Effect of carbon source on the carbothermal reduction nitridation for synthesis of (Ti, W, Mo, V)(C, N) nanocrystalline powders

The effect of carbon source on the carbothermal reduction-nitridation during synthesizing (Ti, W, Mo, V)(C, N) nanocrystalline powders was investigated. For a systematic comparison, activated carbon, graphite and two kinds of carbon black powder were used as reducing agents in this study. Ultrafine (Ti, W, Mo, V)(C, N) powders with a particle size of ~ 200-500 nm have been produced at 1450 °C for 2 h by using nanosized carbon black source with small particle size. The presence of phases in the reaction products was characterized with X-ray diffraction (XRD) and the microstructure of carbon source powders and final products was studied by scanning electron microscopy (SEM). The results show that the formation of the Ti(C, N) phase is strongly dependent on the particle size of carbon source powders, and the synthesizing temperature of the Ti(C, N) phase decreases significantly from 1750 °C to 1300 °C by using nanosized carbon black, as compared with micron graphite. In addition, activated carbon with a particle size of 5-50 μm does not favor the dissolution of tungsten or molybdenum carbides into Ti(C, N) despite its large specific surface area.     

Influence factors and microstructure evolution during preparation of nanocrystalline (Ti, W, Mo, V)(C, N)–Ni composite powders

Nanocrystalline (Ti, W, Mo, V)(C, N)–Ni composite powders with crystalline size of about 35 nm were synthesized at 1300 °C from oxides by a simple and cost-effective route which combines traditional low-energy milling plus carbothermal reduction–nitridation techniques. Influence of main technological parameters was investigated by X-ray diffraction, and microstructure of the milled powders and reaction products was studied by scanning electron microscopy. The results show that the phase evolution of TiO₂ follows TiO₂ → Ti₃O₅ → Ti(C, N), and (Ti, W, Mo, V)(C, N)–Ni composite powders with higher nitrogen content and smaller crystalline size can be produced by introducing high nitrogen pressure. By contrast with high nitrogen pressure, high synthesizing temperature and long isothermal time can contribute to dissolution of W, Mo and V atoms into Ti(C, N). In addition, synthesizing temperature has a significant effect on the microstructure evolution of (Ti, W, Mo, V)(C, N)–Ni composite powders.     

Effect of secondary carbides addition on the microstructure and mechanical properties of (Ti, W, Mo, V)(C, N)-based cermets

(Ti, W, Mo, V)(C, N)-based cermets were prepared by mixing Mo₂C, WC and TaC with ultrafine (Ti, W, Mo, V)(C, N) powders, and then processed via a conventional P/M technique. The effect of Mo₂C, WC and TaC on the microstructure and mechanical properties of (Ti, W, Mo, V)(C, N)-8 wt.% Ni-7 wt.% Co systems was investigated. The Mo₂C content was varied from 0 to 10 wt.% and additive WC or TaC was added at a level of 5 wt.% with Mo₂C addition. The results show that the densification of (Ti, W, Mo, V)(C, N)-8 wt.% Ni-7 wt.% Co cermets was improved significantly by the addition of Mo₂C. With the increase of Mo₂C content, there is a coarsening tendency in the microstructure of (Ti, 20W, 15Mo, 0.2V)(C, N)-8Ni-7Co system, but the refinement for (Ti, 15W, 5Mo, 0.2V)(C, N)-8Ni-7Co. TaC addition decreases the density of (Ti, 15W, 5Mo, 0.2V)(C, N)-10Mo₂C-8Ni-7Co cermet and thus weakens its bending strength. (Ti, 15W, 5Mo, 0.2V)(C, N)-10Mo₂C-5WC-8Ni-7Co cermet has optimal mechanical properties: bending strength of 1999 MPa, hardness (H_v) of 1677 MPa and toughness of 9.95 MPa m^1/2 respectively by adding WC, which is due to its ultrafine and weak core/rim structure.     

Synthesis of ultrafine (Ti, W, Mo, V)(C, N)–Ni composite powders by low-energy milling and subsequent carbothermal reduction–nitridation reaction

Ultrafine (Ti, W, Mo, V)(C, N)–Ni composite powders with globular-like particles of 50–300 nm were synthesized at static nitrogen pressure from oxides by a simple and cost-effective route which combines traditional low-energy milling plus carbothermal reduction–nitridation (CRN) techniques. Reaction path of the (Ti, W, Mo, V)(C, N)–Ni system was discussed by X-ray diffraction (XRD) and thermogravimetry–differential scanning calorimetry (TG–DSC), and microstructure of the milled powders and final products was studied by scanning electron microscopy (SEM) and transmission electron microscope (TEM), respectively. The results show that CRN reaction has been enhanced by nano-TiO₂ and nano-carbon powders. Thus, the preparation of (Ti, 15W, 5Mo, 0.2V)(C, N)–20Ni is at only 1300 °C for 1 h. During synthesizing reaction, Ni solid solution phase forms at about 700 °C and reduction–carbonization of WO₂ and MoO₂ occurs below 900 °C. The reactions of TiO₂ → Ti₃O₅, Ti₃O₅ → Ti(C, O) and Ti(C, O) → Ti(C, N) take place at about 930 °C, 1203 °C and 1244 °C, respectively.     

Effect of (Ti,W, Mo,V)(C,N) powder size on microstructure and properties of (Ti,W, Mo,V)(C,N)-based cermets

Three kinds of (Ti, 15 W, 5Mo, 0.2 V)(C, N) powders with different particle size were prepared from a mixture of oxides and carbon powders by carbothermal reduction-nitridation method. (Ti, W, Mo, V)(C, N)-based cermets were obtained by mixing Co, Ni, WC, MoC₂ and (Ti, 15 W, 5Mo, 0.2 V)(C, N) powders, and then processed via a conventional P/M technique. The influence of (Ti, 15 W, 5Mo, 0.2 V)(C, N) particle size on the microstructure and mechanical properties of (Ti, 15 W, 5Mo, 0.2 V)(C, N)-5WC-10MoC₂-7Co-8Ni cermets has been studied. When the particle size of (Ti, W, Mo, V)(C, N) is 0.2–0.5 μm, (Ti, 15 W, 5Mo, 0.2 V)(C, N)-based cermets can be characterized by weak core/rim structure. With the particle size of (Ti, W, Mo, V)(C, N) increasing to 1–1.5 μm, the microstructure of (Ti, 15 W, 5Mo, 0.2 V)(C, N)-based cermets develops into composite structure that consists of typical core/rim and no core/rim. Accordingly, typical core/rim structure is obtained in the case of the particle size of 3–5 μm. With the coarsening of raw (Ti, 15 W, 5Mo, 0.2 V)(C, N) powders, the fracture toughness of (Ti, 15 W, 5Mo, 0.2 V)(C, N) cermets is greatly improved, but the hardness continues to decline. (Ti, 15 W, 5Mo, 0.2 V)(C, N) cermets with composite structure have higher bend strength of 2165 MPa.     

Synthesis of WC nanopowders from novel precursors

Nano-WC powders with granular particle of ~ 20-80 nm were synthesized by a new precursor method, namely carbothermal reduction-carburization of amorphous WO₃-C mixture, which was made initially from salt solution containing tungsten and carbon elements by air drying and subsequent calcining at 400 °C for 1 h. The reaction products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) techniques. The results show that the synthesizing temperature of WC powders was reduced greatly by the novel precursor method. Thus, the preparation of the single-phase nano-WC powders is at only 1000 °C for 2 h. The lowering of synthesizing temperature is mainly due to the homogeneous chemical composition of the amorphous oxide-carbon mixture.     

Ultrafine (Ti, M)(C, N)-based cermets with optimal mechanical properties

A tough and strong cermet with the composition (Ti,20M,0.2V)(C,N)-16M-20Ni/Co (M = W,Mo) was prepared by mixing WC and Mo₂C with ultrafine (Ti,M)(C,N) powders, and then, processed via a conventional P/M technique. It has an ultrafine and distinct core/rim structure, resulting in excellent mechanical properties: bending strength of 2210 MPa, HV hardness of 14.7 GPa and toughness of 10.1 MPa m^1/2. The small concentration gradient in core/rim composition and the disappearance of inner rims benefit the reduction of the stress concentration at the core/rim interface in (Ti,M)(C,N)-M_xC cermets, and thus improve their toughness. In addition, ultrafine microstrucure improves mainly their bending strength and hardness.     

Synthesis of (Ti,W, Mo,V)(C,N) powders by carbothermal reduction–nitridation with NH4HCO3 addition

(Ti, W, Mo, V)(C, N) powders were synthesized by carbothermal reduction–nitridation in an open system. Effect of NH₄HCO₃ addition on the phase composition and microstructure of the synthesized powders were investigated using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that NH₄HCO₃ addition plays a facilitating role in preparation of high-purity (Ti, W, Mo, V)(C, N) powders. With the temperature increasing, the residual carbon content decreases in the products but the nitrogen content is more stable. It is found that the morphologies of the synthesized powders exhibit high-porosity structure when NH₄HCO₃ additive is added.     

Fabrication of W-20wt.%Ti alloy by pressureless sintering at low temperature

A powder metallurgical technology of low temperature and pressureless is used to fabricate a W-20wt.%Ti alloy using milled TiH₂ powders and micro-sized W powders. The microstructure of the milled TiH₂ powders and the bulk W–Ti alloy were studied. It is indicated that TiH₂ nanoparticles with the size of 8 to 15 nm were obtained after milling for 48 h and the decomposition temperature decreased from 520.2 °C to 395.5 °C. The W-20wt.%Ti alloy prepared at 1200 °C for 80 min had a relative density of 97.8% which was composed of α-Ti, W and β(W/Ti) solid solution. A preparation mechanism of the W–Ti alloy is also proposed based on the experimental results.     

The aluminothermic reduction of boric acid

The effect of metallic aluminium powder on the production of boron carbide–alumina composite was studied. Boric acid, carbon and aluminium powders were mixed in stoichiometric ratio, ball milled and heat treated at temperatures between 1300 and 1650 °C for 1–5 h in the presence of argon flow. Depending on the ratio of boron oxide to carbon, the formation of boron carbide by the carbothermal reduction, was possible at a temperature of around 1500 °C, but with the addition of metallic aluminium to the mixture of boric acid and carbon, the carbide formation temperature was reduced at least 300 °C. At 1300 °C, B₄C was the major phase with alumina in the reaction products. The liquid–solid reaction mechanism, which occurred during the aluminothermic process, had a specific influence on the formation of boron carbide.     

Stability of (Ti, M)C (M = Nb, V, Mo and W) carbide in steels using first-principles calculations

The lattice parameters, formation energies and bulk moduli of (Ti, M)C and M(C, Va) with the B1 crystal structure have been investigated using first-principles calculations, where M = Nb, V, Mo and W. The replacement at 0 K of Ti by Mo or W in the TiC lattice is found to be energetically unfavorable with respect to the formation energy. However, it decreases the misfit strain between the carbide and ferrite matrix, a factor which is of critical importance during the early stages of precipitation, thus favoring the substitution of Ti by Mo, as is observed in practice. The effect of Mo in enhancing the coarsening resistance of (Ti, Mo)C precipitates is discussed in terms of its role in the nucleation process, but followed by a more passive contribution during coarsening itself. The role of tungsten has been predicted to have a similar effect to molybdenum on the nucleation and coarsening process. Analysis of precipitates in Ti-, Ti-Mo- and Ti-W-bearing steels shows results consistent with the calculations.     

Deposition of BN films on metal substrates from a fluorine-containing plasma

Boron nitride (BN) films were deposited on Mo, W, Ni, Ti and Zr substrates by DC arc jet chemical vapor deposition using a gas mixture of Ar-N₂-BF₃-H₂ at 50 Torr, a substrate temperature of 850-1150 °C, and a − 85 V substrate bias. Cubic BN (c-BN) films showing clear c-BN Raman peaks were obtained on Mo and W, but they did not adhere well to the substrates. Hexagonal or turbostratic BN was deposited predominantly on Ni substrates, which is similar to the preferable deposition of graphitic carbons in diamond CVD. High quality c-BN films with good adhesion were obtained on Ti and Zr. The reasons for these differences among metal substrates are discussed.     

纳米TiN复合Ti(C,N)基金属陶瓷烧结过程中的相演变

本文采用XRD与SEM对纳米复合Ti(C,N)基金属陶瓷烧结过程中的相演变进行了研究,结果发现:对于缺碳体系,Mo在800℃即可以夺取TiC中的C,生成Mo2C;1 000℃时开始生成Ni2(Mo,W,Ti)4C相,其含量在1 250℃时达到最大,随着温度的进一步升高而部分分解并进入Ti(C,N)晶格,生成非化学计量的(Ti,Mo,W)(C,N),导致Ti(C,N)的相对含量升高,晶格常数减少。纳米TiN与亚微米TiN相比并没有显示出更高的烧结活性。当添加适量的C时,纳米TiN复合的Ti(C,N)基金属陶瓷与同一体系的亚微米金属陶瓷烧结过程中的相变规律基本相同。     

(Ti,W,Ta)(C,N)_p/Ti(C,N)基金属陶瓷的组织与性能

采用自制的多元复式碳氮化物陶瓷粉末 ((Ti,W,Ta) (C,N) p)制备 (Ti,W,Ta) (C,N) p/Ti(C,N)基金属陶瓷。研究了 (Ti,W,Ta) (C,N) p 粉末的组织结构特征及其加入对金属陶瓷的组织及性能的影响。结果表明 ,多元复式碳氮化物粉末的晶格常数与元素的固溶度有很好的对应关系 ,调整粉末中元素的固溶度可控制粉末的晶格常数 ,进而控制材料的性能。 Ti(C,N)基金属陶瓷中 (Ti,W,Ta) (C,N) p 粉末的加入 ,有利于重金属元素 W和 Ta向粘结相中扩散 ,从而降低了硬质相在粘结相中的溶解度 ,阻碍了晶粒长大。(Ti,W,Ta) (C,N) p/Ti(C,N)基金属陶瓷各项性能指标优于 Ti(C,N)基金属陶瓷和国外对应的金属陶瓷牌号 CT5 2 5的产品。强化机制主要表现为细晶强化与固溶强化。     

Microstructure of model cermets with high Mo or W content

The microstructure of (mol%) TiC–18TiN–24Ni–(10–29)WC and TiC–18TiN–24Ni–(5–14)Mo₂C has been investigated using X-ray diffraction (XRD), optical microscopy (OM), scanning electron microscopy (SEM) and analytical electron microscopy (AEM). When the WC content in the raw materials was increased the W content in the outer rim of (Ti, W)(C, N) grains increased until it had a composition similar to that of the inner rim. If the WC content was high undissolved WC was present after sintering. When the Mo₂C content in the raw materials was increased, the volume fraction of inner rim increased and the Mo content in both inner and outer rim increased. Thermodynamical calculations on the Ti–W–C–N system suggest that the inner rim is formed during solid state sintering when there is an open porosity and thus a low nitrogen activity. The composition of the outer rim can be explained by the equilibrium at the sintering temperature if the volume fraction of undissolved Ti(C, N) cores is subtracted. Calculations on the Ti–Mo–C–N system show that (Ti, Mo)(C, N) decomposes into two phases with different Mo content and that the Ti(C, N) cores might be regarded as a stable phase.     

Formation of titanium nitride produced from nanocrystalline titanium powder under nitrogen atmosphere

The initially globular-shaped Ti powder particles were flattened to ‘pan-cake’ like shape after 12, 16, and thin flakes after 20 h of mechanical milling. Although no change peak positions of HCP Ti crystal structure, the increase in peak intensity with milling time was evident. It is found that the greater surface to volume ratio of the milled Ti powders accelerated the N₂ uptake and subsequent formation of TiN at lower temperatures (884, 856 and 833 °C for 12, 16 and 20 h, respectively) than in the unmilled powder (∼ 1100 °C). Higher nitrogen content of 41–44 at.% by EDS analysis confirmed the high rate of dissolution on the milled powders.     

High thermal stability of TiAlSiCN coatings with “comb” like nanocomposite structure

The aim of this work was to understand the reasons for the exceptionally high thermal stability of the TiAlSiCN coatings. The hardness of the coatings increased from 41.5 to 43 GPa between 25 and 900 °C, reached a maximum value of 49 GPa at 1000 °C, and then decreased to 37 GPa at 1300 °C. The structural investigations performed before and after annealing at 1000, 1200, and 1400 °C using X-ray diffraction, scanning and transmission electron microscopy (TEM), and high-resolution TEM showed that the as-deposited “comb” like nanocomposite structure, in which (Ti,Al)(C,N) columnar grains, 10–30 nm wide, were separated by a well developed amorphous tissue, possessed a very high thermal stability as its dominant cubic phase was stable in the temperature range of 25–1400 °C. Further thorough characterization by means of energy-dispersive spectroscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy revealed structural modifications inside crystalline and amorphous phases during annealing in vacuum. Such modifications associated with a short-range rearrangement of elements are shown to be responsible for the high hardness of the TiAlSiCN coatings observed up to 1300 °C, with peak hardness at 1000 °C.     

The comparison of W/Cu and W/ZrC composites fabricated through hot-press

In this study the W/Cu and W/ZrC composites have been fabricated by hot-press and then their mechanical properties were compared in addition to their ablation resistance. To produce W-20vol.%Cu composite at first stage the elemental W and Cu powders were ball milled for 3 h in rotation speed of 200 rpm, in which 2% nickel was added in order to reduce the density. The mixed powders were hot-pressed for 1 h at 1400 °C and compact pressure of 30 MPa. Additionally W/40vol.%ZrC composite has been fabricated by hot-pressing of mixed W and ZrC powders in 30 MPa and 2200 °C for 1 h. Since these materials are used at elevated temperature applications, where ablation is the main source of material failure, after producing the composites their ablation resistance was evaluated in a real condition. The results show that not only W–ZrC composite is better than W–Cu composite in mechanical properties, but also in ablation resistance.     

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.     

A simple and novel route to synthesize nano-vanadium carbide using magnesium powders, vanadium pentoxide and different carbon source

Vanadium carbide (VC) was prepared via a simple and novel route by the reaction of metallic magnesium powders with vanadium pentoxide (V₂O₅), citric acid (C₆H₈O₇) at 650 °C or potassium acetate (CH₃COOK) at 500 °C in an autoclave. During the formation reaction, citric acid and potassium acetate were used as carbon sources because they were much easier to manipulate, lower toxic and lower cost than other carbon sources, such as carbon tetrachloride(CCl₄), melamine (C₃N₃(NH₂)₃) and cyanamide (CN₂H₂). Phase structures and morphologies were characterized by X-ray powder diffraction and scanning electron microscopy. The results indicated that all the products were cubic VC, which consisted of particles with an average size of about 50 nm and 80 nm in diameter. This method can be carried out at a mild condition, which may find potential industrial applications due to the economy and efficiency of the synthesis of VC nanopowders.