamond, PCD, compacts are usually produced by high pressure–high temperature (HP–HT) sintering. This technique always introduces strong internal stresses into the compacts, which may result in self-fragmentation or graphitization of diamond. This may be prevented by a bonding phase and Ti₃(Si,Ge)C₂ was so investigated. This layered ceramic was produced by Self Propagating High Temperature Synthesis and the product milled. The Ti₃(Si,Ge)C₂ milled powder was mechanically mixed, in the range 10 to 30 wt.%, with 3–6 μm diamond powder (MDA, De Beers) and compacted into disks 15 mm in diameter and 5 mm high. These were sintered at a pressure of 8.0 GPa and temperature of 2235 K in a Bridgman-type high pressure apparatus. The amount of the bonding phase affected the mechanical properties: Vickers hardness from 20.0 to 60.0 GPa and Young's modulus from 200 to 500 GPa, with their highest values recorded for 10 wt.% Ti₃(Si,Ge)C₂. For this composite fracture toughness was 7.0 MPa m^1/2, tensile strength 402 MPa and friction coefficient 0.08. Scanning and transmission electron microscopy, X-ray and electron diffraction phase analysis were used to examine the composites.