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 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.     

Experimental and thermodynamic investigation of gradient zone formation for Ti(C,N)-based cermets sintered in nitrogen atmosphere

The influence of N₂ atmosphere on the microstructure of gradient zone in Ti(C,N)-Mo₂C-Ni cermet was systematically investigated by the coupling analysis of experimental characterization and thermodynamic calculation. Under the guidance of calculated carbon window, the composition of Ti(C,N)-Mo₂C-Ni cermet was designed, and the cermet was produced via liquid-phase sintering at 1450 °C for 2 h under N₂ pressure of 20, 200, 400 and 600 mbar. The microstructure and element distribution of cermet were analyzed by using Scanning Electron Microscopy (SEM) equipped with Energy Dispersive X-ray spectroscopy (EDX). A homogeneous microstructure was obtained for cermet sintered in 20-mbar nitrogen atmosphere, whereas the thickness of gradient layer increased with nitrogen pressure. EDX mapping demonstrate that Mo and Ti are enriched in gradient zone, while Ni is lacking and partially segregated near the surface. The diffusion of elements in cermet is caused by the different nitrogen activity between surface and interior. The carbonitride grains show typical black core and gray rim structure in the bulk of cermets, while it present light-gray core and gray rim in the surface gradient layer. In addition, the Vickers microhardness measurement was performed for the gradient zone of cermets, and the hardness increased for cermets sintered in higher nitrogen pressures, which exhibit slower grain growth phenomena.     

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.     

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.     

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.     

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.     

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.     

Mechanical properties of (TixW1−x)C–Co cermet prepared by carbothermal reduction of high energy ball milled TiO2–WO3–C

A series of solid–solution carbides, (Ti_xW_1−x)C (x=0.9, 0.8, 0.7, 0.6), was prepared by the high-energy milling of TiO₂–WO₃–C mixtures via subsequent carbothermal reduction. With high-energy milling, only the size reduction of the constituent powders was apparent without any chemical reaction. The milled mixture powder was transformed to a single–phase (Ti_xW_1−x)C solid solution by heat treatment in a vacuum at 1200 °C. (Ti_xW_1−x)C–Co cermets were consolidated by isothermal sintering at 1300, 1400, and 1500 °C. The powders were fully densified by liquid-phase sintering at 1500 °C because the Co melted at 1430 °C. The mechanical properties of the (Ti_xW_1−x)C–Co cermet (H_v: ~24 GPa) were significantly better than those of the conventional WC–Co (H_v: ~13 GPa) or TiC–Co cermets (H_v: ~16 GPa). The use of a solid–solution carbide instead of conventional WC almost doubled its hardness values without a loss of toughness. It is indicated that the improved hardness of the (Ti_xW_1−x)C–Co cermet originates from the high hardness of (Ti_xW_1−x)C, and the solid–solution carbide would be a valuable substitute for conventional carbide cermets.     

Preparation and characterization of Si3N4-based composite ceramic tool materials by microwave sintering

Si₃N₄-based composite ceramic tool materials with (W,Ti)C as particle reinforced phase were fabricated by microwave sintering. The effects of the fraction of (W,Ti)C and sintering temperature on the mechanical properties, phase transformation and microstructure of Si₃N₄-based ceramics were investigated. The frictional characteristics of the microwave sintered Si₃N₄-based ceramics were also studied. The results showed that the (W,Ti)C would hinder the densification and phase transformation of Si₃N₄ ceramics, while it enhanced the aspect-ratio of β-Si₃N₄ which promoted the mechanical properties. The Si₃N₄-based composite ceramics reinforced by 15 wt% (W,Ti)C sintered at 1600 °C for 10 min by microwave sintering exhibited the optimum mechanical properties. Its relative density, Vickers hardness and fracture toughness were 95.73 ± 0.21%, 15.92 ± 0.09 GPa and 7.01 ± 0.14 MPa m^1/2, respectively. Compared to the monolithic Si₃N₄ ceramics by microwave sintering, the sintering temperature decreased 100 °C,the Vickers hardness and fracture toughness were enhanced by 6.7% and 8.9%, respectively. The friction coefficient and wear rate of the Si₃N₄/(W,Ti)C sliding against the bearing steel increased initially and then decreased with the increase of the mass fraction of (W,Ti)C., and the friction coefficient and wear rate reached the minimum value while the fraction of (W,Ti)C was 15 wt%.     

Microstructural design of BaTiO3-based ceramics for temperature-stable multilayer ceramic capacitors

In order to satisfy EIA X8R specification, a new type of BaTiO₃-based ceramic with hierarchical structure in a formula scheme “a ferroelectric ABO₃ + another ferroelectric ABO₃”, was designed. There were (Ba, Bi)TiO₃ and Ba(Ti, Zr)O₃ phases with different Curie temperatures coexisting in the grains from inside to outside, prepared by wet chemical method under 100 °C. The hierarchical structure of the ceramic grains was proved by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX). The dielectric constant of (Ba, Bi)TiO₃–Ba(Ti, Zr)O₃ ceramic was ～6000, the ΔC/C_20 °C was ?12.0%, 14.1%, and ?8.3% at ?55 °C, 130 °C, and 160 °C, respectively, and the dielectric loss is less than 0.1, which is obviously superior to (Ba, Bi)TiO₃ and Ba(Ti, Zr)O₃. The results of this work showed that the formula scheme “a ferroelectric ABO₃ + another ferroelectric ABO₃” for solid solutions is a promising approach to prepare high performance temperature-stable capacitor materials.     

Structural,thermal, dielectric and ferroelectric properties of K0.5Bi0.5TiO3 ceramics

Dense K_0.5Bi_0.5TiO₃ (KBT) lead-free ceramics were prepared by conventional solid reaction route. Their temperature behavior (up to 600 °C) was investigated by X-ray diffraction, DSC, dielectric spectroscopy and electric field-polarization technique. The first temperature dependent Raman scattering studies were also performed. X-ray and Raman scattering results show that samples exhibit a single perovskite structure with cubic symmetry at temperatures higher than approximately 400 °C and with coexistence of the cubic and tetragonal phases below this temperature. Two structural phase transitions between tetragonal phases in temperature range 200–225 °C and between tetragonal and cubic ones near 400 °C are observed. The content of the tetragonal phase increases with decreasing temperature and at room temperature it reaches more than 70%. Temperature- dependent P-E loops and pyroelectric data revealed a polar behavior in KBT up to about 400 °C, which means that the intermediate phase (～270–380 °C) is rather ferroelectric than antiferroelectric.     

Photocatalytic activities of N-doped nano-titanias and titanium nitride

TiO₂ doped with various loadings of nitrogen was prepared by nitridation of a nano-TiO₂ powder in an ammonia/argon atmosphere at a range of temperatures from 400 to 1100 °C. The nano-TiO₂ starting powder was produced in a continuous hydrothermal flow synthesis (CHFS) process involving reaction between a flow of supercritical water and an aqueous solution of a titanium salt. The structures of the resulting nanocatalysts were investigated using powder X-ray diffraction (XRD) and Raman spectroscopy. Products ranging from N-doped anatase TiO₂ to phase-pure titanium nitride (TiN) were obtained depending on post-synthesis heat-treatment temperature. The results suggest that TiN started forming when the TiO₂ was heat-treated at 800 °C, and that pure phase TiN was obtained at 1000 °C after 5 h nitridation. The amounts and nature of the Ti, O and N at the surface were determined by X-ray photoelectron spectroscopy (XPS). A shift of the band-gap to lower energy and increasing absorption in the visible light region, were observed by increasing the heat-treatment temperature from 400 to 700 °C.     

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.     

Enhanced photocatalytic activity of porous single crystal TiO2/CNT composites by annealing process

To improve the photocatalytic performance of anatase TiO₂ (a-TiO₂), it is necessary to simultaneously increase its crystallinity and surface area. Our approach to achieve the desired morphology is to develop a porous single crystal that can be transformed from its mesocrystal form via annealing. We synthesized a-TiO₂ mesocrystals onto multiwalled CNTs using a facile one-pot chemical approach, and investigated the effect of the annealing temperature (200–600 °C) on the crystallinity, morphology, chemical bonding state, and photocatalytic performance of the TiO₂/CNT composites. The as-grown sample and sample annealed at 200 °C consisted of spindle-like a-TiO₂ mesocrystals. As the annealing temperature increased to 400 °C, the morphology of a-TiO₂ changed from mesocrystals into porous single crystals and the surface area enlarged due to the thermo-decomposition of organic residues between the subunits. The chemical bonding (Ti–O–C) between TiO₂ and CNT was also strengthened with increasing annealing temperature. On the other hand, the TiO₂ was separated from the CNT at 600 °C because of the large difference in the thermal expansion coefficients. The photocatalytic performance of the TiO₂/CNT composites was the highest at 400 °C due to the increased crystallinity, removal of the by-products, and strengthened Ti–O–C bonds, resulting in an increase in the photocatalytic active sites and efficient charge separation.     

Formation of TiC particle during carbothermal reduction of TiO2

Formation of TiC particle during carbothermal reduction of titanium dioxide (TiO₂) was investigated. The mixture with TiO₂ and carbon resin was reacted at 1500 °C for 0–45 min under flowing Argon atmosphere. The powders were characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The partially reduced TiO₂ particles were conglomerated in the initial stage of the reduction and the size of this conglomerate ranged from 500 to 1000 nm. After the complete reaction between Ti as a reduction product and C, the large conglomerates separated to homogeneous and fine TiC particles with a size of 80 nm.     

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.     

Microstructure and elastic modulus of electrospun Al2O3-SiO2-B2O3 composite nanofibers with mullite-type structure prepared at elevated temperatures

In the present work, Al₂O₃-SiO₂-B₂O₃ composite nanofibers with mullite-type structure were prepared using electrospinning technique. The microstructure and elastic modulus of the composite nanofibers obtained at elevated temperatures were studied. The results showed that Al₄B₂O₉ phase formed at 900 °C and then transformed to Al₁₈B₄O₃₃ at 1100 °C. Mullite was also detected in the nanofibers prepared at 1100 °C. Amorphous SiO₂ existed in all samples even the calcination temperature reached up to 1400 °C. The continuous and uniform structure of the composite nanofibers was kept after calcining at different temperatures, while rougher surface was evident due to the growth of the grain caused by the elevated temperature. An increase of elastic modulus of the samples from 9.47 ± 1.91 GPa to 27.30 ± 2.61 GPa was observed when calcination temperatures increased from 800 °C to 1400 °C.     

The phase formation process of Bi0.5(Na0.8K0.2)0.5TiO3 thin films prepared using the sol-gel method

Lead-free Bi_0.5(Na_0.8K_0.2)_0.5TiO₃ (abbreviated as BNKT) thin films were grown on Pt(111)/Ti/SiO₂/Si substrates using a sol-gel/spin coating technique and were then annealed at different temperatures (350 °C, 550 °C, 750 °C and 850 °C). Analysis of the XRD patterns and FT-IR spectra were used to determine the main reactions and the phase formation process of BNKT thin films during the sol-gel process. The results show that the dielectric constant of the thin films attains a maximum at a set temperature and then decreases at higher annealing temperatures, which can be attributed to phase formation and transformation. Moreover, the morphologies of the BNKT thin films improve with the increase in grain size and the formation of distinct grain boundaries. Furthermore, through increasing the pH of the precursor solutions, the size of the sol-gel colloidal particles increases slightly and the grains formed from the corresponding solutions tend to be small and uniform.     

Effects of (Ti,Ta,Nb,W)(C,N) on the microstructure,mechanical properties and corrosion behaviors of WC-Co cemented carbides

Homogeneous solid-solution (Ti, Ta, Nb,W)(C,N) powders were synthesized through carbothermal reduction-nitridation method. The effects of (Ti, Ta, Nb,W)(C,N) powders on the microstructure, mechanical properties and corrosion resistance of WC-10Co cemented carbides were investigated using XRD, SEM, electrochemical test and mechanical properties tests. The results showed that cemented carbides with pre-alloyed powder addition had a similar microstructure appearance: weak core/rim structure consisting of solid-solution phase embedded in the WC-Co system. The black core and gray rim, both of which contained similar elements, were identified as (Ti, Ta, Nb,W)(C,N), but the latter contained higher amount of heavy elements.With the addition of (Ti, Ta, Nb,W)(C,N) powders, the density, transverse rupture strength and fracture toughness of samples decreased monotonously. However, the hardness rose sharply at first, reached a peak at 15 wt% solid-solution addition, then slightly decreased, and finally increased again. Results also revealed that increasing (Ti, Ta, Nb,W)(C,N) made the open circuit potential (OCP) in 1 M sulphuric acid solution more negative than that of WC-Co, and all specimens exhibited pseudo-passivation phenomenon in the test solution. In addition, increasing pre-alloyed powders led to decreasing corrosion current density, which implies that (Ti, Ta, Nb,W)(C,N) could remarkably improve the corrosion resistance of WC-Co cemented carbides.