Production of finely dispersed titanium powder by volumetric reduction of its ions with sodium dissolved in the BaCl2–CaCl2–NaCl melt

The research is intended to develop a technology for the production of finely dispersed (10 to 100 μm) powders of titanium and its alloys suitable for use in additive technologies after classification and spheroidization. A eutectic mixture was used as electrolyte, mole fractions: BaCl₂ – 0.16, CaCl₂ – 0.47, NaCl – 0.37, melting point of 452 °C. Electrolytes with a similar composition are used in industry for the electrolytic production of sodium with high current efficiency. No titanium salts were added to electrolyte. Sodium losses due to evaporation, corrosion, and ion recharge were replenished by a periodic increase in electrolysis current. A VT1-0 titanium plate was used as an anode. The walls of a steel crucible served as a cathode. Sodium was released on these walls and dissolved in electrolyte. Titanium ions were reduced in the bulk of electrolyte and in the anode layer. It is the first time that the results obtained were interpreted using the data on the electrode potentials of Ti³⁺/Ti, Ti²⁺/Ti, Ti³⁺/Ti²⁺ systems. It was shown that the concentration of slowly moving complex Ti3+ ions increases in the anode layer, and sodium dissolved in electrolyte reduces mainly Ti²⁺ ions in the electrolyte volume in the first 12 min of electrolysis. Starting from the 20th min, the concentration of Ti²⁺ ions in the anode layer begins to increase rapidly according to the reaction: 2Ti³⁺ + Ti = 3Ti²⁺ as titanium powder accumulates in the electrolyte volume. At the same time, the proportion of sodium consumed for the reduction of Ti³⁺ ions to Ti²⁺ decreases, which contributes to an increase in current efficiency and cathode potential stabilization for 30 minutes at –2.963 V. After the 50^th min, the reactivity of the salt melt begins to decrease, the concentration of Ti³⁺ ions increases steadily until it levels off with the concentration of Ti²⁺ ions at the 85th min. This sharply increased the current consumption for ion recharge and made it necessary to stop electrolysis after switching on a current of 12 A for a short time (for 40 s). After 10 s, judging by the change in the cathode potential, sodium dissolved in electrolyte was almost completely consumed for titanium ion reduction. After 6 min, the potentials of electrodes returned to the initial anode potential value indicating that the system returned to its original state with the near-zero content of titanium salts and dissolved sodium. 95 % of powder was obtained in the electrolyte volume. Current efficiency was 84.0 % and turned out to be close to the value calculated from the average valence of titanium ions and the loss of anode weight (87.0 %). After ultrasonic dispersion, more than 80 % of powder was in the 10–100 μm range with a maximum at 36 μm. X-ray phase analysis showed that this is practically pure α-titanium (93.06 %) and oxygenated α-titanium (5.45 %). The originality of the research consists in the use of a volumetric, intensive, electrolytic method for producing finely dispersed titanium powders with no dissolved sodium and titanium chlorides in the initial and final electrolytes, in a stepwise increase in the current and potentiometric process control. The uniqueness of the research consists in the titanium powder obtained where the major part is in the melt volume in the form of intergrowths that are easily crushed by ultrasonic dispersion into individual crystals. Over 80 % of these crystals were in the range of 10–100 μm required for additive technologies with an average size of 36 μm.

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