CN112719266A - Electrochemical deoxidation sintering method for metal powder - Google Patents
Electrochemical deoxidation sintering method for metal powder Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 120
- 239000002184 metal Substances 0.000 title claims abstract description 120
- 239000000843 powder Substances 0.000 title claims abstract description 60
- 238000005245 sintering Methods 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 39
- 150000003839 salts Chemical class 0.000 claims abstract description 80
- 239000001301 oxygen Substances 0.000 claims abstract description 60
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 32
- 239000010439 graphite Substances 0.000 claims abstract description 32
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 31
- -1 rare earth chloride Chemical class 0.000 claims abstract description 26
- 239000003792 electrolyte Substances 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims description 51
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 44
- 229910052719 titanium Inorganic materials 0.000 claims description 33
- 229910052750 molybdenum Inorganic materials 0.000 claims description 21
- 238000005868 electrolysis reaction Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000005292 vacuum distillation Methods 0.000 claims description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 229910001508 alkali metal halide Inorganic materials 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 229910052720 vanadium Inorganic materials 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910000048 titanium hydride Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 150000008045 alkali metal halides Chemical class 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 41
- 239000010936 titanium Substances 0.000 description 36
- 238000005498 polishing Methods 0.000 description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 24
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 23
- 239000011733 molybdenum Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 12
- 150000002910 rare earth metals Chemical group 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 239000012535 impurity Substances 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000012300 argon atmosphere Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 5
- 229910001182 Mo alloy Inorganic materials 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 150000003841 chloride salts Chemical class 0.000 description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 4
- 229910009523 YCl3 Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910000599 Cr alloy Inorganic materials 0.000 description 2
- 229910052689 Holmium Inorganic materials 0.000 description 2
- 229910002249 LaCl3 Inorganic materials 0.000 description 2
- 229910018057 ScCl3 Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000788 chromium alloy Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- BUKHSQBUKZIMLB-UHFFFAOYSA-L potassium;sodium;dichloride Chemical compound [Na+].[Cl-].[Cl-].[K+] BUKHSQBUKZIMLB-UHFFFAOYSA-L 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910002420 LaOCl Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- XSQMSOYAHMZLJC-UHFFFAOYSA-N [Cr].[Ti].[V] Chemical compound [Cr].[Ti].[V] XSQMSOYAHMZLJC-UHFFFAOYSA-N 0.000 description 1
- WFISYBKOIKMYLZ-UHFFFAOYSA-N [V].[Cr] Chemical compound [V].[Cr] WFISYBKOIKMYLZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- PCMOZDDGXKIOLL-UHFFFAOYSA-K yttrium chloride Chemical compound [Cl-].[Cl-].[Cl-].[Y+3] PCMOZDDGXKIOLL-UHFFFAOYSA-K 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1039—Sintering only by reaction
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrolytic Production Of Metals (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides an electrochemical deoxidation sintering method for metal powder, which comprises the following steps: performing metal powder to obtain an intermediate forming body; using molten salt at least comprising rare earth chloride as electrolyte, using the intermediate formed body as cathode and graphite as anode, and carrying out electrolytic sintering deoxidation under the conditions of temperature above 800 ℃ and voltage above 2.5V to obtain the low-oxygen metal product. The method can realize the preparation of the low-oxygen metal product by using the high-oxygen metal powder, greatly reduce the production cost and ensure that the metal product has the product characteristics of good strength, toughness and the like.
Description
Technical Field
The invention relates to the technical field of metal deoxidation, in particular to an electrochemical deoxidation sintering method for metal powder.
Background
Powder metallurgy is commonly used to produce products composed of pure metals or metal alloys. The metal powder or metal powders blended together are pressed into an intermediate compact of a desired shape, and then sintered by heating the intermediate compact until the metal powder particles are bonded together.
The presence of oxygen in metal powders (such as titanium) often compromises sintering and final product properties such as strength and toughness. In the existing metal powder sintering process, which does not have the deoxidizing capability, for example, in the molding sintering process of a titanium spectacle frame, high-quality (low-oxygen content) metal powder is generally used as a raw material to obtain a low-oxygen metal product through sintering, but the high-quality (low-oxygen content) metal powder is expensive, so that the production cost is greatly increased; if a relatively inexpensive high-oxygen metal powder is directly used as a raw material for sintering, the oxygen content of the metal product tends to be high, and the properties of the metal product such as strength and toughness tend to deteriorate.
Disclosure of Invention
In view of the deficiencies in the prior art, it is an object of the present invention to address one or more of the problems in the prior art as set forth above. For example, one of the objects of the present invention is to provide an electrochemical deoxidation sintering method which can simultaneously deoxidize during the sintering process of metal powder so that the oxygen content of a metal product is less than 200 ppm.
The invention provides an electrochemical deoxidation sintering method for metal powder, which comprises the following steps: performing metal powder to obtain an intermediate forming body; using molten salt at least comprising rare earth chloride as electrolyte, using the intermediate formed body as cathode and graphite as anode, and carrying out electrolytic sintering deoxidation under the conditions of temperature above 800 ℃ and voltage above 2.5V to obtain the low-oxygen metal product.
The method of the invention uses the molten salt as the electrolyte, and sintering deoxidation is carried out under the condition of high-temperature electrolysis, so that sintering and deoxidation are carried out simultaneously. The specific principle and the reaction process include:
cathode: RE3++3e-＝RE (1)
3[O]inA(s)+2RE(s,l)+RECl3(l)→3A(s)+3REOCl(s)↓ (2)
Anode: c(s) + xO2-＝COx(g)↑+2xe- (3)
A in the formula (1) can be one metal or the combination of more than two metals of Ti, V, Cr, Zr, Hf, Nb, Ta, Mo and W, or A can be TiH2. RE is rare earth metal, and can be any one of Sc, Y, La, Ce, Tm, Ho, Sm, Gd, Dy, Lu and Pr. [ O ]]inARepresents solid-solution oxygen in the metal A. Specifically, the reactions occurring at the cathode are as follows:
RE3++3e-＝RE (4)
2RE+3[O]inA＝RE2O3 (5)
RE2O3＝2RE3++3O2- (6)
O2-+RE3++Cl-＝REOCl (7)
the reactions (4) to (7) are carried out on the cathode in sequence, and firstly molten salt is electrolyzed to chlorinate rare earth RECl3Rare earth metal simple substance RE can be separated out, and then the rare earth metal simple substance RE reacts with oxygen in the metal powder A to generate RE2O3。RE2O3Will dissolve to form RE3+And O2-，O2-A part and RECl3(i.e., RE)3+With Cl-) Reaction to produce REOCl, and transferring part of the REOCl to the anode to react with C to produce COx。
As shown in fig. 1, fig. 1 is a schematic diagram of an electrochemical deoxidation sintering process of metal powder. At the cathode, oxygen ([ O ]) contained in the intermediate formed body obtained by the production of the metal powder A]inA) With cathodically deposited rare earth metal and rare earth chloride (in the electrolyte as RE)3+Ions and Cl-Ion) reaction, oxygen in the intermediate formed body is removed under the high temperature condition, so that a metal product with the oxygen content of less than 200ppm is obtained, and meanwhile, a byproduct rare earth oxychloride (REOCl) precipitate is generated; in additionExternal partial deoxygenation product (O)2-) Reacting with carbon at the anode to produce COX(CO or CO)2). Since the electrolyte consists mainly of chloride, Cl is also present on the anode-Cl formation after loss of electrons2. A titanium or high temperature corrosion resistant metal frame may be sleeved outside the intermediate forming body, as shown by the dotted line frame outside the intermediate forming body in fig. 1, and the metal frame is provided to facilitate the recycling of metal products.
For example, when the metal powder is titanium metal powder and the rare earth metal is yttrium (Y), the reaction that occurs between the anode and the cathode can be:
cathode: y is3++3e-＝Y (8)
3[O]inTi(s)+2Y(s,l)+YCl3(l)→3Ti(s)+3YOCl(s)↓ (9)
Anode: c(s) + xO2-＝COx(g)↑+2xe- (10)
Compared with the prior art, the beneficial effects of the invention at least comprise at least one of the following:
(1) the method can realize the preparation of the low-oxygen metal product by using the high-oxygen metal powder, greatly reduce the production cost and ensure that the metal product has the product characteristics of good strength, toughness and the like;
(2) the method can deoxidize while the metal powder is electrolytically sintered, and can ensure that the oxygen content in the metal product is less than 200 ppm;
(3) the method can realize continuous operation of sintering and deoxidation only by replacing the carbon anode and supplementing the molten salt;
(4) according to the invention, the residual molten salt on the surface of the metal product is removed by vacuum distillation cleaning, and an acid solution is not required for cleaning, so that the energy is saved and the environment is protected;
(5) the invention can realize the clean and cyclic utilization of the byproduct rare earth oxychloride (REOCl), has no rare earth consumption and saves resources.
Drawings
The above and other objects and features of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a schematic diagram of electrochemical deoxidation sintering of metal powder.
Detailed Description
Hereinafter, the metal powder electrochemical deoxidation sintering method according to the present invention will be described in detail with reference to the accompanying drawings and exemplary embodiments.
The invention provides an electrochemical deoxidation sintering method for metal powder. In an exemplary embodiment of the electrochemical deoxidation sintering method for metal powder of the invention, the method may comprise:
s01, performing the metal powder to obtain an intermediate formed body.
And S02, taking molten salt at least comprising rare earth metal and rare earth chloride as electrolyte, taking the intermediate forming body as a cathode and graphite as an anode, and electrolyzing at the temperature of above 800 ℃ and the voltage of above 2.5V to obtain the low-oxygen metal product.
Further, in S01, the metal powder may be prefabricated in advance into an intermediate molded body of a desired shape, for example, a metal spectacle frame, a metal tube, a metal block, or the like, for metal powder preforming. The intermediate molded body can be prepared by pressing, molding, or the like. There may be no requirement for the particle size of the metal powder, for example, the particle size of the metal powder may be less than 45 μm.
Further, the method according to the present invention can perform deoxidation treatment on various metal powders. The metal powder may include one of titanium (Ti), vanadium (V), chromium (Cr), zirconium (Zr), hafnium (Hf), niobium (Nb), tantalum (Ta), molybdenum (Mo), and tungsten (W), or an alloy powder composed of two or more of titanium (Ti), vanadium (V), chromium (Cr), zirconium (Zr), hafnium (Hf), niobium (Nb), tantalum (Ta), molybdenum (Mo), and tungsten (W), or titanium hydride (TiH)2) And the like. The alloy of the composition may include vanadium-titanium alloy, vanadium-chromium alloy, vanadium-titanium-chromium alloy, tungsten-molybdenum alloy, and the like.
Further, the rare earth metal RE may include any one of Sc, Y, La, Ce, Tm, Ho, Sm, Gd, Dy, Lu and Pr. La, Ce, Y and Ho may require special attention. The La and Ce used in the preparation method are low in price and low in cost. Under the same electrolytic sintering deoxidation conditions, the oxygen content in the metal powder can be reduced to a lower degree after Y or Ho is used. YOCl or HoOCl is more stable in molten salt than LaOCl or CeOCl, so that the deoxidation reaction in the reaction formula (2) is promoted to be carried out forward, the deoxidation reaction is more thorough, and the deoxidation effect is better.
Further, an alkali metal halide salt may be added to the electrolyte in addition to the rare earth metal and the rare earth metal chloride. The alkali metal halide salt is added, on one hand, compared with the rare earth metal chloride, the price of the alkali metal halide is lower, and the production cost can be reduced; on the other hand, the addition of the alkali metal halide can reduce the melting point of the molten salt, reduce the working temperature and achieve the purposes of energy conservation and consumption reduction. The alkali metal halide salt may include halide salts of Li, Na, K, Mg, Ca or combinations of these salts, and the corresponding halogen may include Cl, Br and I. Further, the alkali metal halide salt added may be NaCl and/or KCl. Of more concern is the addition of NaCl and KCl to give NaCl-KCl-RECl3The melting point of the molten salt electrolyte is lower, so that the energy consumption can be saved.
Further, the addition amount of the rare earth metal and the rare earth chloride may be added in accordance with the theoretical consumption amount of the above reaction formula (1) based on the actual metal powder amount. It is noted that more rare earth metals and rare earth chlorides than theoretically need to be added in order to provide the electrolyte with sufficient oxygen dissolving capacity and to take into account the thoroughness of deoxidation of the metal powders. For example, an amount of 5 wt.% to 30 wt.% more than the theoretical amount may be added. Of course, larger amounts of rare earth metals and rare earth chlorides can be added without regard to cost.
Further, the temperature at the time of electrolysis needs to be set higher than the melting point of the molten salt, and therefore, the temperature at the time of electrolysis is set to 800 ℃ or higher. Since the temperature has a great influence on the deoxidation rate and the deoxidation effect, the higher the temperature is, the higher the deoxidation rate is but the oxygen content in the metal product may become high, and the higher the temperature is, the higher the heat resistance requirement of the equipment is, and the greater the energy consumption is, therefore, the temperature at the time of electrolysis is preferably set at 800 ℃ to 1200 ℃ in consideration of the above-mentioned influence factors in combination. Furthermore, the oxygen content of the metal product can be lower while the energy is saved and the consumption is reduced, and the set electrolysis temperature can be 800-900 ℃. The voltage for electrolysis needs to be set higher than the decomposition voltage of the molten chloride salt to be used, and the RE generated by the electrolysis of the rare earth chloride is deoxidized. Therefore, the voltage during electrolysis is set to 2.5V or more. If the molten salt contains other alkali chloride salts, for example, when the molten salt contains NaCl and/or KCl, the applied voltage is not too high, which may cause decomposition of NaCl and/or KCl to generate alkali and chlorine, thereby reducing the electrolysis efficiency. Therefore, it is necessary for the applied voltage to be greater than the decomposition voltage of the rare earth chloride molten salt and less than the decomposition voltage of the alkali metal chloride salt. For example, the set voltage is 2.6V to 3.1V, which is greater than the decomposition voltage of the rare earth chloride molten salt and less than the decomposition voltage of the alkali chloride salt. For example, the set voltage may be at 2.8V.
The temperature required for electrolysis needs to be set in accordance with the applied voltage. After different temperature and voltage comparisons are applied, the oxygen content of the metal product can be reduced by 3 to 8 percent compared with the oxygen content of other temperature and voltage matched electrolysis under the conditions of 870 ℃ of temperature and 2.6V of voltage and the same electrolysis time.
Further, the method may further comprise: after the low-oxygen metal product is obtained, vacuum distillation is carried out under the conditions that the temperature is 850-1000 ℃ and the pressure is 0.1-1.0 Pa so as to remove residual molten salt on the surface of the metal product. After the metal product is deoxidized, a large amount of molten salt adheres to the surface of the metal product. In order to obtain a metal product with high purity, molten salt on the surface needs to be removed. Distillation is carried out in vacuum, the boiling point of the fused salt can be reduced in a vacuum environment, the fused salt can volatilize under the condition of 850-1000 ℃, the volatilized fused salt can be directly recycled and reused, and waste water and waste of the fused salt after pickling caused by removing the fused salt on the surface by other operations such as pickling are avoided. The distillation temperature is too low, and the molten salt cannot volatilize; the distillation temperature is too high, the energy consumption is increased, and unnecessary waste is caused. For example, the temperature of the vacuum distillation may be 920 ℃ and the pressure 0.6 Pa. The time of vacuum distillation can be 3.5 h-5 h. In the vacuum distillation time, the molten salt can be thoroughly treated, unnecessary vacuum distillation time is avoided, and energy consumption is saved. The molten salt obtained by vacuum distillation can be recycled.
Further, according to the above reaction formula (1), after completion of electrolytic sintering deoxidation, a by-product REOCl precipitate is generated in addition to the low-oxygen metal product. The method can perform electrolysis or carbon thermal chlorination on the by-product REOCl precipitate, and can realize the recovery and cyclic recycle of the RE element.
Further, before electrolytic deoxidation, pretreatment of the molten salt can be carried out, and the method specifically comprises the following steps: controlling the temperature at 350-450 ℃ to carry out vacuum drying on the electrolyte for 8-15 h, then heating until the electrolyte is melted, and carrying out pre-electrolysis under the condition of 2.0-2.2V by taking graphite as an anode and a metal crucible containing the electrolyte as a cathode. The purpose of pre-electrolysis is to remove impurities such as residual gas (oxygen) or metal in the mixed molten salt.
Further, the sintering time may be 13 hours or more. For example, the sintering time may be 13 to 20 hours. For another example, the sintering time may be 17 hours. For the sintering time, if the sintering time is less than 13h, the deoxidation of the metal powder is incomplete, which affects the oxygen content in the metal product and causes the oxygen content in the metal product to be too high. If the sintering time is longer than 20 hours, the oxygen content in the metal product is not greatly reduced. By counting the oxygen content of the metal product under different sintering times, the oxygen content in the metal product is gradually reduced along with the prolonging of the electrolytic sintering time, and the oxygen content in the metal product is slowly reduced after the sintering time reaches 20 hours, so that the sintering time is set to be 13-20 hours in consideration of the cost and the sintering time saving.
Further, the method of the present invention may add a predetermined amount of titanium sponge to the electrolyte. The titanium sponge is capable of absorbing oxygen in the reaction environment. The mass of the added titanium sponge can be determined according to the amount of the molten salt and the amount of the metal powder, and can be a given value or an empirical value. For example, the mass of the titanium sponge added may be 5 to 10 times the mass of the metal powder.
In order that the above-described exemplary embodiments of the invention may be better understood, further description thereof with reference to specific examples is provided below.
For the sake of easy observation and better illustration of the process of the invention, the metal powder preform to obtain the intermediate compact can be prepared by the following method:
pressing the metal powder into small pieces with the diameter of 15-25 mm and the thickness of 4-8 mm under the pressure of 450-600 Mpa to obtain an intermediate forming body.
Example 1
Step 2, 30g of titanium sponge, an intermediate formed body, and 500g of NaCl-KCl-YCl3Molten salt (wherein, the molar ratio of NaCl-KCl is 1:1, YCl)3The mass ratio of (1) is 60%), putting the graphite into a titanium crucible (89mm in outer diameter, 3mm in thickness and 350mm in height), sealing the titanium crucible in a stainless steel reactor, heating the titanium crucible to 400 ℃ by an electric furnace, drying the titanium crucible in vacuum for 12 hours, heating the titanium crucible to 800 ℃ to melt the molten salt, putting the graphite into the molten salt, and pre-electrolyzing the graphite serving as an anode and the titanium crucible serving as a cathode to remove impurities such as oxygen in the molten salt.
And 3, taking the titanium frame filled with the intermediate forming body as a cathode and graphite as an anode, and applying a voltage of 3.1V at the temperature of 800 ℃ for electrolysis for 17.5 h.
Step 4, after the electrolytic deoxidation sintering is finished, taking out the titanium metal product from the molten salt, cooling for 30s in the argon atmosphere, removing the residual molten salt on the surface of the titanium metal product by adopting vacuum distillation (the temperature is 850 ℃, the time is 3.5h, and the system pressure is 0.1Pa), then polishing by adopting acetic acid, then performing physical polishing by using a polishing grinder, and using HF-HNO3–H2O (1:4:10) was chemically polished for 30 seconds, and finally the oxygen content was measured using LECO (TC-400) and found to be 128ppm in the titanium metal article.
Example 2
Step 2, mixing the intermediate formed body with 600g NaCl-KCl-HoCl3Molten salt (wherein, the molar ratio of NaCl-KCl is 1:1, HoCl)370%) into a titanium crucible (89mm outer diameter, 3mm thickness, 350mm height), then placing into a stainless steel reactor for sealing, heating by an electric furnace to 450 ℃, vacuum drying for 15h, then heating to 850 ℃ to melt the molten salt, placing graphite into the molten salt, taking the graphite as an anode and the titanium crucible as a cathode, and pre-electrolyzing to remove oxygen impurities in the molten salt.
And 3, taking the titanium frame filled with the intermediate forming body as a cathode and graphite as an anode, and applying a voltage of 3.0V at 850 ℃ for 20 h.
Step 4, after the electrolytic deoxidation sintering is finished, taking out the titanium metal product from the molten salt, cooling for 30s in the argon atmosphere, removing the residual molten salt on the surface of the titanium metal product by adopting vacuum distillation (the temperature is 1000 ℃, the time is 4.0h, and the system pressure is 0.8Pa), then polishing by adopting acetic acid, then performing physical polishing by using a polishing grinder, and using HF-HNO3–H2O (1:4:10) was chemically polished for 30 seconds, and finally the oxygen content was measured using LECO (TC-400), and the oxygen content in the titanium metal article was 180 ppm.
Example 3
Step 2, 40g of titanium sponge, the intermediate formed body, and 800g of NaCl-NaI-CeCl3Molten salt (wherein, CeCl365%) in a molybdenum crucible (89mm in outer diameter, 3mm in thickness and 350mm in height), then putting the molybdenum crucible into a stainless steel reactor for sealing, heating the molybdenum crucible to 420 ℃ by adopting an electric furnace, vacuum drying the molybdenum crucible for 13 hours, heating the molybdenum crucible to 820 ℃ to melt the molten salt, putting graphite into the molten salt, and pre-electrolyzing the graphite by taking the graphite as an anode and the molybdenum crucible as a cathode to remove oxygen impurities in the molten salt.
And 3, taking the molybdenum frame filled with the intermediate forming body as a cathode and graphite as an anode, and applying a voltage of 2.5V at 1200 ℃ for 14 h.
Step 4, after the electrolytic deoxidation sintering is finished, taking out the vanadium metal product from the molten salt, cooling for 30s in an argon atmosphere, removing the residual molten salt on the surface of the vanadium metal product by adopting vacuum distillation (the temperature is 920 ℃, the time is 3.8h, and the system pressure is 0.9Pa), then polishing by adopting acetic acid, then performing physical polishing by using a polishing grinder, and using HF-HNO3–H2O (1:4:10) was chemically polished for 30 seconds, and the oxygen content was finally determined using LECO (TC-400) and was 192ppm in the vanadium metal article.
Example 4
Step 2, 40g of titanium sponge, the intermediate formed body and 700g of NaCl-LaCl3Molten salt (wherein, LaCl365%) into a titanium crucible (89mm outer diameter, 3mm thickness, 350mm height), then placing into a stainless steel reactor for sealing, heating by an electric furnace to 420 ℃, vacuum drying for 13h, heating to 820 ℃ to melt the molten salt, placing graphite into the molten salt, taking the graphite as an anode and the titanium crucible as a cathode, and pre-electrolyzing to remove oxygen impurities in the molten salt.
And 3, taking the titanium frame filled with the intermediate forming body as a cathode and graphite as an anode, and applying a voltage of 2.7V at 1150 ℃ for 13 h.
Step 4, after the electrolytic deoxidation sintering is finished, taking out the vanadium-titanium metal product from the molten salt, cooling for 30s in an argon atmosphere, removing the residual molten salt on the surface of the vanadium-titanium metal product by adopting vacuum distillation (the temperature is 920 ℃, the time is 3.8h, and the system pressure is 0.9Pa), then polishing by adopting acetic acid, then performing physical polishing by using a polishing grinder, and using HF-HNO3–H2O (1:4:10) chemical polishing for 30 seconds, and finally determining the oxygen content by using LECO (TC-400) to obtain the vanadium-titanium metal productThe oxygen content in (A) was 151 ppm.
Example 5
Step 2, mixing the intermediate molded body with 500g of KCl-ScCl3Molten salt (wherein, ScCl368%) into a molybdenum crucible (89mm in outer diameter, 3mm in thickness and 350mm in height), then placing into a stainless steel reactor for sealing, heating by an electric furnace to 420 ℃, vacuum drying for 10 hours, then heating to 820 ℃ to melt the molten salt, placing graphite into the molten salt, taking the graphite as an anode and the molybdenum crucible as a cathode, and pre-electrolyzing to remove oxygen impurities in the molten salt.
And 3, taking the molybdenum frame filled with the intermediate forming body as a cathode and graphite as an anode, and applying a voltage of 2.9V at 820 ℃ for 20 h.
Step 4, after the electrolytic deoxidation sintering is finished, taking out the zirconium metal product from the molten salt, cooling for 30s in an argon atmosphere, removing the residual molten salt on the surface of the zirconium metal product by adopting vacuum distillation (the temperature is 870 ℃, the time is 3.8h, and the system pressure is 0.2Pa), then polishing by adopting acetic acid, then performing physical polishing by using a polishing grinder, and using HF-HNO3–H2O (1:4:10) was chemically polished for 30 seconds, and the oxygen content was finally measured by LECO (TC-400) and was 191ppm in the zirconium metal article.
Example 6
Step 2, 35g of titanium sponge, an intermediate formed body, and 600g of NaCl-KCl-TmCl3Molten salt (wherein, TmCl368%) into a titanium crucible (89mm outer diameter, 3mm thickness, 350mm height), then placing into a stainless steel reactor for sealing, and adding by adopting an electric furnaceHeating to 420 ℃, vacuum drying for 10h, heating to 820 ℃ to melt the molten salt, putting graphite into the molten salt, and pre-electrolyzing by taking the graphite as an anode and a titanium crucible as a cathode to remove oxygen impurities in the molten salt.
And 3, taking the titanium frame filled with the intermediate forming body as a cathode and graphite as an anode, and applying a voltage of 2.5V at 980 ℃ for 14 h.
Step 4, after the electrolytic deoxidation sintering is finished, taking out the titanium metal product from the molten salt, cooling for 30s in the argon atmosphere, removing the residual molten salt on the surface of the titanium metal product by adopting vacuum distillation (the temperature is 870 ℃, the time is 3.8h, and the system pressure is 0.2Pa), then polishing by adopting acetic acid, then performing physical polishing by using a polishing grinder, and using HF-HNO3–H2O (1:4:10) was chemically polished for 30 seconds, and finally the oxygen content was measured using LECO (TC-400) and the oxygen content in the titanium metal article was 193 ppm.
Example 7
Step 2, 38g of titanium sponge, an intermediate formed body, and 1000g of LiCl-KCl-YCl3Molten salt (wherein, the molar ratio of LiCl to KCl is 1:2, YCl)362 percent of the total weight of the graphite powder is put into a molybdenum crucible (89mm of outer diameter, 3mm of thickness and 350mm of height), then the molybdenum crucible is put into a stainless steel reactor for sealing, the stainless steel reactor is heated by an electric furnace, the temperature is raised to 440 ℃, the molten salt is melted by heating to 840 ℃ after vacuum drying for 10 hours, the graphite is put into the melted molten salt, the graphite is used as an anode, the molybdenum crucible is used as a cathode, and pre-electrolysis is carried out to remove oxygen impurities in the molten salt.
And 3, taking the molybdenum frame filled with the intermediate forming body as a cathode and graphite as an anode, and applying a voltage of 2.7V at 1100 ℃ for 20 h.
Step 4, after the electrolytic deoxidation sintering is finished, taking out the molybdenum metal product from the molten salt, cooling for 30s in the argon atmosphere, carrying out vacuum distillation (the temperature is 870 ℃, the time is 3.8h,system pressure 0.2Pa) to remove residual molten salt on the surface of the molybdenum metal product, then polishing with acetic acid, then performing physical polishing with a polishing grinder, and performing HF-HNO3–H2O (1:4:10) was chemically polished for 30 seconds, and the oxygen content was finally measured using LECO (TC-400) and was 129ppm in molybdenum metal.
Example 8
Step 2, 32g of titanium sponge, an intermediate formed body, and 1000g of NaCl-KCl-HoCl3Molten salt (wherein, the molar ratio of NaCl to KCl is 1:1, HoCl)365%) in a molybdenum crucible (89mm outer diameter, 3mm thickness, 350mm height), then placing in a stainless steel reactor for sealing, heating by an electric furnace to 440 ℃, vacuum drying for 10h, heating to 840 ℃ to melt the molten salt, placing graphite in the molten salt, taking the graphite as an anode and the molybdenum crucible as a cathode, and pre-electrolyzing to remove oxygen impurities in the molten salt.
And 3, taking the molybdenum frame filled with the intermediate forming body as a cathode and graphite as an anode, and applying a voltage of 2.8V at 1000 ℃ for 19 h.
Step 4, after the electrolytic deoxidation sintering is finished, taking out the tungsten-molybdenum alloy metal product from the molten salt, cooling for 30s in the argon atmosphere, removing the residual molten salt on the surface of the tungsten-molybdenum alloy metal product by adopting vacuum distillation (the temperature is 870 ℃, the time is 3.8h, and the system pressure is 0.2Pa), then polishing by adopting acetic acid, then physically polishing by using a polishing grinder, and using HF-HNO3–H2O (1:4:10) is chemically polished for 30 seconds, and finally, the oxygen content is measured by LECO (TC-400), wherein the oxygen content in the tungsten-molybdenum alloy metal product is 186 ppm.
Although the present invention has been described above in connection with exemplary embodiments, it will be apparent to those skilled in the art that various modifications and changes may be made to the exemplary embodiments of the present invention without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The electrochemical deoxidation sintering method for the metal powder is characterized by comprising the following steps of:
performing metal powder to obtain an intermediate forming body;
using molten salt at least containing rare earth chloride as electrolyte, using intermediate formed body as cathode and graphite as anode, and making electrolytic sintering deoxidation under the conditions of temp. above 800 deg.C and voltage above 2.5V so as to obtain the low-oxygen metal product.
2. The electrochemical deoxidation sintering process of claim 1 wherein the rare earth chloride is any one of rare earth metal chlorides of Sc, Y, La, Ce, Tm, Ho, Sm, Gd, Dy, Lu and Pr.
3. The electrochemical deoxidation sintering process of claim 1 wherein the metal powder is an alloy of one or more of Ti, V, Cr, Zr, Hf, Nb, Ta, Mo, and W, or the metal powder is TiH2。
4. The metal powder electrochemical deoxidation sintering method as claimed in claim 1, 2 or 3, further comprising performing vacuum distillation at 850 ℃ to 1000 ℃ and under 0.1Pa to 1.0Pa after obtaining the low-oxygen metal product, thereby obtaining the low-oxygen metal product with the surface from which the residual molten salt is removed.
5. The electrochemical deoxidation sintering method for metal powder as claimed in claim 4, wherein the vacuum distillation time is 3.5h to 5.0 h.
6. The electrochemical deoxidation sintering process of claim 1, 2, 3 or 5 wherein the electrolyte further comprises an alkali metal halide salt.
7. The electrochemical deoxidation sintering process of claim 6 wherein the alkali metal halide is NaCl and/or KCl.
8. The electrochemical deoxidation sintering method of metal powder as claimed in claim 1, 2, 3, 5 or 7 further comprising subjecting the byproduct rare earth oxychloride to electrolysis or carbothermic chlorination after the completion of the electrolytic sintering deoxidation.
9. The electrochemical deoxidation sintering method for metal powder as claimed in claim 1, 2, 3, 5 or 7, further comprising controlling the temperature at 350-450 ℃ to vacuum dry the electrolyte for 8-15 h before heating to 800-1200 ℃, then heating to melt the electrolyte, and pre-electrolyzing under 2.0-2.2V by using graphite as an anode and a metal crucible containing the electrolyte as a cathode.
10. The electrochemical deoxidation sintering method for metal powder as claimed in claim 1, 2, 3, 5 or 7, wherein the low oxygen metal product is obtained by electrolysis at 800-1200 ℃ under 2.6-3.1V for 13-20 h.
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