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Method for preparing refractory active metal or alloy

An active metal and refractory technology, applied in the field of metallurgy of rare earth metals, heavy rare earth metals and their alloys, can solve the problems of electrochemically polarized small metals, achieve short production processes, reduce energy consumption, and avoid secondary The effect of secondary electrolysis

Inactive Publication Date: 2006-09-27
WUHAN UNIV +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the difference between the decomposition voltage of heavy rare earth oxides or oxychlorides and the decomposition voltage of calcium oxide is only 20-50mV, and the deposition of calcium will inevitably occur at the same time when electrolytically reducing solid heavy rare earth oxides. Solid heavy rare earth compounds are difficult to reduce to the corresponding metals because the applied electrochemical polarization is too small, so it is considered that heavy rare earth metals can only be extracted through metallothermal reduction.

Method used

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  • Method for preparing refractory active metal or alloy
  • Method for preparing refractory active metal or alloy
  • Method for preparing refractory active metal or alloy

Examples

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Effect test

Embodiment 1

[0044] Tb with a purity of 99.99% 4 o 7 The powder is mixed with water, pressed into blocks at 2-5MPa, sintered at 1000°C in air for 1-4 hours, and the porosity of the sample is 30-48% ( figure 1 ). Weigh 5-10g sintered body, put it in molybdenum / tungsten / tantalum basket, drop to CaCl 2 The melt is used as the cathode, and the graphite crucible is used as the anode. In an argon atmosphere, at 900°C, the cell pressure is controlled at 3.4V, and the electrolysis is performed for 5-18 hours. The electrolysis product can be smelted by vacuum to remove the salt attached to the product. The impurity CaCl in the product can also be washed out by dimethyl sulfoxide 2 . After its electrolysis product was washed with dimethyl sulfoxide solvent, SEM ( figure 2 ) to observe its morphology and EDAX analysis components ( image 3 ), confirmed that the spongy rare earth metal terbium was obtained by electrolysis.

Embodiment 2

[0046] Dy with a purity of 99.9% 2 o 3 The powder is mixed with water, pressed into blocks at 2MPa, and sintered in air at 700°C for 5 hours, and the porosity of the sample is 50-60%. Weigh 5-10g sintered body, put it in molybdenum / tungsten / tantalum basket as cathode in CaCl 2 - Using graphite rod as anode in NaCl mixed melt, in argon atmosphere, electrolyzing at 650°C with a cell pressure of 4.5V for 5-18 hours. The electrolysis product was confirmed to be Dy metal element ( Figure 4 ), the oxygen content is 1000-5000ppm.

Embodiment 3

[0048] Tb with a purity of 99.99% 4 o 7 powder with 10wt% NH 4 HCO 3 Mix well, press into blocks at 2-5MPa, pre-fire in air at 300°C for 1-3 hours, then heat up to 1000°C and sinter for 2-4 hours to obtain a sample with a porosity of 65-75%. Filled with CaCl at 600°C 2 + LiCl mixed molten salt titanium crucible, bound Tb with molybdenum wire 4 o 7 The powder sintered block is used as the cathode, and the graphite is used as the anode, and the electrolysis is carried out at a controlled voltage of 4.2V for 8-16 hours in an argon atmosphere.

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Abstract

This invention relates to a method for preparation of refractory active metals or alloys, which comprises the following steps: selecting CaCl2 or mixed salt electrolyte mainly including CaCl2 as flux, coining or perfusing refractory active metals to be block-shaped, sintering them to get sintered cake, compounding sintered cake and liquid of conductive cathode group and making them as cathode, making graphite or inert electrode as anode; making electrolyzation voltage no lower than academic decomposition voltage of melted salt, and making electrochemical reduction carryed out on cathode, but not forming compact sedimentary deposit to prevent the touch of compounds and electrolyte, controlling electrolyzation temperature at 500-1000 degrees, controlling the electrolyzation time according to 1-4 times theoretical electrical energy demand, making sure inert atmosphere in electrolytic process; then getting refractory metals or alloys which is electrolyzation product. The invention has short flow of production, low energy consumption, little contamination, and is easy to product continuously.

Description

technical field [0001] The invention relates to a method for electrolytically refining refractory active metals and alloys from refractory active metal compounds, which is particularly suitable for the extraction of heavy rare earth metals and their alloys, and belongs to metallurgy of rare earth metal materials. Background technique [0002] Rare earth metals are important raw materials for magnetic materials, and various new magnetic functional alloys (such as permanent magnets, magnetostrictive, magneto-optical recording materials, etc.) composed of heavy rare earth metals and iron-based metals have been more and more widely used. At present, there are two methods for preparing heavy rare earth metals: metallothermic reduction and reduction-distillation. These methods require the use of pure active metal reducing agents and are carried out in an oxygen-free environment. Usually, the oxides need to be chlorinated or fluorinated in advance. The process is complicated, the p...

Claims

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Application Information

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IPC IPC(8): C25C3/26C25C3/34C25C3/36
Inventor 汪的华陈政邱国红金先波
Owner WUHAN UNIV
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