Fabrication of TiC from the Cu–Ti–C system under the super-gravity field
Graphical abstract
An innovative approach of fabricating TiC via the solid carbon dissolution in the CuxTi melt and separation with super-gravity by blending the reactant mixtures composed of titanium sponge, copper and carbon particles.
Introduction
Titanium carbide (TiC), with face-centered and cubic crystal structure of NaCl, is an attractive compound and has been widely applied in many fields, such as grinding wheels, turbine engine seals, cutting tools, abrasives, bullet-proof vests, wear-resistant coatings, aerospace materials, magnetic recording heads, conducting diffusion barriers in chemistry, microelectronics and machinery industry, etc. [[1], [2], [3]]. Moreover, it can be used as a reinforced phase in advanced engineering composite materials or hardening phase in the superalloy [4,5]. As a result of its outstanding and superior properties, such as high Young’s modulus (410–450 GPa), high melting point (3140 °C), high boiling point (4820 °C), ultrahigh hardness (3000 kg/mm2), high Vickers hardness (28–35 GPa), high electrical conductivity (30 × 106 S/cm), as well as excellent chemical and thermal stability, high resistance to wear, corrosion, abrasion and thermal shock, good thermal conductivity, and high solvency with other carbides, and so on [[6], [7], [8]].
Particularly, it is meaningful to synthesize the fine-grained and narrow size-distributed TiC due to the fact that the mechanical properties of fine TiC are much higher than conventional bulk material [9]. The general industrial process of synthesizing TiC powders is the carbothermal reduction of titanium dioxide (TiO2) powders in the presence of carbon black or carbonaceous organic materials [10]. Nevertheless, it has the disadvantages of long reaction time (10–24 h) coupled with high reaction temperature (1700–2100 °C) demand, and multiple unreacted titanium dioxides and residual carbon will exist in the product [11].
In recent years, several methods that have been used to synthesize TiC powders are direct reaction between titanium powders and carbon black, carbonization of titanium hydride, self-propagating high temperature synthesis (SHS), gas phase reaction between TiCl4 and appropriate gaseous hydrocarbons, carbothermal reduction of polymeric precursors obtained from titanium alkoxides, thermal plasma processing of titanium rich slag, mechanical alloying (MA), mechanically activated sintering (MAS), Mg-thermal reduction of TiCl4 and CxCll4 solution, and vacuum metallurgy, etc. [[12], [13], [14], [15], [16], [17], [18], [19]]. Ma et al. [20] reported a convenient route to synthesize nanocrystalline titanium carbide by the reaction of metallic magnesium powder with titanium dioxide and basic magnesium carbonate in an autoclave at relatively low temperature. M. Razavi et al. [21] proposed the synthesis of TiC nanocomposite powder from commercially pure TiO2 and carbon black using mechanically activated sintering. B.H. Lohse et al. [22] investigated the effect of starting composition on the synthesis of nanocrystalline TiC of titanium and carbon under a helium atmosphere using a magneto ball mill. Sen et al. [23] reported the preparation of fine TiC powders by the carbothermal reduction of TiO2 in vacuum which is easier than in atmospheric pressure. However, most of the above methods will lead to the high energy consumption, requirements of the high purity for initial titanium powder, the complexity of process and equipment, the long post milling process, formation of the non-stoichiometric composition (TiC0.7–0.9) and contamination of a product [24,25]. In addition, these processes present the weaknesses of the non-uniform shape and agglomeration of TiC particles [26]. Accordingly, it is expected to investigate innovative methods for the fabrication of titanium carbide.
Nowadays, in order to reduce the reaction temperature and improve the mass transformation, the second metals such as Cu, Al, Fe, Ni and Mo have been incorporated into the reactant mixtures of Ti–C system which can serve as diluent and binder with low melting point [[27], [28], [29], [30]]. Li et al. [31] found that TiC powders with particle size ranging from 1.0 to 4.0 μm could be fabricated using Al, Ti and C powders by laser ignited self-propagating high-temperature synthesis (LISHS). Zhang et al. [32] reported the formation behavior of TiC in the Fe–Ti–C system during combustion synthesis, and Fe played an important role in controlling the reaction behavior and morphology of products. Yang et al. [33] studied the effect of C particle size on the ignition and combustion characteristics of the SHS reaction in the 20 wt% Ni–Ti–C system. Liang et al. [34] investigated the reaction behavior of self-propagating high-temperature synthesis of TiC ceramic in the Cu–Ti–C system, the DTA results showed that TixCuy compounds were formed firstly during the solid-state reaction between Cu and Ti elements and then the Cu–Ti eutectic liquids were formed with continued heating, TiC particles were precipitated finally when C particles diffusing into the Cu–Ti melt. The formation reaction of TiC in the Cu–Ti–C system can be summarized as follows: CuxTi + C = xCu + TiC, more importantly, the synthesis temperature can be decreased dramatically due to the melting point of the Cu–Ti melt is only about 1173 K. Inspiring by this, Cu can be selected as the additive metal to help precipitating TiC from the Cu–Ti–C system [35,36].
To effectively separate the precipitated TiC from the Cu–Ti–C system, a new approach of super-gravity technology was proposed in this study. Super-gravity technology, inspired by Ramshaw’s utilization of centrifugal apparatus [37], can greatly overcome the mass transfer resistance and the limited reaction area during the interfacial reaction of precipitating TiC. Up to now, multiple investigations such as removing impurity phases from metal melts, recovering metals from molten slags and separating valuable metals from electronic wastes have been carried out under the super-gravity field. For instance, Yang et al. [38] reported that the copper impurity could be effectively removed from Pb-3wt%Cu alloy melt in a super-gravity field and the separation efficiency reached 96.18%. Guo et al. [39] studied the removal of tramp elements within 7075 alloys by super-gravity aided rheorefining method. In addition, it is an effective method to separate the suanite (Mg2B2O5) crystals from boron bearing slag [40], the Fe-bearing and P-bearing phases from steelmaking slag [41], the anosovite crystals [42] and the perovskite crystals [43] from molten Ti-bearing slag, the copper phase and iron-rich phase from copper slag [44], and so on. Meng et al. [45,46] proposed the super-gravity separation of Pb, Sn, Al, Zn, Cu and precious metals from waste printed circuit boards in the heating process, and the process can achieve closed-loop, clean recycling of electronic waste with significant efficiency. Moreover, the super-gravity method also could be used to prepare functional graded materials [47,48], porous materials [49], and metal matrix composites [50], etc.
Therefore, it is speculated that fabricating TiC from the Cu–Ti–C system under the super-gravity field is a practical method based on the above-mentioned results. The main characteristics to synthesize TiC are as follows: (1) using carbon particles and bulk metals as raw materials can be conducive to cost savings; (2) the reaction temperature is reduced compared with carbothermal reduction method; (3) the precipitated TiC are well dispersibility with homogeneous and fine particles. In this work, the theoretical analysis of precipitating TiC in the Cu–Ti–C system was investigated, and the influences of copper content, separating temperature, gravity coefficient and separating time on the separation of precipitated TiC from the Cu–Ti–C melt have been studied. Additionally, the particle size distribution and stoichiometric of TiC were calculated. Simultaneously, the detailed mechanism of fabricating TiC by super-gravity was discussed.
Section snippets
Experimental apparatus
Fig. 1 depicts the separation apparatus which can generate an adjustable super-gravity field and was used to continually separating the precipitated TiC from the Cu–Ti–C system in this study. It mainly configured by a counterweight and a resistance-heating furnace, which were symmetrically fixed onto a centrifugal rotor. Especially, the resistance-heating furnace had a cylindrical corundum chamber with an isothermal zone of 80 mm in length. In addition, the two hanging chambers could rotate
Feasibility analysis of precipitating TiC in the Cu–Ti–C system
Multiple intermetallic phases such as Ti2Cu, TiCu, TiCu4 and Ti3Cu4 can form initially by solid-state diffusion reactions between titanium and copper particles based on previous literatures as shown in Fig. 3. Afterwards, the TiC particulates gradually precipitated from the Cu–Ti–C system, and it were formed due to the solid carbon particles dissolved into the Cu–Ti liquids. Therefore, the variation of its composition during the evolution process demonstrated that CuxTi melts could dissolve the
Conclusions
In summary, the solid carbon dissolution in the CuxTi melt and separation with super-gravity was an innovative approach of fabricating TiC by blending the reactant mixtures composed of titanium sponge, copper and carbon particles. The main results are as follows:
- (1)
The near-spheroidal and small TiC grains could be precipitated from the Cu–Ti–C system due to the dissolution of solid carbon in the CuxTi melt based on the theoretical and feasibility analysis.
- (2)
In the super-gravity field, the copper
CRediT authorship contribution statement
Xiaochun Wen: Methodology, Investigation, Formal analysis, Software, Writing - original draft. Lei Guo: Conceptualization, Data curation, Validation, Methodology, Writing - review & editing. Qipeng Bao: Visualization, Validation, Writing - review & editing. Zhancheng Guo: Supervision, Conceptualization, Resources, Writing - review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Acknowledgment
This work was financially supported by the National Natural Science Foundation of China (No. 51804030), and the project of State Key Laboratory of Advanced Metallurgy (41618024).
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