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.     

Microstructure evolution and performance improvement of TiN‐based cermets with carbon addition

In this work, TiN‐based cermets with excellent performance and uniform microstructure were successfully manufactured by conventional vacuum sintering with 0‐5 wt% carbon addition at 1500°C. Influence of carbon addition on the microstructure and mechanical properties of cermets was investigated by scanning electron microscope, transmission electron microscope, X‐Ray diffraction, electron probe microanalysis, and mechanical tests. The results showed that small amount of carbon helped to improve significantly the wettability between TiN and Ni/Co, leading to well‐distributed structure and perfect core‐rim phases. As the carbon content increased from 0 to 5 wt%, mechanical properties of cermets increased initially, displayed a maximum and then decreased. For the experimental conditions considered, the cermets with 3 wt% carbon addition revealed best mechanical properties. The relative density, the transverse rupture strength, fracture toughness, and Rockwell hardness of the cermets were 99.78%, 1836 MPa, 14.7 MPa m^1/2, and 88, respectively.     

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 short carbon fibre concentration on microstructure and mechanical properties of TiCN-based cermets

Short carbon fibre (C_f) reinforced TiCN-based cermets (C_f/TiCN composites) were produced by powder metallurgy method with pressureless sintering technology. The phase evolution, microstructure and fracture morphology of C_f/TiCN composites were investigated. The results showed that TiC, TiN, WC, Cr₃C₂ and Mo phases disappeared gradually and diffused into core and rim phases by dissolution–reprecipitation process, finally formed new hard TiCN core phases and complex compound (Cr, W, Mo, Ti)(CN) rim phases, with the sintering temperature increasing. The added C_f did not change the ‘core–rim’ microstructure but improved the mechanical properties of TiCN-based cermets. The C_f/TiCN composite containing 3?wt-% C_f achieved the best comprehensive mechanical properties, with fracture toughness and bending strength increasing by about 14.4% and 30.8%, respectively, when compared with the composite without C_f. Toughening and strengthening mechanisms of C_f/TiCN composite were concluded as crack deflection and branch, as well as the pull-out, fracture and bridging of carbon fibres.     

Microstructure and mechanical properties of TiC–TiN–Zr–WC–Ni–Co cermets

Cermet cutting tools are widely used for semi-finishing and finishing work on steel and cast iron. However, their brittleness is still an unavoidable limitation for their utilizations. Zirconium was added to improve the fracture toughness of Ti(C, N) based cermets. The microstructure and the fracture surfaces of cermets were studied by using scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The experimental results reveal that Zr dissolved and formed solid solutions during the sintering process. The amount of grains with typical core/rim structure decreases and that of coreless grains increases with increasing Zr addition. Moreover, the fracture toughness is improved clearly due to the increased amount of the coreless grains, the spinodal decomposition in cermets, as well as the crack deflection and crack branching mechanisms. Additionally, hardness and relative density were also measured, respectively.     

Microstructure evolution and characteristic of Ti(C,N)-based cermets prepared by in situ carbothermal reduction in TiO2

Ti(C,N)-based cermets were prepared by in situ carbothermal reduction in TiO₂ and subsequent liquid phase sintering under vacuum. The prepared cermets were examined using XRD, SEM, TEM, and EDX. During solid-state sintering, fine TiC particles were formed through the carbothermal reduction in TiO₂. A great number of (Ti,W,Mo)C complete solid solutions containing more W and Mo subsequently formed through the counter diffusion of the fine TiC and carbides. The majority of the coarse TiN particles in the raw powders remained undissolved. During liquid phase sintering, Ti-based carbonitride complex solid solutions with less W or Mo precipitated on the coarse TiN particles and fine (Ti,W,Mo)C particles, resulting in black core/gray rim structures and white core/gray rim structures, respectively. Moreover, small amounts of Ti-based carbonitride complex solid solutions precipitated directly from the liquid binder phase in some areas enriched in W and Mo during the cooling stage after sintering, resulting in coreless grains. Ultimately, after being sintered at 1400°C for 1 hour, the present cermets were characterized with white core/gray rim grains, black core/gray rim grains and a few gray grains. In addition, the interfaces between the black core/gray rim grains and binder phase were atomically smooth, exhibiting a orientation relationship with a perfect coherency state.     

Ti(C,N)基金属陶瓷的力学性能与显微结构的研究

烧压烧结制备了不同Mo2C和Cr3C2含量的Ti(C0.7N0.3)-(Ni—Co)-Mo2C—Cr3C2金属陶瓷，对其性能测试表明，低Mo2C，Cr3C2含量材料具有良好力学性能。利用透射电镜、能谱分析和扫描电镜对低Mo2C，Cr3C2含量金属陶瓷显微组织进行了分析。研究表明，材料显微组织中没有发现明显可见的环形相，Mo元素富集在硬质相颗粒边缘附近，Cr元素富集在粘结相中。未完全溶解的Cr3C2分布在粘结相内和相界上抑制了裂纹的扩展，断口上沿晶断裂面弯曲不规整以及穿晶解理条纹较多，这是材料具有较高的断裂韧性的原因。     

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.     

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.     

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.     

Microstructure and mechanical properties of SiC platelet reinforced BaOAl2O32SiO2 (BAS) composites

BaOAl₂O₃2SiO₂ (BAS) glass–ceramic powders were prepared by sol–gel technique. SiC platelet reinforced BAS glass–ceramic matrix composites with high density and uniform microstructure were fabricated by hot-pressing. The effect of additional crystalline seeds on hexagonal to monoclinic phase transformation of Barium aluminosilicate was studied. The effects of SiC platelet content on the microstructure and mechanical properties of the composites were also investigated. The results showed that the flexural strength and fracture toughness of the BAS glass–ceramic matrix composites can be effectively improved by the addition of silicon carbide platelets. The main toughening mechanism was crack deflection, platelets' pull-out and bridging. The increased value of flexural strength is contributed to the load transition from the matrix to SiC platelets.     

ß-sialon ceramics with TiN particle inclusions

Fully dense composites of 0–30 wt% discrete TiN particles distributed in a ß-sialon matrix of overall composition Si_5·5Al_0·5O_0·5N_7·5 have been prepared by hot isostatic pressing at 1650 and 1750°C. Pressureless sintering at 1775°C gave materials with an open porosity. Typical sizes of the TiN particles were 1–3 μm, and no intergranular glassy phase was observed in the prepared materials. The grain size of ß-sialon was below 1 μm in the materials HIPed at 1650°C, and 1–2 μm at 1750°C. The Vickers hardness was fairly constant for the TiN-ß-sialon composites with up to 15 wt% TiN added: H_v10 around 17·5 GPa for materials HIPed at 1650° and around 17 GPa at 1750°C, whereas at higher TiN contents the hardness decreased to around 16 GPa. The indentation fracture toughness of the ß-sialon ceramic increased approximatively from 3 to 4 MPam^1/2 at an addition of 15 wt% TiN particulates. The fracture toughness could be further increased to 5 MPam^1/2 by addition of small amounts of Y₂O₃ and A1N to a ß-sialon composite with 30 wt% TiN.     

Improvement of microstructure,mechanical properties and cutting performance of Ti(C,N)-based cermets by ultrafine La2O3 additions

Ti(C,N)-WC-Mo₂C-TaC-Co-Ni cermets with various content of La₂O₃ were prepared by gas-pressure sintering at 1450 °C. The effects of ultrafine La₂O₃ additions (0, 0.05, 0.1 and 0.2 wt%) on the microstructure, mechanical properties, wear resistance and cutting performance of cermets were explored. In the microstructure of cermets, the La₂O₃ particles and dissolved La element in binder phases were observed, which could inhibit the dissolution-precipitation process of ceramics phases during liquid-sintering. Furthermore, the La₂O₃ could absorb and react with the impurity Al element with low melting point from raw powders, avoiding the appearance of liquid phase at the low temperature and partial overheating during sintering process. These mechanisms could inhibit the abnormal growth of Ti(C,N) core-(Ti,W,Mo,Ta)(C,N) rim structures effectively, leading to the thinning of brittle rim phases and coarsening of wear-proof Ti(C,N) particles. The decrease of proportion of brittle rim phase and ultrafine Ti(C,N) particles promoted the fracture toughness. The increase of proportion and grain size of Ti(C,N) improved the hardness, wear resistance and cutting performance significantly. However, the excessive addition of La₂O₃ would result in the agglomeration of La₂O₃, causing the sharp decline of mechanical properties and cutting performance. The cermet with 0.1 wt% La₂O₃ addition possessed the optimal mechanical properties with Vickers hardness, transverse rupture strength and fracture toughness of 1710 (HV30) Kgf/mm², 2480 MPa and 11.7 MPa m^1/2, respectively.     

Fabrication of Ti(C,N)‐based cermets by in situ carbothermal reduction of MoO3 and subsequent liquid sintering

Ti(C,N)‐based cermets were fabricated by in situ carbothermal reduction of MoO₃ and subsequent liquid sintering in a single heating process. The densification behavior, phase formation, and microstructure evolution of the cermets were characterized by DSC, XRD, SEM, and TEM. The results showed that near‐fully dense Ti(C,N)‐based cermets with fine carbonitride grains could be obtained by the above‐mentioned method. The carbonitride grains of the cermets still exhibited typical core/rim structures and evenly distributed in the binder phase, but the rim phase was more complete and thinner compared with traditional cermets. In addition, the interfaces between the ceramic phase and binder phase of the cermets were atomically smooth, having the orientation relationship of ()_R//(110)_B with a perfect coherency state. The prepared Ti(C,N)‐based cermets produced with MoO₃ showed excellent comprehensive mechanical properties having a transverse rupture strength of 2461±62 MPa, a Rockwell hardness of 88.0±0.1 HRA, and a fracture toughness of 22.3±0.4 MPa·m^1/2, respectively.     

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.     

Characterization of the textural properties of metal loaded ZSM-5 zeolites

The textural properties of metal ion over-exchanged zeolites, Co–, Cu–, Ni–ZSM-5, were compared with those of the parent ZSM-5 by nitrogen adsorption measurements and photoelectron spectroscopy. The treatment of the adsorption isotherms permitted a thorough characterization of the microstructure of the samples. A first estimation of the microporous volume was made by the Dubinin–Radushkevich method. The “t-plot” method was used to determine the external surface and to obtain another estimation of the microporous volume. Effective micropore size distribution was obtained with the Horvath–Kawazoe approach. The Dubinin–Radushkevich method overestimated the microporous volume of the zeolites, in particular when the solid had an important external surface. It is shown that Cu–ZSM-5 had micropore size and micropore size distribution very close to those of ZSM-5, whereas Co–ZSM-5 and Ni–ZSM-5 had lower microporous volumes and larger external surfaces. The external to internal (microporous) surface ratios, r_s, and the mesoporous to microporous volume ratios, r_v, are proposed as practical parameters to classify the solids with respect to their microstructure. ZSM-5, a pure microporous solid, has low values of both r_s and r_v parameters. Ni– and Co–ZSM-5 have high r_s ad r_v parameters, indicative of some degree of mesoporous character. Cu–ZSM-5 has intermediate characteristics, typical for micro-mesoporous solid. XPS measurements confirmed that copper ions penetrated to a greater extent in the channels of ZSM-5 zeolite than cobalt and nickel ions, which merely deposited on the external surface of ZSM-5 zeolite as oxidic aggregates.     

Preparation of Ni–Mo–C/Ti(C,N) coated powders and its influence on the microstructure and mechanical properties of Ti(C,N)-based cermets

Ni–Mo–C/Ti(C,N) coated powders, namely Ni–Mo alloy and Mo₂C coated Ti(C,N) composite powders, were synthesized by using a heterogeneous precipitation and thermal reduction method, then pressed and vacuum sintered to fabricate cermets. The chemical composition, microstructure and phases of the composite powders and the microstructure and properties of sintered cermets were experimentally investigated. The results show that a fine and uniform microstructure of (Ti,Mo)(C,N)-Ni cermets without the conventional core-rim structure is obtained. The phases formed during the preparation of the coated powders as well as the cermets were analyzed by means of a X-ray diffraction (XRD) technique. The XRD result confirms the formation of the Ni₃Ti phase in the cermets. Due to the formation of the non-magnetic Ni₃Ti and the dissolution of Mo in Ni binder phase, the magnetic properties are strongly retarded. The fracture of the cermets is mainly characterized by inter-granular and dimple fractures. Better mechanical properties can be obtained in comparison with conventionally fabricated ones.     

Effect of WC content on microstructure and mechanical properties of Ni3Al-bonded cermets

The effect of WC content on microstructure and mechanical properties of the TiC–Ni₃Al system cermets was investigated. Ni₃Al-bonded cermets showed a core–rim structure with carbide particle coupled with rim embedded in Ni₃Al binder. With WC content increasing, TiC grains were refined and the white rim became complete and got thicker gradually. Interface between core and rim showed a completely coherent relationship. The rim enriched in W constituted an ideal coherence between hard phase and Ni₃Al binder phase. With WC content increasing, the densification of cermets was enhanced, and hardness and TRS were increased firstly and then reduced, reaching peak values 90.9 HRA (HV₃₀ 15 GPa) and 1629 MPa, respectively in cermet N5 (25 wt% WC). Similarly, fracture toughness got a peak value (11.6 MPa m^1/2), at the composition with 20 wt% WC.     

WC含量对Ti(C,N)基金属陶瓷组织和性能的影响研究

用传统的粉末冶金方法制备了不同WC含量的超细Ti(C,N)基金属陶瓷试样,运用SEM,EDX等手段对材料的显微组织进行了表征分析,并用这些显微组织的特征和差异解释了材料宏观力学性能的特点.结果表明,金属陶瓷的组织为典型的两相结构特征,其中陶瓷相的芯、壳结构(core/timstructure)与溶解析出机制有关.少量WC的加入能提高材料的力学性能.断口SEM分析表明:断裂机理为典型的混合型断裂(穿晶断裂和沿晶断裂),金属相存在着明显撕裂的痕迹.     

Microstructure and mechanical properties of TiN-based cermet reinforced by Cr3C2 addition

TiN-based cermets with different Cr₃C₂ addition were prepared by conventional vacuum sintering. Effect of Cr₃C₂ on microstructure and properties of TiN-based cermets were discussed. Owing to the formation of sound rims on TiN cores, ultrafine TiN-based cermets with more uniform microstructure and finer grains were obtained with 1 wt% Cr₃C₂. When the added Cr₃C₂ content enhanced from 0 to 2 wt%, the transverse rupture strength (TRS) and fracture toughness increased firstly and then decreased, while the hardness increased monotonically. For the experimental conditions considered, the cermet with 1 wt% Cr₃C₂ addition had optimal combination of hardness (91HRA), fracture toughness (14.7 MPa m^1/2) and TRS (2123 MPa).