Preparation of Titanium Deposit in Chloride Melts

Zhang

Proceedings of the 13th World Conference on Titanium

2016

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The electrochemical behavior of titanium ions at liquid metal cathodes, such as Sn, in molten chloride salts has been studied by cyclic voltammetry and chronopotentiometry. The results show that the titanium is favoured to deposit at the liquid metal cathodes compared to the solid cathode. Titanium and its alloys were obtained by galvanostatic electrolysis under different current density. The cathodic product prepared was analyzed by XRD, SEM and EDS. The results revealed that the less current density, the more depth the titanium diffused into the cathodic metal.

Section: Methodssupporting

confidence: 79%

Electrochemical Behavior of Titanium Ions at Liquid Metal Cathodes in Molten Salts

Zhang

Proceedings of the 13th World Conference on Titanium

2016

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“…In order to reduce the cost, titanium oxycarbides could be obtained by carbothermal reduction of titanium‐iron ores . However, the oxygen content in the TiC 1− x O x anode material has great effect on the product . The lack of thermodynamic data and structure properties of TiC 1− x O x with different oxygen content has restricted the further research, so it is very important to evaluate the thermodynamic and structure properties of TiC 1− x O x with different oxygen content.…”

Section: Introductionmentioning

confidence: 99%

Experimental and first‐principles study of Ti–C–O system: Interplay of thermodynamic and structural properties

et al. 2017

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The thermodynamic properties and vacancy formation mechanism of Ti–C–O system were investigated by means of empirical calorimetry method and first‐principles calculations. The heat of combustion of titanium oxycarbides (TiC1−xOx, 0≤x≤1) solid solution were first measured by burning the materials in oxygen bomb calorimeter through sophisticated design experimental environment. The mixing enthalpy of the reaction (1−x)TiC + xTiO=TiC1−xOx was further calculated based on the measured data. Mixing enthalpy was also calculated via efficient first‐principles method based on the density functional theory. The vacancies in TiC1−xOx were described as two kinds of models that are disordered and segregated vacancies in titanium oxycarbides solid solution. The calculation results with segregation model show good agreement with the calorimetric results. The heat capacity values were further calculated to deduce the mixing and formation Gibbs free energy. The additive law of the heat capacity and entropy means that the structure of titanium oxycarbides tends to be in order, and this result shows a good agreement with the segregated model in TiC1−xOx. These results are explained on the basis of the interplay between thermodynamic and structural properties, which offered the important theoretic foundation for the novel titanium production process.

“…4 (b) has only one cathodic peak (about -1.6 V vs. Cl 2 /Cl -). 28,29 = 0.61 n The result indicates that the titanium (III) ions are liable to be directly reduced as titanium at liquid cathode.…”

Section: Fig 4 (A)mentioning

confidence: 97%

Electrochemically depositing titanium(iii) ions at liquid tin in a NaCl–KCl melt

et al. 2015

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The electrochemical behavior of titanium ion at liquid tin cathode has been investigated by cyclic voltammetry and square wave voltammetry in a NaCl-KCl melt at 1023 K. The resultsshow that the deposition potentials of alkali metals and titanium at liquid tin are more positive than those at a solid tungsten cathode. Meanwhile, the results prove that titanium (III) ions can be reduced at liquid tin with a one-step reduction Ti 3+ + 3e = Ti, which is a quasi-reversible process with diffusion-controlled mass transfer. The diffusion coefficient of titanium (III) ions is 1.05×10 -5 cm 2 s -1 . Additionally, galvanostatic electrolysis has been carried out to clear the effect of current density on the cathodic products. The result demonstrates that a more depth of titanium will be diffused into the liquid tin cathode at the electrolysis with a lower current density.The electrolyte consisted of an equimolar of NaCl-KCl (reagent grade, AladdinIndustrial Corporation) melt. The electrolyte was pre-dried in an alumina crucible under vacuum by heating it from ambient temperature to 573 K, and then maintaining at this temperature for 24 h. Afterwards, the cooled and pre-dried electrolyte was placed and added 45 mM TiCl 3 prepared beforehand in a glove box for electrochemical test. The working temperature was measured by a thermocouple (protected by an alumina tube) inseted into the melt. All experiments were carried out in a sealed vessel under dried argon atmosphere at 1023 K.A three-electrode setup was applied to investigate the electrochemical behavior of titanium ion. The working electrode, as shown in Fig. 1, was liquid tin stored in a quartz U-bent tube with a 4 mm inner diameter. For comparison, the solid tungsten wire and glass carbon with a 1 mm diameter were served as working electrodes as well. The counter electrode was high purity graphite rod (99.9995%, Alfa Aesar) with a 6 mm diameter. The reference electrode was an Ag/AgCl electrode, referring to a silver wire with a 1mm diameter contained in a mullite tube and dipped into a solution of AgCl (4 wt%) in a NaCl-KCl melt.The reference electrode was calibrated with respect to the Cl 2 /Clelectrode and all experiments potentials were recorded versus the Cl 2 /Clelectrode potential.The electroanalytical techniques including linear polarization, cyclic voltammetry and square wave voltammetry were performed under the same conditions (at 1023 K, under dried argon atmosphere) using a PAR Model 263 potentiostat/galvanostat communicated with a