Ti(C,N)-based cermets with strengthened interfaces: Roles of secondary cubic carbides

Core-rim structure, concerning its interface structure and internal stress, plays an important role in mechanical performance of Ti(C,N)-based cermets. Four types of cermets containing equimolar TaC, VC, ZrC, and NbC were fabricated, in order to reveal the synergetic relationship between core-rim structure and mechanical properties. VC and ZrC effectively inhibited the grain growth, while TaC and NbC favored for coarser core-rim grains. A thin distortion layer at the rim-binder interface was confirmed, formed during the solidifying stage. Compared to the TaC, ZrC and NbC, VC shrunk the lattice parameters of rims and effectively decreased the lattice misfit of the distortion zone from around 4.0%-0.8%. Cermets containing VC showed satisfactory bending strength of 2099 MPa and toughness of 10. 3 MPa m^1/2, owing to the strengthened rim-binder interface. TaC and NbC exhibited the similar roles in cermets with comparable mechanical properties, while addition of ZrC increased the lattice misfit of core-rim structure, resulting in poor mechanical performance. Decreased lattice misfit of rim-binder interface changed the fracture mode of cermets from intergranular to transgranular fracture, with in-situ formed dimples.     

Ti(C,N)-based cermets containing uniformly dispersed ultrafine rimless grains: Effect of VC additions on the microstructure and mechanical properties

Difference in lattice parameters and physical properties of core-rim structure leads to mismatch at the core-rim interfaces. In this respect, VC was adopted to shrink the lattice of rims and intended to reduce the lattice misfit. Small amount of VC (0.8 wt%) effectively decreased the grain size from 0.77 μm to 0.57 μm, with an increased lattice parameter of the core-rim phase. Higher VC content accelerated the dissolution and precipitation process, resulting in the formation of thicker rims and smaller lattice parameters of core-rim structure. The same lattice parameters of core-rim phases were achieved with 4.8 wt% of VC addition. A distortion zone with a thickness of 3–5 atomic layers was confirmed, which located at the boundary of binder and gray rim. VC induced the formation of spherical rimless grains, which were uniformly dispersed in the binder and usually attached to the coarse core-rim grains. Black ultrafine rimless grains exhibited larger lattice parameters than Ti(C,N) cores due to the increased C/N ratios. Ti(C,N)-based cermets with uniformly dispersed rimless grains were achieved, which showed effectively improved the bending strength of cermets, with in-situ formed dimples inside the binders during the fracture.     

碳化钛粒径对碳氮化钛基金属陶瓷微观结构和力学性能的影响

用粉末冶金真空烧结法制备了超细晶粒碳氮化钛[Ti(C,N)]基金属陶瓷.研究了原始粉末粒径对Ti(C,N)基金属陶瓷微观结构和力学性能的影响.结果表明:在化学成分相同的条件下,晶粒细化使材料的Vickers硬度和抗弯强度上升,但断裂韧性有所下降.在超细晶粒Ti(C,N)基金属陶瓷微观组织中出现了一种新型的白芯/灰壳结构和一种特殊化合物(Ni2Mo2.5W1.3)Cx.初步研究表明:由于原始粉末粒径微小,促进了扩散反应因而生成了这种芯/壳结构.芯/壳结构有利于提高材料的抗弯强度和断裂韧性.(Ni2Mo2.5W1.3)Cx有利于提高材料的Vickers硬度,但是降低了Ti(C,N)基金属陶瓷的抗弯强度和断裂韧性.     

Effect of WC content on the microstructures and corrosion behavior of Ti(C,N)-based cermets

The influence of WC content on the microstructure and corrosion behavior of Ti(C, N)-based cermets in 2 mol/L nitric acid solution was studied in this paper. There exists typical core/rim structure in the cermets. The cores appear black or white, and the rim is divided into white inner rim and grey outer rim. The undissolved Ti(C, N) particles normally appear as black cores, while the white core, inner rim and outer rim are (Ti, W, Mo) (C, N) solid solution formed at different sintering stages. The inner rim and white core appear brighter atomic contrast than the outer rim and black core, which is attributed to their higher W and Mo content. The thickness of the inner rim increases with WC addition, but the grain size of core/rim phase becomes finer. Meanwhile, the amount of white cores increases and that of black cores decreases. WC is more easily oxidized and dissolved in the nitric acid solution, compared with Ti(C, N). Therefore, the degradation of inner rim phase and the white core becomes more considerable with the increase of WC content. Consequently, the corrosion rate of cermets increases and the corrosion resistance of Ti(C, N)-based cermets is deteriorated with the increase of WC content.     

Ti(C,N)-based cermets with fine grains and uniformly dispersed binders: Effect of the Ni–Co based binders

Metallic binder is a key factor affecting the microstructure and mechanical properties of Ti(C,N)-based cermets. To optimize the overall performances, cermets with various weight ratios of Ni/(Co + Ni) ranging from 0 to 1 were fabricated by gas pressure sintering. Microstructure, phase formation, interface structure and related mechanical properties of the sintered cermets were investigated. With the increase of the Ni/(Co + Ni) ratios, the black cores became smaller and grains of Ti(C,N) dispersed uniformly. Compared to the pure Ni or Co, Ni–Co binders accelerated the formation of rim phases, and avoided the nonuniform dispersed binder pools. When the ratio was 0.5, the cermets showed fine grains, uniformly dispersed binders and small lattice misfit of the core-rim interface, exhibiting the optimal mechanical properties, i.e. satisfactory Vickers hardness of 1670 (HV30) Kgf/mm², bending strength of 1970 MPa and Fracture toughness of 8.94 MPa m^0.5. This work sheds light on constructing the relationship between the microstructure, mechanical performance of Ti(C,N)-based cermets and the Ni/Co-based binders.     

Effect of Cr3C2 on Valence-Electron Structure and Plasticity of Rim Phase in Ti(C,N)-Based Cermets

Based on the empirical electron theory of solids and molecules, the valence-electron structure (VES) of the rim phase in Ti(C,N)-based cermets was calculated, and the relationship between the VES and plasticity was determined. The results indicated that the plasticity of the rim phase in a Ti(C,N)-based cermet could be defined using the sum of the n _a values for the covalent bonds, and that chromium dissolution in the rim phase improved the plasticity of the rim phase. Moreover, a series of experiments showed that adding Cr₂C₃ to a typical Ti(C,N)-based cermet strengthened the interface. Based on those results, a Ti(C,N)-based cermet with added Cr₃C₂ was manufactured; the new cermet had more than twice the transverse rupture strength of a typical cermet.     

Morphology evolution of TiC-based cermets via different sintering schedules

Solid state sintering, liquid phase and cooling stages play different roles in determining the final morphology and composition of cermets, especially the well-known core-rim structure. In this work, TiC-(5–25 wt%)WC-11Mo₂C-18(Ni-Co) cermets were prepared and sintered by different sintering schedules. Morphology evolution and rim phase composition during sintering from 1250 °C to 1600 °C were investigated. Effects of sintering stages on the final morphology of cermets were also studied. It was shown that submicron (Ti, W, Mo)C grains tend to precipitate in binder during the cooling for cermets with high WC content. After the formation of outer rims during liquid sintering stage, interface reaction began to take effect between the rims and core. Coreless (Ti_0.76, W_0.13, Mo_0.11)C ceramic grains would be formed under high temperature (1600 °C) for TiC cermets with 25% WC. Long time sintering at solid state favored the formation of black core-thick inner rim and bright core-grey rim phases, while cooling near the melting point could result in submicron bright particles. This study provided not only a better view of the formation of rim-core structure but also an easier way to control the final morphology of cermets via reasonable changing the sintering cycle.     

Effect of WC or NbC addition on lattice parameter of surrounding structure in Ti(C0.7N0.3)–Ni cermets investigated by TEM/CBED

The changes in the lattice parameters of the solid solutions in the Ti(C_0.7N_0.3)–WC–Ni and Ti(C_0.7N_0.3)–NbC–Ni systems were first shown quantitatively by the CBED (Convergent Beam Electron Diffraction) technique together with TEM (Transmission Electron Microscopy) microstructure characterization. The extent of the changes in the lattice parameters between core and rim differs in the case of WC and NbC additions. No change in the lattice parameters is observed in the Ti(C_0.7N_0.3)–WC–Ni cermets, in contrast to the Ti(C,N)–NbC–Ni cermets where significant changes in the lattice parameters are observed. The difference in the parameters is correlated with the core/rim structure, which disappears in the Ti(C,N)–NbC–Ni cermets when a large amount of NbC is added, and is discussed based on thermodynamic arguments. Large strain in the core and rim structure, especially near the core/rim interface, is also observed from the HOLZ (High Order Laue Zone) line splitting.     

Effects of TiC/TiN addition on the microstructure and mechanical properties of ultra-fine grade Ti (C, N)–Ni cermets

Two series of Ti (C, N)-based cermets, one with TiC addition and the other with TiN addition, were fabricated by conventional powder metallurgy technique. The initial powder particle size of the main hard phase components (Ti (C, N), TiC and TiN) was nano/submicron-sized, in order to achieve an ultra-fine grade final microstructure. The TiC and TiN addition can improve the mechanical properties of Ti (C, N)-based cermets to some degree. Ultra-fine grade Ti (C, N)-based cermets present a typical core/rim (black core and grayish rim) as well as a new kind of bright core and grayish rim structure. The average metallic constituent of this bright core is determined to be 62 at% Ti, 25 at% Mo, and 13 at% W by SEM–EDX. The bright core structure is believed to be formed during the solid state sintering stage, as extremely small Ti (C, N)/TiC/TiN particles are completely consumed by surrounding large WC and Mo₂C particles. Low carbon activity in the binder phase will result in the formation (Ni₂Mo₂W)C_x intermetallic phase, and the presence of this phase plays a very important role in determining the mechanical properties of TiN addition cermets.     

Ti(C,N)基金属陶瓷中陶瓷相芯/壳组织的观察与分析

用ＸＲＤ，ＳＥＭ，ＴＥＭ和ＨＲＥＭ观察、分析和方法研究了Ｔｉ（Ｃ，Ｎ）基金属陶瓷中陶瓷相的芯、壳组织。结果表明，在ＳＥＭ，ＴＦＭ观察中，芯、壳之间存在相界面，而ＨＲＥＭ观察显示陶瓷相的芯／壳组织具有连续相同的点阵结构。     

Microstructure and mechanical properties of Ti(C,N)-based cermets fabricated by in situ carbothermal reduction of TiO2 and subsequent liquid phase sintering

Ti(C,N)-based cermets were prepared by in situ carbothermal reduction of TiO₂ and subsequent liquid phase sintering in one single process in vacuum. The densification behavior, phase transformation, and microstructure evolution of the cermets were investigated by DSC, XRD, SEM, and EDX. The results showed that the carbothermal reduction of TiO₂ was completed below 1250 °C, and Ti(C,N)-based cermets with refined grains were obtained after sintered at 1400 °C for 1 h by this method. The hard phase of the cermets mainly exhibited white core/gray rim structure, in great contrast to the typical black core/gray rim structure of hard phase in traditional cermets. Ti(C,N)-based cermets prepared by this novel method showed excellent mechanical properties with a transverse rupture strength of 2516±55 MPa, a Rockwell hardness of 88.6±0.1 HRA, and a fracture toughness of 18.4±0.7 MPa m^1/2, respectively.     

Microstructural evolution and phase transition mechanism of Ti(C,N)-based cermets during vacuum sintering process

Ti(C,N)-based cermets were fabricated using section vacuum sintering. The density and shrinkage ratio of sintered samples were recorded and analyzed. Phase transition, microstructure and interface behaviors of cermets were examined by transmission electron microscope, X-ray diffractometer and scanning electron microscope. As the sintering temperature rising, the number of pores in cermets was decreased and the density of samples was increased. Moreover, with the progress of sintering, atoms of various elements were constantly diffusing and gathering, affecting the formation of different microstructure, and the angle and intensity of each XRD peak were also constantly changing slightly, or disappearing at a certain temperature. These relevant results indicated that the proportion of heavy element to Ti in the hard phase would affect its lattice parameter. After the appearance of liquid phase, the densification mechanism changed from surface diffusion to grain boundary diffusion, thus accelerating the densification. With the proceeding of sintering process, various microstructures were formed such as core - rim/rimless structure. Finally, the process of interface change in core rimless phase transition was discussed. This rim phase, formed in solid state sintering process while failing to develop into core-rim structure after liquid sintering, was formed by some heavy elements short-range diffusion into core phase. The orientation different and the misfit between this core and rim were relatively large. While after liquid sintering, the semi-coherency or even coherency state at the interface of core-rimless and binder was formed.     

Submicron Ti(C,N)-based cermets with improved microstructure using high-energy milled and subsequent heat-treated ultrafine Ti(C,N) powders

Ti(C,N)-based cermets with ultrafine or submicron black core-rim grains are attracting candidates for high-quality tools and dies, due to their high hardness and strength. However, high chemical activity of ultrafine Ti(C,N) powders lead to the increased instability and difficulty to control the sintering process, since the denitrification and interface diffusion are accelerated during the solid-state reaction. Based on this, owing to the unrealized commercial ultrafine-grade powders, ultrafine Ti(C,N) powders with an average grain size around 150 nm, low oxygen content and few dislocations are fabricated via the high-energy ball milling and subsequent heat treatment of commercial micron Ti(C,N) powders. Related morphology evolution, microstructure and composition of the ultrafine Ti(C,N) powders are investigated. Dense submicron Ti(C,N)-based cermets with grain size of 0.62 μm and uniform core-rim phases are successfully prepared by using the as-fabricated ultrafine Ti(C,N) powders. Compared to cermets via the conventional high-energy milling route, submicron Ti(C,N)-based cermets exhibit higher hardness of 1750 ± 40 N/mm², bending strength of 1960 ± 135 MPa, and satisfactory fracture toughness of 9.2 MPa m^1/2, owing to smaller grain size, uniform microstructure and partial black core-rim grains.     

Effect of Nano-Size Powders on the Microstructure of Ti(C,N)-xWC-Ni Cermets

Microstructural and compositional analyses of Ti(C,N)– x WC–20Ni cermets were performed to understand the dissolution behavior of nano-size Ti(C,N) and WC, compared with an ultra-fine and a micro-sized system. The WC content was varied from 10 wt% to 70 wt%. The rapid dissolution and reprecipitation of nano-Ti(C,N) powders induced the formation of a coreless microstructure. With an increase in the amount of WC, the concentration of W in the rims increased but was low compared with the ultra-fine or micrometer system. An inversion in W concentration between the inner rim and the outer rim occurred at ∼40 wt% added WC. That is, the outer rim was richer in W than the inner rim. Powder size strongly affected the dissolution and precipitation of particles and was a major determinant of the final microstructure and compositions of the rims. Furthermore, a significant improvement in toughness in the case of simple nano systems was found, compared with that of the corresponding micrometer and ultra-fine systems ( K _{I C} 10–12 vs. 6–10 MPa·m^1/2). The coreless microstructure and the high fraction of rim phase in the nano system are responsible for this difference.     

Influence of ZrC addition on the microstructure,mechanical properties and oxidation resistance of Ti(C,N)-based cermets

In this study, Ti(C,N)-WC-NbC-ZrC-Co-Ni cermets were prepared by sintering-hip at 1450?°C. The effect of ZrC addition on the microstructure, mechanical properties, oxidation resistance and wear resistance of Ti(C,N)-WC-NbC-Co-Ni cermets were explored in detail. The results show that ZrC addition plays the role of inhibitor in the dissolution–reprecipitation process, which can increase the wear-resistant carbide phases and inhibit the precipitation of brittle (Ti,W,Nb)(C,N) rim phase. Therefore, the core-rim structures are refined and the Nb content in binder increases, which enhance mechanical properties and oxidation resistance of cermets. With the increasing ZrC content, the oxidation resistance of cermets can be improved constantly, while the transverse rupture strength, fracture toughness and wear resistance of these cermets increase first and then decrease. The cermet with 1?wt% ZrC exhibits the transverse rupture strength of 2549?MPa and highest fracture toughness of 13.0?MPa?m^1/2. The oxidation weight gain of cermets containing 5?wt% ZrC after holding 100?h at 750?°C in air is 2.8?×?10^?6 g?mm^?2, which is only 22% of that in the cermets without ZrC addition.     

Fabrication and properties of Ti(C,N) based cermets reinforced by nano-CBN particles

Titanium carbontride (Ti(C,N)) based cermets with and without nano-cubic boron nitride (CBN) particles were prepared by microwave sintering in argon and nitrogen environment, respectively. Two kinds of core–rim microstructure, black core–grey rim and white core–grey rim, are shown in the cermets by scanning electron microscopy (SEM) in combination with energy dispersive X-ray analysis (EDX). It is found that, for the cermet with 1.5% nano-CBN particles sintered at 1500 °C for 30 min in argon, its transverse rupture strength (TRS) and hardness are improved to about 25.9% and 1.4%, respectively. The SEM analysis shows that the inhibition effect of nano-CBN particles on the dissolution of Ti(C,N) is weakened with the increase of content of nano-CBN particles. Moreover, for the cermet sintered in argon reinforced by 1.5% nano-CBN particles, more fine black core–grey rims are found in the microstructure compared to the others. For the material sintered in nitrogen, its microstructure accompanied with many white core–grey rims in number and big black core and thin outer rim in size, results in high hardness and low TRS.     

Cr3C2和VC对Ti(C,N)基金属陶瓷中环形相的价电子结构和性能的影响

根据固体与分子经验电子理论，计算了Ti(C，N)基金属陶瓷中界面环形相的价电子结构，讨论了其价电子结构与塑性间的关系。当材料晶体结构相同时，Σna可用来比较其塑性的相对高低。Cr在环形相(Ti，Mo)(C，N)中的固溶，可使其塑性增强，V在环形相中的固溶将使其塑性变差。在计算的基础上进行实验，实验结果表明：Cr3C2的适量加入确实有利于提高金属陶瓷的强度，最终所制备出金属陶瓷的强度比典型成分体系材料的提高了1倍以上；尽管VC的加入能使材料的晶粒得到有效地细化，但它使环形相塑性降低，使金属陶瓷的抗弯强度略有增加。     

Ti(C,N)基金属陶瓷氧化后的显微结构与力学性能

研究了Ti(C,N)基金属陶瓷的高温抗氧化性能。采用X R D、SEM分析了样品氧化后的物相组成及显微结构,并测试了试样氧化前后的抗弯强度和维氏硬度。实验结果表明:Ti(C,N)基金属陶瓷在800℃时氧化不明显,但抗弯强度开始下降;样品在900℃时开始剧烈氧化,材料的抗弯强度呈现明显的下降趋势,试样氧化前后的硬度变化较小。随着氧化温度的升高,氧化层厚度明显增加,Ti(C,N)被氧化变成TiO 2。     

Evolution of microstructure and interfacial characteristics of complete solid-solution Ti(C,N)-based cermets fabricated by mechanical activation and subsequent in situ carbothermal reduction

Complete solid-solution Ti(C,N)-based cermet, with no typical core-rim structure, was synthesized through mechanical activation and subsequent in situ carbothermal reduction method. XRD, SEM, TEM, and C/N analysis were used to investigate the microstructure, phase transformation, and the interfacial characteristics of the present cermets. During solid-state sintering, the (Ti,Mo)C/(Ti,Mo)(C,N) phases formed through the transformation of Mo-based solid solution which generated by mechanical activation. Then, the formed (Ti,Mo)C/(Ti,Mo)(C,N) continuously dissolved into the nickel-based binder above 1100 °C. It was found that in the subsequent stage of liquid sintering, the mechanical activation and also the presence of extremely fine TiC/Ti(C,N) particles accelerated the Mo diffusion into the hard phase, resulting in a large quantity of (Ti,Mo)(C,N) solid solutions formed in the nickel-based binder. Finally, complete (Ti,Mo)(C,N) solid-solution phase was obtained via dissolution and re-precipitation. The higher toughness and transverse rupture strength (TRS) of the synthesized new cermet, as compared with traditional cermets, were mainly caused by the increased crack deflection and transgranular fracture of the novel cermets. Moreover, the interface among the Ni-based binder phase and complete solid solution hard phase exhibited a semi-coherency state with high-density dislocations, which also significantly improved the TRS and toughness of the synthesized cermets.     

Processing and Properties of Ti(C,N)–WC-Based Materials

Two Ti(C,N)–WC powder mixtures, one containing 0.88 wt% Co and the other 6.2 wt% Ni + 2.9 wt% Co, were fabricated by different routes: pressureless and gas-pressure sintering in argon and nitrogen, and hot-pressing under vacuum. The microstructures of all the sintered samples consisted of grains with a core/rim structure, the core being Ti(C,N) and the rim (Ti,W)(C,N). An inner rim also was present at the core/rim interface. The more highly doped materials also had an intergranular Ni-Co-Ti-W binder phase. The compositions and cell parameters of the hard phases, as well as of the binder, were analyzed. The nitrogen partial pressure in the sintering furnace was the main factor that influenced grain growth and phase composition. In fact, sintering under argon enhanced grain growth and was accompanied by a lower tungsten content in the rim. The influence of the microstructure on some mechanical properties (hardness, flexural strength, toughness, and Young's modulus) also was investigated. Flexural-strength values up to 1550 MPa at room temperature and 1200 MPa at 800°C, and fracture-toughness values up to 8 MPa·m^1/2 were measured, depending on the starting composition and processing conditions.