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.     

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.     

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.     

Frictional behavior and wear resistance performance of gradient cermet composite tool materials sliding against hard materials

Gradient cermet composites possessing high surface hardness, flexural strength and interface bonding strength were fabricated using vacuum hot-pressing sintering. Ball-on-disk tests were performed to investigate the tribological properties of the gradient cermet composites against 440 C stainless steel, Al₂O₃ and Si₃N₄ balls at different sliding speed and load in comparison with traditional Ti(C,N) cermets. The tribological behavior was characterized in terms of friction coefficient and wear rate. The results showed that friction coefficient was significantly dependent on the sliding speed and load when sliding against Al₂O₃ and Si₃N₄. However, there was no obvious relation between them during sliding against 440 C stainless steel due to the formation of metal adhesive layer. Gradient cermet composites exhibited a higher friction coefficient but lower wear rate than traditional Ti(C,N) cermets. The main wear mechanism of gradient cermet composites was adhesion wear during sliding against 440 C stainless steel, while abrasion wear was the predominant mechanism during sliding against Al₂O₃ and Si₃N₄. It was expected that gradient cermet composites would be excellent candidates for cutting tool materials.     

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.     

TiC whisker reinforced ultra-fine TiC-based cermets: Microstructure and mechanical properties

TiC whisker reinforced ultra-fine TiC-based cermets were fabricated and their microstructures as well as mechanical properties were characterized and compared with microsized and ultra-fine cermets. The effects of high energy milling and subsequent annealing on the composition and microstructure of microsized TiC powders were studied. It was shown that the particle size distribution of TiC powders played a critical role in determining cermets׳ microstructure and properties. Inverse grain (White core with grey rim) only exists in ultra-fine cermet with a narrow size distribution of annealed TiC powders. Large discrepancy of larger TiC powders (microsized particles or whiskers) and ultra-fine particles in size resulted in a bimodal grain size feature. Additionally, mechanical property testing was conducted and was related to the microstructural features. The whisker reinforced cermets own much higher toughness of 12.43 Mpa m^1/2 than the microsized and ultra-fine cermets, with a hardness (Hv₃₀, 1620) between them.     

Effect of Nb2O5 content and sintering temperature on the microstructure and bending strength of porous Ni-YSZ cermets

Porous Ni-YSZ cermets are prepared by reducing NiO-YSZ composites upon exposure to (Ar+6% H₂) gas. The porous cermets are prepared by the addition of carbon black (0.123 mol) to mixed NiO-YSZ powders and the conversion of NiO to Ni in the NiO-YSZ composites. The microstructure and bending strength of porous Ni-YSZ cermets as functions of sintering temperature and Nb₂O₅ content are discussed. The Ni-YSZ cermets consist of uniformly distributed Ni and YSZ grains as well as pores. Both higher sintering temperature and higher Nb₂O₅ content yield lower porosity, thus increasing the bending strength. The bending strength of 0.00470 mol% Nb₂O₅–containing Ni-YSZ cermets sintered at 1400 °C (111 MPa) is about two times higher than that of Nb₂O₅–free Ni-YSZ cermets sintered at 1400 °C (59 MPa).     

Fast preparation of ZTA-TiC-FeCrNi cermets by high-gravity combustion synthesis

ZTA-TiC-FeCrNi cermets are prepared by a fast and furnace-free way called high-gravity combustion synthesis. The synthesized cermet samples show the maximum relative density of 97.6% and a hierarchical microstructure with grain sizes from submicron to >50 µm. The content of TiC has a strong influence on the microstructure and mechanical properties of the cermet samples. A higher TiC content results in refined microstructure, improved hardness, and reduced coefficient of friction. With increasing TiC content, the strength and toughness of the samples first increase and then drops, and reach the maximum of 469±26 MPa and 11.3±0.2 MPa m^1/2 at 20% TiC. Compared with commercial polycrystalline Al₂O₃ ceramics, the ZTA-TiC-FeCrNi cermets exhibit better wear resistance, and the volume loss is lower by one magnitude than Al₂O₃ under the same condition.     

Densification and properties of transition metal borides-based cermets via spark plasma sintering

Engineering borides like TiB₂ and ZrB₂ are difficult to sinter materials due to strong covalent bonding, low self-diffusion coefficient and the presence of oxide layer on the powder particles. The present investigation reports the processing of hard, tough and electrically conductive transition metal borides (TiB₂ and ZrB₂) based cermets sintered with 6 wt.% Cu using spark plasma sintering (SPS) route. SPS experiments were carried out with a heating rate of 500 K/min in the temperature range of 1200–1500 °C for a varying holding time of 10–15 min and the optimization of the SPS conditions is established. A maximum density of ∼95% ρ_th in ZrB₂/Cu and ∼99% ρ_th in TiB₂/Cu is obtained after SPS processing at 1500 °C for 15 min. While the optimized TiB₂/Cu cermet exhibits hardness and fracture toughness of ∼17 GPa and ∼11 MPa m^1/2, respectively, the optimized ZrB₂/Cu cermet has higher hardness of ∼19 GPa and fracture toughness of ∼7.5 MPa m^1/2, respectively. High electrical conductivity of ∼0.20 MΩ⁻¹ cm⁻¹ (TiB₂/Cu) and ∼0.15 MΩ⁻¹ cm⁻¹ (ZrB₂/Cu) are also measured with the optimally sintered cermets.     

Densification,microstructure, elastic and mechanical properties of reactive hot-pressed ZrB2–ZrC–Zr cermets

In this study, cermets composed of zirconium diboride and zirconium carbide with intergranular zirconium were sintered by reactive hot-pressing. Relative density exceeding 97% was obtained for the sintered cermets having four distinct compositions varying in concentration of excess Zr. Their densification behaviour was examined by monitoring displacement during sintering. The microstructure was characterized by scanning electron microscopy and X-ray diffraction, and the elastic and mechanical properties were evaluated at room temperature. The effects of Zr concentration on the densification and mechanical properties were assessed. The ZrB₂ and ZrC micron-grains coarsened with increasing amount of Zr starting material. In addition, the cermets exhibited high flexural strength (546–890 MPa) and fracture toughness (6.63–10.24 MPa m^1/2), which simultaneously increased with increasing Zr concentration. However, the elastic moduli and hardness (11–18 GPa) decreased with increasing Zr. The shear modulus and Young's modulus were in the range of 150–190 GPa and 360–440 GPa, respectively.     

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.     

Spark plasma assisted carbothermal reduction-nitridation synthesis of (Ti,W, Mo)(C,N)-(Ni,Co) powders

Ultrafine (Ti, W, Mo)(C, N)-(Ni, Co) cermet powders were rapidly synthesized from various metal oxides, mainly anatase-TiO₂, by spark plasma assisted carbothermal reduction-nitridation (SPCRN) at low temperature. The phase evolution of the SPCRN reaction was investigated using X-ray diffraction (XRD) and the microstructure of the product powders was observed using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). NiO, Co₃O₄ and MoO₃ were converted to Ni, Co and Mo₂C by CR reaction at temperatures below 900 °C. WO₃ was successively transformed from W₂C to WC by CR reaction up to 1100 °C. Finally, at up to 1350 °C, (Ti, W, Mo)(C, N) formed into the sequence of TiO₂, Ti₄O₇, Ti₃O₅, Ti(O, N), Ti(C, N), (Ti, W)(C, N) and (Ti, W, Mo)(C, N). The crystal structure of (Ti, W, Mo)(C, N)-(Ni, Co) cermet powders was analyzed by the Rietveld method and transmission electron microscopy (TEM). The findings demonstrated that the pure (Ti, W, Mo)(C, N)-(Ni, Co) cermet powders with grain size of below 0.5 µm were synthesized from metal oxides by SPCRN reaction at 1400 °C for 10 min.     

In-situ fabrication of TiC-Fe3Al cermet

Titanium carbide has high hardness, resistance to oxidation and abrasion while iron aluminide has proper ductility as well as good strength and excellent oxidation resistance up to high temperatures. Therefore, it can be expected TiC-iron aluminide cermet to have excellent mechanical properties as a cutting tool and a wear-resistance material. In this study, mechanical milling and hot press sintering processes were used to manufacture in-situ TiC-Fe₃Al cermet, whose microstructure and mechanical properties were examined according to the changes in volume fraction of TiC and milling time. After 48 h of milling each mechanically alloyed powder crystallized in a TiC and Fe₃Al biphasic material. The milled powder was hot-pressed at 1250 ℃ and 50 MPa for 30 min to obtain sintered bodies also consisting of only TiC and Fe₃Al phases. The hard phase, TiC, had a size of 100–300 nm with overall uniform distribution decreasing as the volume fraction of TiC increased. The hardness of each sintered body showed a linearly increasing tendency according to the increase in TiC content, the hardness for 90 vol% TiC cermet being as high as 1813Hv. On the other hand, the bending strength was 1800 MPa and 1780 MPa when TiC volume fraction was 50% and 70%, respectively, while it showed an abrupt decrease up to 580 MPa at 90% TiC volume fraction. Fe₃Al phase is effective to toughening of TiC-Fe₃Al cermet and the volume fraction of Fe₃Al phase significantly influences the bending strength of the cermet.     

Ti(C,N)基金属陶瓷氮化处理后的表面组织结构及形成机理

对Ti(C，N)基金属陶瓷进行了表面氮化处理。用SEM，EPMA，TEM／EDX分析了材料表面显微组织的特征。研究发现，材料表面形成了富N、富Ti的相，它们包覆在硬质颗粒的表面。硬质颗粒周围的环形相的体积分数大大减少。晶粒尺寸也明显减小。紧邻表面硬化层，出现了一层金属粘接相含量较高的过渡层。表面氮化处理使Ti(C，N)基金属陶瓷的表面硬度得到明显的提高，而基本上不影响其抗弯强度。表面较高的-N的活度是促使各合金元素扩散，形成上述特征组织的驱动力。     

Sinterability,microstructures and electrical properties of Ni/Sm-doped ceria cermet processed with nanometer-sized particles

Ni/Sm-doped ceria (SDC) cermet was prepared from two types of NiO/SDC mixed powders: Type A—Mechanical mixing of NiO and SDC powders of micrometer-sized porous secondary particles containing loosely packed nanometer-sized primary particles. The starting powders were synthesized by calcining the oxalate precursor formed by adding the mixed nitrate solution of Ce and Sm or Ni nitrate solution into oxalic acid solution. Type B—Infiltration of Ni(NO₃)₂ solution into the SDC porous secondary particles subsequently freeze-dried. Type B powder gave denser NiO/SDC secondary particles with higher specific surface area than Type A powder. The above two types powders were sintered in air at 1100–1300 °C and annealed in the H₂/Ar or H₂/H₂O atmosphere at 400–700 °C. Increased NiO content reduced the sinterability of Type A powder but the bulk density of Type B powder compact showed a maximum at 34 vol.% NiO (25 vol.% Ni). Type B cermet was superior to Type A cermet in achieving fine-grained microstructure and a homogeneous distribution of Ni and SDC grains. The electrical resistance of the produced cermet decreased drastically at 15 vol.% Ni for Type B and at 20 vol.% Ni for Type A.     

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.     

Effect of microstructure on the electrochemical performance of Ni-ScSZ anodes

The effects of NiO powder morphology and sintering temperature on the microstructure and the electrochemical performance of Nickel-scandia-stabilized zirconia (Ni-ScSZ) cermet anodes for solid oxide fuel cells (SOFCs) were investigated. The particle size and agglomeration of the starting powders were found to affect both the microstructure and electrochemical performance of the Ni-ScSZ cermet anodes. The lowest polarization resistance, 0.690 Ω cm² at 700 °C, was measured for the Ni-ScSZ anode prepared with fine NiO powder (~0.5 µm grain size). This was attributed to the increase in the number of reaction sites afforded by the small grains and well-dispersed Ni and ScSZ phases. The effect of the anode sintering temperature was also found to affect the anode microstructure, adhesion with the electrolyte, and consequently anode polarization resistance. The lowest polarization resistance was observed for the anode sintered at 1400 °C and this was 3–5 times lower than the corresponding values for anodes sintered at lower temperatures.     

Effects of partial pressure of oxygen on sintering of a ZrO2-30 mol% Ti powder mixture

A powder mixture of ZrO₂-30 mol% Ti was sintered at 1500 °C/h under various controlled partial pressures of oxygen (PaO₂). The microstructure of each sintered sample was characterized using x-ray diffractometry and analytical transmission electron microscopy/energy-dispersive spectroscopy. TiO and highly oxygen-deficient zirconia were found after sintering at PaO₂ ~2.1×10⁻⁴ atm, which implies that the oxidation–reduction reaction is a controlling mechanism when there is a trace of residual oxygen. When the PaO₂ was increased to 1.05×10⁻¹ atm, the dissolution of residual oxygen and nitrogen in the chamber into the titanium led to the formation of TiO(N) with nitrogen in solid solution. It was inferred that the oxygen in TiO(N) was also supplied by zirconia since the zirconia became oxygen-deficient in the sintered composites. After sintering in air (PaO₂ ~2.1×10⁻¹ atm), TiO₂ and TiN were formed along with nearly stoichiometric zirconia, indicating that oxygen and nitrogen in air played a major role in the oxidation and nitridization reaction of titanium. The degree of oxygen deficiency x in ZrO_2−x decreased with increasing oxygen partial pressure, which led to an increased volume fraction of the monoclinic phase.     

Structured porous Ni- and Co-YSZ cermets fabricated from directionally solidified eutectic composites

NiO-YSZ and CoO-YSZ eutectic rods were produced by directional solidification using the laser floating zone method (LFZ). This technique produces highly structured material consisting of alternate lamellae of transition metal oxide and zirconia with variable interlamellar spacing depending on growth conditions. We have chosen conditions for interlamellar spacing of about 1 μm. The microstructure is homogeneous and mechanically stable during thermochemical reduction. Complete reduction of the transition metal oxide produces a lamellar porous cermet with porous metallic lamellae alternated with the YSZ phase. The thermal expansion coefficients of the cermets are those of the YSZ skeleton. Reaction kinetics at different temperatures during the reduction process were studied by gravimetric methods. The reduction process within the complete temperature range studied for NiO-YSZ, and at high temperatures for CoO-YSZ seems to be controlled by the O²⁻ diffusion through the YSZ phase. The amount of Ni²⁺ and Co²⁺ ions dissolved in the YSZ phase is 2 and 5 mol%. Resistivity values for the cermets along the solidification axis are 50 μΩ cm for Co-YSZ and 130 μΩ cm for Ni-YSZ. These materials are porous, ionic and electronic conductors and could be used as textured anodes for solid-oxide fuel cells (SOFC).     

Mechanical properties of reactively processed W/Ta2C-based composites

The mechanical properties of reactively processed W/Ta₂C cermet composites were studied. Dense W/Ta₂C cermets with a nominal composition of 40.4 vol% W(Ta)ss, 48.9 vol% Ta₂C and 10.6 vol% Ta₂WO₈ were fabricated using a pressureless reactive processing method. Four-point bend strength, fracture toughness, elastic modulus, and microhardness were measured at room temperature. The average flexure strength was 584 MPa which is lower than for pure W; however the strength of pure Ta₂C is unknown. The fracture toughness was 8.3 MPa m^1/2 which fits a rule of mixtures between literature values for the fracture toughness of the W and Ta₂C phases. The elastic modulus was 476 GPa, and the microhardness was 13.4 GPa. Both Young's modulus and hardness were higher than values reported for other W-based cermets.