Microstructure and cutting performance of Ti（C, N）-based cermets heat-treated in nitrogen

Ti（C, N）-based cermets were treated using hot isostatic pressing （HIP） at 1423 K in nitrogen. The microstructures compared with the as-sintered cermets were investigated using X-ray diffraction, scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray analysis, and electron microprobe analysis. It was found that high nitrogen activity in the surface zone resulted in the formation of gradient structure. Approximately 20-1am-deep, nitrogen-rich and titanium-rich hard surface zone was introduced by the heat treatment. The nitrogen activity was the driving force that caused the transportation of the atoms through the binder, titanium towards the surface, and tungsten and molybdenum inwards. In the surface zone, the particle size became fine, the inner rim disappeared, and the volume fraction of the outer rim and the binder phase considerably reduced. Small grains of TiN, WC, Mo2C, and nitrogen-rich carbonitlide phases formed in the surface zone during the heat treatment, improving the tlibological property of the heat-treated cermet.     

Microstructure of the surface zone in a heat-treated cermet material

The microstructure of a Ti(C, N)-(Ti, W)(C, N)-(Ti, Ta)(C, N)-WC-Mo₂C-Co cermet with a heat-treatment induced surface gradient has been studied. The post-sintering heat-treatment was performed at 1200 °C in a nitrogen atmosphere and the resulting microstructure was compared to that of the as-sintered material. The microstructures were characterised with optical microscopy, X-ray diffraction, electron microprobe analysis, scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray analysis, electron energy-loss spectroscopy and energy-filtered transmission electron microscopy. It was found that a 50-μm deep nitrogen-rich surface zone was introduced by the heat treatment. η-phase was observed in the surface zone. The nitrogen gradient caused diffusion of titanium towards the surface, thereby forcing the cobalt-rich binder to be transported inwards. The composition of the binder phase and outer rim of the carbonitride grains showed only minor changes with depth. The variations in binder composition may be a direct consequence of the heat treatment, but are also likely to be influenced by the formation of η-phase. A nitrogen-rich phase was present in the surface zone of the heat-treated material both as thin layers (≈ 70 nm) surrounding the carbonitride grains and as small parts of some carbonitride grains. In addition, the Ti(C, N) cores in the surface region were found to have different N/(C + N) ratios.     

Ni_3Al粘结相对Ti(C,N)基金属陶瓷组织性能的影响

采用粉末冶金法制备了Ni3Al做粘结相的Ti(C,N)基金属陶瓷,研究了添加不同含量Ni3Al粘结相的金属陶瓷的力学性能和显微组织并与Ni做粘结相的金属陶瓷进行了对比。结果表明,Ni3Al作粘结相的金属陶瓷综合力学性能总体上不如Ni做粘结相的金属陶瓷,随着金属陶瓷中Ni3Al含量的增加,其洛氏硬度值不断下降,而抗弯强度和断裂韧性却不断增加;显微组织分析表明,Ni3Al做粘结相的金属陶瓷同样具有芯环结构,Ni3Al可以控制环形相的厚度,抑制晶粒异常长大,使硬质相芯相棱角圆润。Ni3Al含量为30wt%左右的金属陶瓷能够兼顾硬度和抗弯强度等力学性能,此时的主要力学性能指标为:抗弯强度1 045±80 MPa,洛氏硬度HRA89.7±0.25,断裂韧性KIC为14.26 MPa·m1/2。     

Effects of Cr3C2 addition on the corrosion behavior of Ti(C,N)-based cermets

The Ti(C, N)-based cermets with different Cr₃C₂ addition were prepared and the effects of Cr₃C₂ addition on the microstructure and properties of cermets were discussed. The corrosion behavior of the cermets with different Cr₃C₂ addition was investigated emphatically in 2 mol/L HNO₃ solution. The results indicate that there is no obvious effect of Cr₃C₂ addition on the densification of the cermets, and all cermets are almost fully densified during sintering. The thickness of rim phase is reduced and the core size is increased remarkably in the cermets with 1 wt.% and 3 wt.% Cr₃C₂ addition; the grains are refined significantly in the cermets with the increase of Cr₃C₂ addition to 5 wt.%. The hardness and transverse rapture strength of the cermets are improved with Cr₃C₂ added properly. In HNO₃ solution, the corrosion resistance of cermets is improved remarkably by Cr₃C₂ addition. The corrosion of binder phase is predominant in the cermets in which the Ni binder phase without Cr has lower corrosion resistance than the rim phase; whereas the corrosion resistance of binder phase with high Cr content is better compared to the rim phase, so that the degradation of rim phase is predominant and a reticulate binder phase forms. With the increase of Cr₃C₂ addition, the Mo content in rim increases, and it is bad for the corrosion resistance of rim phase. Additionally, the inner rim phase has lower corrosion resistance than the outer rim phase owing to the higher Mo content.     

Preparation of self-lubricating Ti(C,N)-based cermets by solid carburization and wear behavior

In this work, self-lubricating Ti(C,N)-based cermets were prepared by solid carburization. The sintered cermets were wrapped by carburizing agent and sintered again at 1440 °C with different time. The microstructure and composition of cermets were studied. The wear behavior of cermets containing graphite phase was also evaluated using a block-on-ring tribometer. The results showed that the carbon content increased gradually in binder phase with carburizing time. When the carburizing time was 3 h, the carbon got saturated in binder phase. When the carbon content exceeded the solubility in the binder, excessive carbon precipitated and formed graphite phase. Uniformly distributed graphite clusters formed in cermets after carburization for 4 h. The graphite clusters consisted of flocked graphite particles. With the carburizing time extended to 5 h, the graphite clusters became large and some of them interlaced together. Besides, the wear results indicated that the volume loss of cermets containing graphite phase was half of that without graphite due to the formation of smooth tribofilm on the worn surface of cermets.     

Influence of WC addition on the microstructure and mechanical properties of NbC–Co cermets

NbC–24.5 wt.% Co cermets with up to 30 wt.% WC were obtained by solid state hot pressing at 1300 °C under a pressure of 45 MPa for 10 min and pressureless liquid phase sintering at 1360 °C for 60 min. The effect of WC addition on the microstructure and mechanical properties of NbC–Co based cermets was investigated. The hot pressed cermets exhibited interconnected and irregular niobium carbide (NbC) or (Nb,W)C grains, whereas the shape of the NbC grains changed from faceted with rounded corners to spherical, as the WC content increased in the pressureless sintered cermets. The undissolved WC increased with increasing WC addition. A clear core/rim structure was observed in the hot pressed cermets with 10–30 wt.% WC additions, whereas this structure was gradually eliminated when pressureless sintering. The hardness remains nearly constant whereas the fracture toughness slightly increases with increasing WC addition. The dissolution of WC in the Co binder and NbC grains, as well as the formation of a solid solution (Nb,W)C phase were supported by thermodynamic calculations.     

Effect of carbon content and cooling mode on the microstructure and properties of Ti(C,N)-based cermets

Ti(C,N)-based cermets were prepared by vacuum liquid sintering. The effects of carbon content as well as cooling mode on the microstructure, magnetic and mechanical properties of the cermets were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM) and vibrating sample magnetometer (VSM). Hardness and transverse rupture strength (TRS) were also measured. The grains of Ti(C,N)-based cermets became finer and solid solubility of titanium, molybdenum, tungsten in binder phases decreased with increasing carbon content. The thickness of the rim phases increased when the cermet was annealed at 1360 °C for 30 min during cooling, which resulted in the decrease of the hardness and the transverse rupture strength (TRS). On the other hand, the magnetic saturation of Ti(C,N)-based cermets increased with increasing carbon content, which was due to the decrease of the solid solution of alloy elements in binder phases.     

铣削刀片用纳米改性金属陶瓷的显微组织和力学性能

研究了铣削刀片用纳米改性金属陶瓷的显微组织与力学性能。SEM观察结果表明,铣削刀片用纳米改性金属陶瓷组织仍由陶瓷相和金属相组成,其中粗大的陶瓷相颗粒为芯/壳结构;Mo元素添加能有效细化金属陶瓷陶瓷基体组织。抗弯测试表明,随金属相含量增加,金属陶瓷的抗弯强度和断裂韧性增加,而硬度则降低;断口分析可知,沿晶断裂为其主要的断裂方式。     

Influence of Mo on the microstructure and mechanical properties of TiC-based cermets

The microstructures and mechanics properties of TiC-based cermets composed of TiC, WC, Ni, Co, Mo, and Cr₃C₂ were investigated. The results show that Mo has a great effect on the sintering densification, microstructures, and mechanical properties. The microstructures and distribution of Mo and Ti in the TiC-based cermets were analyzed. It was indicated that a new phase with Ti, Mo, W, and C was formed on the rim of (Ti,W)C grains by means of an addition of Mo into the TiC-based cermets. The new phase with a surrounding structure was of great aid to improve the wettability of the liquid phase on the solid phase surface of TiC, decrease the porosity and refine the grains of the hard phase, which gave rise to the increase in strength and hardness. The properties of the TiC-based cermets could be further improved to some extent by adding WC, Cr₂C₃, and Co.     

CO冷却对Ti(C,N)基金属陶瓷表层结构和切削性能的影响

为改善Ti(C,N)基金属陶瓷刀具的抗冲击性能,从烧结碳势对表层粘结相分布影响的角度出发,制备了不同压力CO冷却的Ti(C,N)基金属陶瓷刀片.借助扫描电镜和能谱仪研究了CO冷却下金属陶瓷表层的组织结构以及粘结相分布情况.对比了CO冷却和真空冷却对金属陶瓷刀片切削性能的影响.结果表明:CO冷却对金属陶瓷常规性能影响微小...     

Absence of the core–rim microstructure in TixTa1 − xCyN1 − y-based cermets developed from a pre-sintered carbonitride master alloy

(Ti,Ta)(C,N) solid solution-based cermets with cobalt as the binder phase were synthesised by a two-step milling process. The titanium–tantalum carbonitride solid solution (the ceramic phase) was obtained via a mechanically induced self-sustaining reaction (MSR) process from stoichiometric elemental Ti, Ta, and graphite powder blends in a nitrogen atmosphere. Elemental Co (the binder phase) was added to the ceramic phase, and the mixture was homogenised by mechanical milling (MM). The powdered cermet was then sintered in a tubular furnace at temperatures ranging from 1400 °C to 1600 °C in an inert atmosphere. The chemical composition and microstructure of the sintered cermets were characterised as ceramic particles grown via a coalescence process and embedded in a complex (Ti,Ta)–Co intermetallic matrix. The absence of the typical core–rim microstructure was confirmed.     

Ti(C,N)基金属陶瓷断口形貌及增韧机理

采用真空烧结工艺制备Ti(C,N)基金属陶瓷,测定了材料的力学性能。结果表明,其力学性能与未加纳米粉的金属陶瓷相比,硬度略有升高,但横向断裂韧性提高了近一倍。断口形貌和微观组织分析表明:金属陶瓷的断口形貌与其强韧性有着密切的关系。纳米粉的加入降低了原始粉末的平均粒度,使得金属陶瓷硬质相的粒度降低,减小了晶粒间的平均自由程。镶嵌于大颗粒环形相和弥散分布于粘结相中的细小硬质相颗粒,对裂纹的形成和扩展起到阻碍作用,会使金属陶瓷因裂纹扩展途径发生偏转而增韧。     

Effect of Mo addition on microstructure and mechanical properties of (Ti,W)C solid solution based cermets

(Ti,W)C solid solution was synthesized by milling a mixture of C and oxides and then reducing it at 1350 °C for 2 h. The microstructure and mechanical properties of (Ti,W)C solid solution based cermets with various Mo additions were systemically studied. The dark core–gray rim carbide grains and/or gray carbide grains embedded in black Ni based binder phase were observed. The grain size of the cermets decreased with increasing Mo addition, while excessive Mo addition would result in agglomeration and inhomogeneity of the grains. The dark core was transformed from (Ti,W)C into (Ti,W,Mo)C and Mo concentration in the dark core increased with increasing Mo content. The fracture toughness of the cermets decreased with the increase of Mo content, while the hardness and TRS reached a peak value at 10 wt.% and 15 wt.% Mo additions respectively, and declined with the further increase of Mo content.     

Microstructure and mechanical properties of (Ti,W,Ta)C-xMo-Ni cermets

(Ti,W,Ta)C-xMo-20Ni (x = 0–20 wt.%) system cermets were prepared by using (Ti,W,Ta)C solid solution as hard phase, without adding secondary carbides in this work. The microstructures exhibited two kinds of carbide grains observable in the BSE mode: one had a dark core–gray rim structure; the other had a dark core–white inner rim–gray outer rim structure. Several (Ti,W)C white particles with high W content were also observed in the microstructures. Results showed that molybdenum has completely dissolved in the Ni binder and mainly was found in the rims of the carbide particles. As the Mo content increased, the wettability between (Ti,W,Ta)C particles and metallic phase was improved, and the shrinkage of cermets increased, the porosity decreased. Results also revealed that finer microstructures were obtained with the increase of Mo addition. But excess Mo addition caused the aggregation of particles. Mechanical properties such as hardness and TRS improved with the increase of Mo content, but the TRS of cermets reached a peak value at the 15 wt.% Mo addition, then declined with the further increase of Mo addition.     

Effect of partial substitution of Cr for Ni on densification behavior, microstructure evolution and mechanical properties of Ti(C,N)-Ni-based cermets

Four cermets of composition TiC-10TiN-16Mo-6.5WC-0.8C-0.6Cr₃C₂-(32 − x)Ni-xCr (x = 0, 3.2, 6.4 and 9.6 wt%) were prepared, to investigate the effect of the partial substitution of Cr for Ni on densification behavior, microstructure evolution and mechanical properties of Ti(C,N)-Ni-based cermets. The partial substitution of Cr for Ni decreased full densification temperature, and the higher the content of Cr additive was, the lower full densification temperature was. The partial substitution of Cr for Ni had no significant effect of the formation of Mo₂C and Ti(C,N) and the dissolution of WC, and however, it had a significant effect on the dissolution of Mo₂C. Cr in Ni-based binder phase diffused into undissolved Mo₂C to form (Mo,Cr)₂C above 1000 °C at 6.4-9.6 wt% Cr additive, and a small amount of (Mo,Cr)₂C did not dissolve after sintering at 1410 °C for 1 h at 9.6 wt% Cr additive. In the final microstructure, Cr content in Ni-based binder phase increased with increasing the content of Cr additive, and however, regardless of the content of Cr additive, coarse Ti(C,N) grains generally consisted of black core, white inner rim and grey outer rim, and fine Ti(C,N) grains generally consisted of white core and grey rim. The partial substitution of Cr for Ni increased hardness and decreased transverse rupture strength (TRS). Ni-based binder phase became hard with increasing the content of Cr additive, therefore resulting in the increase of hardness and the decrease of TRS. TRS was fairly low at 9.6 wt% Cr additive, which was mainly attributed hardening of Ni-based binder phase and undissolved (Mo,Cr)₂C.     

Microstructure and performance of a cermet material heat-treated in nitrogen

A Ti(C,N)–TiN–WC–Co cermet material was subjected to a heat-treatment in nitrogen which substantially improved the plastic deformation resistance during cutting. The microstructure was characterised using analytical electron microscopy. It was found that a surface zone rich in titanium and nitrogen was induced by the heat-treatment. The high nitrogen activity in the surface region was the driving force for outward transport of titanium and inward transport of tungsten in the cobalt binder. An irregularly shaped nitrogen-rich titanium carbonitride reprecipitated from the binder phase during the heat-treatment, often as surrounding layers on already existing carbonitride grains. The morphological change of the hard phase might explain the dramatically improved plastic deformation resistance by obstructing grain boundary sliding. The experimental findings were in accordance with thermodynamic calculations performed using the Thermo-Calc software.     

Microstructural evolution during sintering of cermets studied using interrupted sintering experiments and novel 2D and 3D FESEM based techniques

During sintering of cermets the dissolution and precipitation of dissolved MeCs lead to the well-known formation of a core-rim structure. To investigate the microstructural evolution during sintering the sintering process was interrupted at different temperatures and the formation of the core-rim structure traced. EDS mappings and point scans as well as 3D-FIB tomography scans were carried out to study the distribution of added MeCs like Mo₂C or WC on ion-beam prepared samples. The studied cermet consisted of a Ti(C,N) hard phase with a mixed Co and Ni binder and added Mo₂C. The results show i.e. that within the rim area not only a high amount of MeC exists, but also that during the final stages of sintering in some grains binder inclusions within the rim area and Mo inclusion within the core appear.     

烧结工艺对Ti(C,N)基金属陶瓷性能的影响

采用粉末冶金法制备Ti(C,N)基金属陶瓷,利用金相图像分析系统和扫描电镜观察陶瓷表面孔洞和微观组织形貌,分析了热处理和烧结气氛工艺对不同碳氮比的Ti(C,N)基金属陶瓷性能的影响.结果表明:真空烧结后的热处理工艺可使Ti(C,N)基金属陶瓷的横向断裂强度提高10%以上,硬度也有不同程度的提高,其中Ti(C0.5 N0.5)基金属陶瓷适合采用低压工艺处理,Ti(C0.7 N0.3)基金属陶瓷适合采用热等静压工艺处理.氮气气氛烧结中,Ti(C0.5 N0.5)基金属陶瓷在氮分压值为2kPa时的横向断裂强度达到最大值,而硬度变化不明显,这可归因于合适的氮分压阻碍了金属陶瓷内氮化物的分解,提高了材料的致密度,细化了晶粒组织.     

Effect of VC addition on sinterability and microstructure of ultrafine Ti(C, N)-based cermets in spark plasma sintering

The effect of vanadium carbide (VC) addition on the sinterability and the microstructure of ultrafine Ti(C, N)-based cermets consolidated through spark plasma sintering (SPS) was systematically investigated using optical microscope, scanning electron microscope (SEM) with X-ray energy dispersive spectrometer (EDS), X-ray diffractometer (XRD) and transmission electron microscope (TEM). Our results reveal that the addition of VC increases the porosity of sintering body and depresses the sinterability of Ti(C, N)-based cermets. It is also found that the VC addition has a significant influence on the microstructure of ultrafine Ti(C, N)-based cermets, which inhibits the dissolution of titanium-containing compounds and the formation of inner rim phase and outer rim phase, thus preventing from grain growth. Owing to the depressed dissolution and precipitation, nitrogen liberation is mitigated, therefore resulting in less amount of graphite phase in the samples. In substance, VC changes the solubility of metallic elements in the binder, which makes more elements of Mo and W to be reserved in the binder and thus greatly decreases the content of titanium dissolved into the binder. The re-building solubility rule determines the development of phases and microstructure.     

ZrC含量对TiC基金属陶瓷组织和性能的影响

真空烧结制备了TiC-ZrC-Co-Ni系金属陶瓷,研究了ZrC对TiC基金属陶瓷显微组织和室温力学性能的影响。结果表明:未加ZrC的TiC基金属陶瓷的显微组织表现为经典的黑芯-灰壳组织,硬质相形状多为球形;而加入ZrC后的金属陶瓷随着ZrC加入量的增多,组织逐渐细化,硬质相形状大多数为方形,硬质相与粘结相界面呈现直线,在黑芯周围出现白色球状(Ti,Zr)C固溶体。由于Co、Ni对ZrC的润湿性不理想,金属陶瓷的致密度随着ZrC含量的增加而下降,室温力学性能(抗弯强度、硬度、断裂韧性)也随之降低。