CN102424986A - Method for preparation of titanium-tungsten alloy through molten salt electrolysis - Google Patents
Method for preparation of titanium-tungsten alloy through molten salt electrolysis Download PDFInfo
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- CN102424986A CN102424986A CN2011103766574A CN201110376657A CN102424986A CN 102424986 A CN102424986 A CN 102424986A CN 2011103766574 A CN2011103766574 A CN 2011103766574A CN 201110376657 A CN201110376657 A CN 201110376657A CN 102424986 A CN102424986 A CN 102424986A
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Abstract
The invention relates to a method for preparation of titanium-tungsten alloy through molten salt electrolysis. Oxygen in mixture of titanium oxide and tungsten oxide is removed through electrolysis in molten calcium chloride to prepare the titanium-tungsten alloy. TiO2 powder and WO3 powder are mixed according to a certain proportion, adhesives and pore-forming agents are added, and sintering is carried out after formation to prepare an electrode, and the titanium-tungsten alloy with controllable composition can be obtained through electrolysis. The temperature for preparation of the TiW alloy can be reduced significantly, the high-purity and small-sized TiW alloy with the controllable composition can be obtained at the lower temperature; and the preparation method and equipment are simple, the manufacturing process is simple and controllable, and the preparation of high-purity products can be facilitated.
Description
Technical field
The present invention relates to a kind of novel preparation technology of titanium-tungsten alloy, particularly a kind of fused salt electrolysis process prepares the method for titanium-tungsten alloy.
Background technology
The TiW alloy has application widely because of having good performance in fields such as microelectronics and biomedicines; Add the alloy that forms behind the W among the Ti and have higher intensity and hardness; And the ductility loss is very little; Non-magnetic W solid solution can reduce the Young's modulus of Ti in the Ti matrix, and increases radiation resistance; Medically, do not reduce the biocompatibility of Ti behind the interpolation W, but help alleviating the stress that implant produces with the different of matrix, improve the X-ray identity of interfibrous stress distribution of blood vessel and health and thin cross section blood vessel.At electronic information field, along with the development of semi-conductor VLSI industry, highly purified TiW alloy can be used for electrode materials, diffusion impervious layer and wiring material etc. with form of film.Mainly be to adopt methods such as high-temperature vacuum melting, powder metallurgy and mechanical alloying to prepare the TiW alloy at present; But these methods all exist production cost height, complex process or the not high shortcoming of product purity; Reduced the performance of titanium-tungsten alloy, to a great extent limit its apply.
The fusing point of Ti is 1670 ℃ approximately; The fusing point of W is about 3522 ℃, and the fusing point of W and density are all much higher than Ti, is difficult to during melting directly add; Even used master alloy; The time that W stops in liquid Ti molten bath in the process of setting is very short, and very fast condensation is not perhaps dissolved in the metal pool of vacuum remelting, and the delaminating deposition phenomenon takes place.In addition, composition is difficult to accurate control during melting TiW alloy, because the fusing point of titanium is high, active big, is easy to receive the pollution of impurity such as C, O, N simultaneously, and its processing characteristics and use properties are worsened, and the yield of gained TiW alloy is low, production cost is high.And when using powder metallurgic method, because raw material Titanium Sponge 40-60 mesh complex manufacturing, energy consumption is high, efficient is low, is prepared into and carries out alloying process again behind the powder and need increase new energy consumption, cause the production cost of alloy higher.Adopt high-energy ball-milling process (mechanical alloying) but the adjustable TiW alloy of prepared composition, and obtain tiny particle size, but easy impurity, the increase O content introduced.
Fused salt electrolysis process (FFC method) can prepare multiple HMP or refractory metal and the alloy thereof that ordinary method is difficult to production; There is not liquid metal in the whole technological process; Technical process is short, facility investment is few, temperature of reaction is low, energy consumption is little; Being the novel method of a kind of Ti of preparation and other refractory metal and alloy thereof, also is the novel environment-friendly process than the tool development prospect.Electrolysis TiO in fused salt
2-WO
3Mixture utilizes electrochemical reduction to prepare titanium-tungsten alloy, can eliminate uneven components and reduce oxygen level, and produce the alloy product of new constituent.
The report that relevant both at home and abroad fused salt electrolysis process prepares titanium-tungsten alloy seldom; The interim one piece of paper " Direct electrochemical production of Ti-10W alloys from mixed oxide preform precursors " of having delivered of " Journal of Alloys and Compounds " magazine the 419th volume 1-2 in 2006; Introduced the process of the Ti-10W alloy of the low W content of fused salt electrolysis process preparation; But its W content of the titanium-tungsten alloy of reporting in the document is lower, and W content is no more than 10%.Chinese invention patent CN101985763A has proposed " a kind of fused salt electrolysis prepares the method for tungsten-base alloy powder "; With alkali and earth alkali metal villaumite is supporting electrolyte; With tungstate and MOX is electroactive substance; Do the cathode and anode material with carbon material, under 750～900 ℃, 2.0～3.0V voltage, prepare tungsten-base alloy powder through fused salt electrolysis, this method is that common electrolytic process prepares tungstenalloy.Electrolysis TiO in fused salt
2-WO
3Mixture prepares the higher titanium-tungsten alloy of W content, does not see relevant report at present as yet; And use the titanium-tungsten alloy of molten salt electrodeoxidation method (FFC) preparation high W content also not see report.
Summary of the invention
Technical problem to be solved by this invention provides the method that a kind of fused salt electrolysis process prepares titanium-tungsten alloy; Shortcoming to traditional titanium-tungsten alloy production; Utilize the advantage of fused salt electrolysis process, use better simply equipment and technology, the titanium-tungsten alloy that prepared composition is controlled, oxygen level is low.
For the purpose that realizes solving the problems of the technologies described above, the present invention has adopted following technical scheme:
Fused salt electrolysis process of the present invention prepares the method for titanium-tungsten alloy, comprising:
(1), with mean particle size 2
μBelow the m, purity is greater than 98% TiO
2And WO
3Powder is pressed the mixed of 9:1～3:7; Adding the carbon dust be equivalent to two kinds of powder gross weights 5～10% or carbon dust and titanium hydride powder ratio is 10: mixture (1-10) is made pore-forming material; Z 150PH (PVA) solution or the zero(ppm) water that add solid amount 6～12% are again made tackiness agent; Use the method for machinery to mix, make mixed powder;
(2), to (1) preparation mixed powder carry out mold pressing, pressure 3～15MPa, pressurize 1～3min processes biscuit; Perhaps in the mixed powder of preparation, continue to add the slurry that zero(ppm) water is processed 60～80% concentration, injection forming in mould makes molding blank; The electrode base substrate of processing is that diameter is not less than 60mm, highly is the cylindrical of 3～10mm, or the length of side 50～150mm, height 3～10mm's is lamellar;
(3), be not higher than 5%, at 900～1200 ℃ of sintering 3～10h, do not make TiO to the base substrate seasoning at room temperature of (2) moulding or being dried to moisture below 150 ℃
2-WO
3The mixture electrode is done negative electrode, is anode with the high purity graphite, under the argon gas atmosphere protection, with CaCl
2For fused salt carries out electrolysis, 800～1100 ℃ of electrolysis temperatures, electrolysis voltage is 2.8～3.2V, at first is evacuated to before the electrolysis to be superior to 10Pa, charges into argon gas then, argon shield in the experiment whole process; After electrolysis finishes, the solid electrolytic product on the negative electrode is proposed fused salt, be cooled to room temperature; To cool off back electrolysate cleaning and removing fused salt, make titanium-tungsten alloy.
Described Z 150PH (PVA) solution, concentration can be 2 ~ 20%.
The method of cooling back electrolysate flush away electrolysis fused salt can be: using distilled water flushing earlier, is 1～2% hydrochloric acid soln washing in the UW then, washing again, and in the oven dry of the temperature below 100 ℃, the product of acquisition is a titanium-tungsten alloy at last.
Described TiO
2-WO
3The mixture electrode is that diameter is not less than 60mm, highly is the cylindrical of 3～10mm, more than the substance 25g; Or adopt the length of side 50～150mm, highly be the lamellar sample of 3～10mm, more than the substance 25g.
Described TiO
2And WO
3Powder is analytically pure TiO
2And WO
3Powder, TiO
2Powder is a Detitanium-ore-type, WO
3Powder is a close-packed hexagonal structure.
Described Z 150PH, titanium hydride, carbon dust are the analytical pure product.
The electrolysis temperature-rise period is: be evacuated to earlier and be superior to 10Pa, charge into argon gas, be warming up to 350 ℃ and be incubated more than the 2h, make CaCl
2The fused salt thorough drying is warmed up to electrolysis temperature then and begins electrolysis; After electrolysis finishes, stop heating, make the stove naturally cooling, during charge into argon gas continuously.
The dc electrolysis voltage of electrolytic process is 2.8～3.2V; Perhaps compound intermittent pulsed current, pulsewidth 5～10
μS is between arteries and veins 10～30
μS, pulsed current 0～20A.
Behind 900～1200 ℃ of sintering, TiO
2-WO
3The porosity of electrode is 35～55%, TiO
2Crystalline structure change rutile-type into by Detitanium-ore-type, WO
3Do not change; TiO
2And WO
3Between chemical reaction does not generally take place, work as WO
3When content was low, chemical reaction or part chemical reaction possibly take place between the two.
These technical schemes also can mutual combination perhaps combine, thereby reach better technique effect.
Through adopting technique scheme, the present invention has following beneficial effect:
(1) the present invention can obviously reduce the preparation temperature of TiW alloy, can under lower temperature, obtain the tiny TiW alloy of high purity, controllable component and crystal grain.
(2) simple, the device simple of preparation method of the present invention, ME simple controllable.
(3) the present invention helps the preparation of high purity product.
Embodiment
Below specify several kinds of embodiment of the present invention, but the present invention is not limited to this, for a person skilled in the art, under the prerequisite that does not break away from the inventive method, can also make some distortion and improvement, all should belong to protection scope of the present invention.
Embodiment 1:
Mean particle size is respectively 0.7
μM and 0.9
μThe TiO of m
2And WO
3Powder is pressed mass ratio 1:1 and is mixed, and after adding PVA solution and carbon dust mechanically mixing and stirring, the use mould is pressed into cylindrical electrode.Elder generation is seasoning 48h at room temperature, in vacuum atmosphere oven, vacuumizes earlier and charges into argon shield again, gets rid of PVA through 350 ℃ of annealing, and 900 ℃ of high temperature sinterings make TiO then
2-WO
3The mixture electrode, the about 27g of weight, the about 25g of boring back weight.The processing parameter of electrode preparation is seen table 1.
Table 1 technology for preparing electrode parameter
The TiO that makes
2-WO
3About 41%, the two kind of oxide powder of pores rate still keeps very tiny particulate state, has sintering to a certain degree to connect between particle.Through the XRD material phase analysis, behind the sintering, TiO
2Change rutile-type into from Detitanium-ore-type, WO
3Powder does not have recurring structure to change, and does not react between two kinds of powder.
With the high purity graphite is anode, TiO
2-WO
3The mixture electrode is connected on and makes negative electrode on the molybdenum rod, and the gross weight of electrolyte is about 50g, in special electrolytic furnace, is electrolyzer with the high-density graphite crucible, CaCl
2Fused salt is placed in one and carries out electrolysis.Vacuumize earlier, when vacuum tightness is superior to 10Pa, charge into argon gas continuously, CaCl
2Fused salt is dried 2h to drive away moisture at 350 ℃; Then continue to heat up, treat that the fused salt temperature is elevated to 900 ℃ also after a period of stabilisation, begins to carry out electrolysis.The preelectrolysis 1h under 2.0V voltage of elder generation, purpose is to remove moisture remaining in the fused salt and impurity; Under the voltage of 3.0～3.2V, carry out formal electrolysis then, the stable state Faradaic current is about 16A, and electrolysis proposes fused salt with electrode after finishing, and in stove, naturally cools to room temperature, and whole process is all carried out under argon shield.
Electrolysate is used earlier the distilled water flushing specimen surface, remove the remaining fused salt duricrust in electrode sample surface, then auxiliary down with 2% aqueous hydrochloric acid washing by soaking at UW, remove the CaCl in the product
2Fused salt and some other impurity continue to clean with zero(ppm) water then, dry at 80 ℃ of counter electrode products at last.
After electrolysate cleaning, drying and the polishing, have metalluster, intensity higher, become alloy, particle grow up and each other sintering together, porosity obviously reduces.Electrode after the electrolysis is carried out XRD analysis, formed single-phase Ti-W alloy (sosoloid).In electrolytic process, WO
3And TiO
2Progressively deoxidation forms earlier than suboxide, forms elemental metals subsequently, simultaneously Ti with W diffusion dissolve each other and formed near monophasic TiW sosoloid, the electrolysis deoxidation process is from outward appearance to inner essence, progressively revert to low price again to the process of metal and alloy from high price.
Electrode about gross weight 50g, behind the electrolytic reduction 16h, the deoxidation process of oxide compound is accomplished, and has made Ti-60%W (wt.%) alloy after the electrolysis, and is approaching with theoretical composition Ti-57%W, and TiO is described
2And WO
3Mixed oxide can prepare the controlled titanium-tungsten alloy of composition through electrolysis.Because have the solid state sintering effect in the electrolysis, the TiW alloy grain of formation is obviously grown up, oxygen level is 0.35% in the titanium-tungsten alloy that makes, and purity is higher, and the current efficiency in the electrolytic process is 45～60%.
Embodiment 2:
Mean particle size is respectively 0.7
μM and 0.9
μThe TiO of m
2And WO
3Powder is pressed mass ratio 1:1 and is mixed, the zero(ppm) water of interpolation 10% and 6% carbon dust and mixing, and other operation is identical with embodiment 1 with experimental technique.Electrolytic technology has part different with process with embodiment 1, and the key distinction is that except the voltage that applies 3.0～3.2V, every separated 1h applies the square topped pulse electric current about 5 minutes in the electrolysis.The pulsewidth of pulsed current is 5
μS is 15 between arteries and veins
μS, maximum output pulsed current is 20A.
Electrode about gross weight 50g, behind the electrolysis 15h, the reduction process of oxide compound is accomplished, and Ti and W element have formed TiW alloy (sosoloid), its outward appearance, microtexture and become to grade similar with embodiment 1, current efficiency slightly improves.
Embodiment 3:
Mean particle size is respectively 0.7
μM and 0.9
μThe TiO of m
2And WO
3Powder is pressed mass ratio 1:1 and is mixed, and behind interpolation PVA solution, carbon dust and the titanium hydride mixed powder mixing, compression molding is the cylindrical electrode base substrate.Behind the at room temperature dry 48h, carry out the following 1200 ℃ high temperature sintering of argon shield, make TiO
2-WO
3The mixture electrode, processing parameter is seen table 2.About electrode weight 30g, boring back weight is about 28g.
Table 2 technology for preparing electrode parameter
Technology with embodiment 2 is carried out electrolysis; Altogether after the process of the electrode about the 56g 14h electrolysis; The reduction process of oxide compound is accomplished, and Ti and W metal have formed TiW alloy (sosoloid), and its outward appearance and microtexture etc. are similar with embodiment 1; Made Ti-58%W (wt.%) alloy, approaching with theoretical composition Ti-57%W.Oxygen level is 0.39% in the TiW alloy that makes, and purity is higher, and the current efficiency in the electrolytic process is about 56%.
Embodiment 4:
Mean particle size is 0.9
μThe TiO of m
2And WO
3Powder is pressed mass ratio 6:4 and is mixed, and adds carbon dust and more zero(ppm) water, and the formation slip that stirs pours into cylindrical electrode in gypsum mold, and the demoulding is taken out behind the placement 72h.Behind drying at room temperature 48h, in vacuum oven, carry out high temperature sintering under the argon shield environment, make TiO
2-WO
3The mixture electrode, porosity is about 38%, and about electrode weight 30g, boring back weight is about 28g.Technology for preparing electrode is seen table 3.
Table 3 technology for preparing electrode parameter
With the technology electrolysis of embodiment 1, altogether the electrode about 56g through the 16h electrolysis after, the reduction process of oxide compound is accomplished, and has made Ti-49wt%W alloy (sosoloid), and is approaching with theoretical composition Ti-47%W, its outward appearance and microtexture etc. are similar with embodiment 1.
Embodiment 5:
Mean particle size is respectively 1.0
μM and 0.9
μThe TiO of m
2And WO
3Powder is pressed mass ratio 4:6 and is mixed, and behind interpolation PVA solution and the carbon dust mixing, compression molding is the plate-shaped electrode.Behind the at room temperature dry 48h, make TiO at 1100 ℃ of sintering
2-WO
3The mixture electrode, about electrode weight 30g, boring back weight is about 28g.The technology for preparing electrode parameter is seen table 4.
Table 4 technology for preparing electrode parameter
With the technology electrolysis of embodiment 1, after the process of the electrode about the 56g 16h electrolysis, the reduction process of oxide compound is accomplished altogether.The electrolysate cleaning, drying and the polishing after, metalluster is arranged, have higher-strength, become alloy, the mutual sintering of particle together, porosity obviously reduces.Electrolysate is carried out XRD analysis, and it mainly is made up of single-phase Ti-W alloy (sosoloid).Made Ti-64%W (wt.%) alloy after the electrolysis, approaching with theoretical composition Ti-66%W, oxygen level is 0.37% in the TiW alloy that makes, and purity is higher.
Claims (8)
1. a fused salt electrolysis process prepares the method for titanium-tungsten alloy, and it is characterized in that: the method that fused salt electrolysis process prepares titanium-tungsten alloy comprises:
(1), with mean particle size 2
μBelow the m, purity is greater than 98% TiO
2And WO
3Powder is pressed the mixed of 9:1～3:7; Adding the carbon dust be equivalent to two kinds of powder gross weights 5～10% or carbon dust and titanium hydride powder ratio is 10: mixture (1-10) is made pore-forming material; Add total weight of solids 6～12% Z 150PH (PVA) solution or zero(ppm) water again and make tackiness agent; Use the method for machinery to mix, make mixed powder;
(2), to (1) preparation mixed powder carry out mold pressing, pressure 3～15MPa, pressurize 1～3min processes biscuit; Perhaps in the mixed powder of preparation, continue to add the slurry that zero(ppm) water is processed 60～80% concentration, injection forming in mould makes molding blank; The electrode base substrate of processing is that diameter is not less than 60mm, highly is the cylindrical of 3～10mm, or the length of side 50～150mm, height 3～10mm's is lamellar;
(3), be not higher than 5%, at 900～1200 ℃ of sintering 3～10h, do not make TiO to the base substrate seasoning at room temperature of (2) moulding or being dried to moisture below 150 ℃
2-WO
3The mixture electrode is done negative electrode, is anode with the high purity graphite, under the argon gas atmosphere protection, with CaCl
2For fused salt carries out electrolysis, 800～1100 ℃ of electrolysis temperatures, electrolysis voltage is 2.8～3.2V, at first is evacuated to before the electrolysis to be superior to 10Pa, charges into argon gas then, argon shield in the experiment whole process; After electrolysis finishes, the solid electrolytic product on the negative electrode is proposed fused salt, be cooled to room temperature; To cool off back electrolysate cleaning and removing fused salt, make titanium-tungsten alloy.
2. the method for preparing titanium-tungsten alloy according to the said fused salt electrolysis process of claim 1; It is characterized in that: the method for described cooling back electrolysate flush away electrolysis fused salt is: use distilled water flushing earlier; The washing of 1～2% hydrochloric acid soln, ultrasonic cleaning, washing again; In the oven dry of the temperature below 100 ℃, the product of acquisition is a titanium-tungsten alloy at last.
3. prepare the method for titanium-tungsten alloy according to the said fused salt electrolysis process of claim 1, it is characterized in that: described TiO
2-WO
3The mixture electrode is that diameter is not less than 60mm, highly is the cylindrical of 3～10mm, more than the substance 25g; Or the length of side 50～150mm, highly be the lamellar sample of 3～10mm, more than the substance 25g.
4. prepare the method for titanium-tungsten alloy according to the said fused salt electrolysis process of claim 1, it is characterized in that: described TiO
2And WO
3Powder is analytically pure TiO
2And WO
3Powder, TiO
2Powder is a Detitanium-ore-type, WO
3Powder is a close-packed hexagonal structure.
5. prepare the method for titanium-tungsten alloy according to the said fused salt electrolysis process of claim 1, it is characterized in that: described Z 150PH and titanium hydride analytical pure, carbon dust are the CP product.
6. prepare the method for titanium-tungsten alloy according to the said fused salt electrolysis process of claim 1, it is characterized in that: the electrolysis temperature-rise period is: be evacuated to earlier and be superior to 10Pa, charge into argon gas, be warming up to 350 ℃ and be incubated more than the 2h, make CaCl
2The fused salt thorough drying is warmed up to electrolysis temperature then and begins electrolysis; After electrolysis finishes, stop heating, make the stove naturally cooling, during charge into argon gas continuously.
7. prepare the method for titanium-tungsten alloy according to the said fused salt electrolysis process of claim 1, it is characterized in that: the dc electrolysis voltage of electrolytic process is 2.8～3.2V; Perhaps compound intermittent pulsed current, pulsewidth 5～10
μS is between arteries and veins 10～30
μS, pulsed current 0～20A.
8. prepare the method for titanium-tungsten alloy according to the said fused salt electrolysis process of claim 1, it is characterized in that: described Z 150PH (PVA) strength of solution is 2 ~ 20%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103409774A (en) * | 2013-07-09 | 2013-11-27 | 中国船舶重工集团公司第七二五研究所 | Method for preparing titanium or titanium alloy in molten salt by use of pulse power supply |
| CN106946292A (en) * | 2017-03-08 | 2017-07-14 | 重庆大学 | A kind of preparation method of titanium dioxide/tungsten trioxide nano-rod composite |
| CN111874948A (en) * | 2020-08-26 | 2020-11-03 | 华能国际电力股份有限公司 | System and method for separating and recycling waste SCR denitration catalyst |
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| CN1936088A (en) * | 2006-09-21 | 2007-03-28 | 上海大学 | Method and apparatus for directly preparing refractory metal and alloy from metal oxide |
| CN101985763A (en) * | 2010-10-29 | 2011-03-16 | 江西理工大学 | Method for preparing tungsten-base alloy powder by fused-salt electrolysis |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1936088A (en) * | 2006-09-21 | 2007-03-28 | 上海大学 | Method and apparatus for directly preparing refractory metal and alloy from metal oxide |
| CN101985763A (en) * | 2010-10-29 | 2011-03-16 | 江西理工大学 | Method for preparing tungsten-base alloy powder by fused-salt electrolysis |
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| 《Journal of Alloys and Compounds》 20061231 K. Dring etal Direct electrochemical production of Ti-10W alloys from mixed oxide preform precursors , * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103409774A (en) * | 2013-07-09 | 2013-11-27 | 中国船舶重工集团公司第七二五研究所 | Method for preparing titanium or titanium alloy in molten salt by use of pulse power supply |
| CN106946292A (en) * | 2017-03-08 | 2017-07-14 | 重庆大学 | A kind of preparation method of titanium dioxide/tungsten trioxide nano-rod composite |
| CN111874948A (en) * | 2020-08-26 | 2020-11-03 | 华能国际电力股份有限公司 | System and method for separating and recycling waste SCR denitration catalyst |
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