CN102424986B - Method for preparation of titanium-tungsten alloy through molten salt electrolysis - Google Patents
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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 a kind of method of novel preparation technology of titanium-tungsten alloy, particularly preparation of titanium-tungsten alloy through molten salt electrolysis.
Background technology
TiW alloy has a wide range of applications in fields such as microelectronics and biomedicines because having good performance, in Ti, add the alloy forming after W and there is higher intensity and hardness, and ductility loss is very little, non-magnetic W solid solution can reduce the Young's modulus of Ti in Ti matrix, and increases radiation resistance; Medically, after interpolation W, do not reduce the biocompatibility of Ti, be but conducive to alleviate the stress that implant produces from the different of matrix, improve the X-ray identity of the 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 super large-scale integration industry, highly purified TiW alloy can be with form of film for electrode materials, diffusion impervious layer and wiring material etc.Mainly to adopt the methods such as high-temperature vacuum melting, powder metallurgy and mechanical alloying to prepare TiW alloy at present, but these methods all exist, and production cost is high, complex process or the shortcoming such as product purity is not high, reduced the performance of titanium-tungsten alloy, limited to a great extent it and applied.
The fusing point of Ti is approximately 1670 ℃, the fusing point of W is 3522 ℃ of left and right, the fusing point of W and density are all much higher than Ti, during melting, be difficult to directly add, even used master alloy, the time that in process of setting, W stops in liquid Ti molten bath is very short, and delaminating deposition phenomenon occurs for very fast condensation or do not dissolve in the metal pool of vacuum remelting.In addition, during melting TiW alloy, composition is difficult to accurate control, and simultaneously the fusing point due to titanium is high, active large, is easy to be subject to the pollution of the impurity such as C, O, N, and its processing characteristics and use properties are worsened, and the recovery rate of gained TiW alloy is low, production cost is high.And while using powder metallurgic method, due to raw material titanium sponge complex manufacturing, energy consumption is high, efficiency is low, be prepared into and carry out again alloying process after powder and need to increase new energy consumption, cause the production cost of alloy higher.Adopt the high-energy ball-milling process (mechanical alloying) can the adjustable TiW alloy of prepared composition, and obtain tiny particle size, but easily introduce impurity, increase O content.
Fused salt electrolysis process (FFC method) can be prepared ordinary method and be difficult to multiple high-melting-point or refractory metal and the alloy thereof produced, in whole technological process, there is not liquid metal, 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, is also the novel environment-friendly process compared with prospects.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 producing the alloy product of new constituent.
The report of relevant preparation of titanium-tungsten alloy through molten salt electrolysis seldom both at home and abroad, 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, introduce fused salt electrolysis process and prepared the process of the Ti-10W alloy of low W content, but its W content of the titanium-tungsten alloy of reporting in the document is lower, W content is no more than 10%.Chinese invention patent CN101985763A has proposed " a kind of method of preparing tungsten-base alloy powder by fused-salt electrolysis ", take alkali and alkaline-earth metal villaumite is supporting electrolyte, take tungstate and metal oxide as electroactive substance, with carbon material, do cathode and anode material, under 750～900 ℃, 2.0～3.0V voltage, by preparing tungsten-base alloy powder by fused-salt electrolysis, this method is that common electrolytic process is prepared tungstenalloy.Electrolysis TiO in fused salt
2-WO
3mixture is prepared the titanium-tungsten alloy that W content is higher, not yet sees at present relevant report; And the titanium-tungsten alloy that uses molten salt electrodeoxidation method (FFC) to prepare high W content is not seen report yet.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method of preparation of titanium-tungsten alloy through molten salt electrolysis, the shortcoming of producing for traditional titanium-tungsten alloy, utilize the advantage of fused salt electrolysis process, use better simply equipment and process, the titanium-tungsten alloy that prepared composition is controlled, oxygen level is low.
In order to realize the object solving the problems of the technologies described above, the present invention has adopted following technical scheme:
The method of preparation of titanium-tungsten alloy through molten salt electrolysis of the present invention, comprising:
(1), by mean particle size 2
μthe TiO that m is following, purity is greater than 98%
2and WO
3powder mixes in the ratio of 9:1～3:7, add that to be equivalent to the carbon dust of two kinds of powder gross weights 5～10% or carbon dust and titanium hydride powder ratio be 10:(1-10) mixture make pore-forming material, add again polyvinyl alcohol (PVA) solution or the distilled water of solid amount 6～12% to make tackiness agent, use mechanical method to mix, make mixed powder;
(2), mixed powder prepared by (1) carries out mold pressing, pressure 3～15MPa, pressurize 1～3min, makes biscuit; Or in the mixed powder of preparation, continue to add distilled water to make the slurry of 60～80% concentration, injection forming in mould, makes molding blank; The electrode base substrate of making is that diameter is not less than 60mm, is highly the cylindrical of 3～10mm, or the length of side 50～150mm, height 3～10mm's is lamellar;
(3), to the at room temperature seasoning of base substrate of (2) moulding or at 150 ℃, be dried to below moisture not higher than 5%,, at 900～1200 ℃ of sintering 3～10h, make TiO
2-WO
3mixture electrode is done negative electrode, take high purity graphite as anode, under argon gas atmosphere protection, with CaCl
2for fused salt carries out electrolysis, 800～1100 ℃ of electrolysis temperatures, electrolysis voltage is 2.8～3.2V, before electrolysis, is first evacuated to and is better than 10Pa, is then filled with argon gas, argon shield in experiment whole process; After electrolysis finishes, the solid electrolytic product on negative electrode is proposed to fused salt, be cooled to room temperature; Cooling rear electrolysate is cleaned and removes fused salt, make titanium-tungsten alloy.
Described polyvinyl alcohol (PVA) solution, concentration can be 2 ~ 20%.
The method that cooling rear electrolysate washes away electrolysis fused salt can be: first use distilled water flushing, be then 1～2% hydrochloric acid soln washing in ultrasonic wave, then wash, finally in the temperature below 100 ℃, dry, the product of acquisition is titanium-tungsten alloy.
Described TiO
2-WO
3mixture electrode is that diameter is not less than 60mm, is highly the cylindrical of 3～10mm, more than substance 25g; Or adopt the length of side 50～150mm, be highly the lamellar sample of 3～10mm, more than substance 25g.
Described TiO
2and WO
3powder is analytically pure TiO
2and WO
3powder, TiO
2powder is Detitanium-ore-type, WO
3powder is close-packed hexagonal structure.
Described polyvinyl alcohol, titanium hydride, carbon dust are analytical pure product.
Electrolysis temperature-rise period is: be first evacuated to and be better than 10Pa, be filled with argon gas, be warming up to 350 ℃ and be incubated 2h more than, make CaCl
2fused salt is fully dry, is then warmed up to electrolysis temperature and starts electrolysis; After electrolysis finishes, stop heating, make stove naturally cooling, during be filled with continuously argon gas.
The DC electrolysis voltage of electrolytic process is 2.8～3.2V; Or compound intermittent pulsed current, pulsewidth 5～10
μs, between arteries and veins 10～30
μs, pulsed current 0～20A.
After 900～1200 ℃ of sintering, TiO
2-WO
3the porosity of electrode is 35～55%, TiO
2crystalline structure by Detitanium-ore-type, change rutile-type into, WO
3do not change; TiO
2and WO
3between generally there is not chemical reaction, work as WO
3when content is lower, may there is chemical reaction or part chemical reaction between the two.
These technical schemes also can combine mutually or combination, thereby reach better technique effect.
By adopting technique scheme, the present invention has following beneficial effect:
(1) the present invention can obviously reduce the preparation temperature of TiW alloy, can at lower temperature, obtain high purity, composition is controlled and crystal grain is tiny TiW alloy.
(2) simple, the device simple of preparation method of the present invention, manufacturing process are simply controlled.
(3) the present invention is conducive to the preparation of high purity product.
Embodiment
Below describe several embodiment of the present invention in detail, but the present invention is not limited to this, for a person skilled in the art, not departing under the prerequisite of the inventive method, can also makes some distortion and improvement, all should belong to protection scope of the present invention.
embodiment 1:
Mean particle size is respectively to 0.7
μm and 0.9
μthe TiO of m
2and WO
3powder in mass ratio 1:1 mixes, and after adding PVA solution and carbon dust mechanically mixing and stirring, uses mould to be pressed into cylindrical electrode.First at room temperature seasoning 48h first vacuumizes and is filled with argon shield again in vacuum atmosphere oven, through 350 ℃ of annealing, gets rid of PVA, and then 900 ℃ of high temperature sinterings make TiO
2-WO
3mixture electrode, the about 27g of weight, the about 25g of weight after boring.Processing parameter prepared by electrode is in Table 1.
Table 1 technology for preparing electrode parameter
The TiO making
2-WO
3approximately 41%, two kind of oxide powder of electrode porosity still keeps very tiny particulate state, has sintering to a certain degree to connect between particle.Through XRD material phase analysis, after sintering, TiO
2from Detitanium-ore-type, change rutile-type into, WO
3powder does not have recurring structure to change, and between two kinds of powder, does not react.
Take high purity graphite as anode, TiO
2-WO
3mixture electrode array is associated on molybdenum rod and makes negative electrode, and the gross weight of electrolyte is 50g left and right, take high-density graphite crucible as electrolyzer, CaCl in special electrolytic furnace
2fused salt is placed in one and carries out electrolysis.First vacuumize, when vacuum tightness is better than 10Pa, be filled with continuously argon gas, CaCl
2fused salt is dried 2h to drive away moisture at 350 ℃; Then continue to heat up, treat that temperature of molten salt is elevated to 900 ℃ also after a period of stabilisation, starts to carry out electrolysis.The preelectrolysis 1h under 2.0V voltage of elder generation, object is to remove moisture remaining in fused salt and impurity; Then under the voltage of 3.0～3.2V, carry out formal electrolysis, stable state Faradaic current is 16A left and right, after electrolysis finishes, electrode is proposed to fused salt, naturally cools to room temperature in stove, and whole process is all carried out under argon shield.
Electrolysate is first used to distilled water flushing specimen surface, remove the remaining fused salt duricrust in electrode sample surface, then auxiliary lower to 2% aqueous hydrochloric acid washing by soaking in ultrasonic wave, remove the CaCl in product
2fused salt and some other impurity, then continue to clean with distilled water, finally at 80 ℃, electrode product dried.
After electrolysate cleaning, drying polishing, have metalluster, intensity higher, become alloy, particle is grown up and is sintered together each other, and porosity obviously reduces.Electrode after electrolysis is carried out to XRD analysis, formed single-phase Ti-W alloy (sosoloid).In electrolytic process, WO
3and TiO
2progressively deoxidation first forms compared with suboxide, forms subsequently elemental metals, and simultaneously Ti and W diffusion dissolved each other to have formed and approached single-phase TiW sosoloid, and electrolysis deoxidation process is from outward appearance to inner essence, from high price, progressively revert to low price again to the process of metal and alloy.
The electrode of gross weight 50g left and right, after electrolytic reduction 16h, the deoxidation process of oxide compound completes, and has made Ti-60%W(wt.% after electrolysis) alloy, approach with theoretical composition Ti-57%W, TiO is described
2and WO
3mixed oxide can be prepared the controlled titanium-tungsten alloy of composition through electrolysis.Owing to there is solid state sintering effect in electrolysis, the TiW alloy grain of formation is obviously grown up, and in the titanium-tungsten alloy making, oxygen level is 0.35%, and purity is higher, and the current efficiency in electrolytic process is 45～60%.
embodiment 2:
Mean particle size is respectively to 0.7
μm and 0.9
μthe TiO of m
2and WO
3powder in mass ratio 1:1 mixes, and the distilled water of interpolation 10% and 6% carbon dust also mix, and other operation and experimental technique are identical with embodiment 1.The technique of electrolysis has part different with process from embodiment 1, and the key distinction is, in electrolysis, except applying the voltage of 3.0～3.2V, every 1h, applies the square topped pulse electric current about 5 minutes.The pulsewidth of pulsed current is 5
μs is 15 between arteries and veins
μs, maximum output pulsed current is 20A.
The electrode of gross weight 50g left and right, after electrolysis 15h, the reduction process of oxide compound completes, and Ti and W element have formed TiW alloy (sosoloid), and its outward appearance, microstructure and chemical composition etc. are similar to embodiment 1, and current efficiency is slightly improved.
embodiment 3:
Mean particle size is respectively to 0.7
μm and 0.9
μthe TiO of m
2and WO
3powder in mass ratio 1:1 mixes, and after interpolation PVA solution, carbon dust and titanium hydride mixed powder mix, compression molding is cylindrical electrode base substrate.At room temperature, after dry 48h, the high temperature sintering that carries out lower 1200 ℃ of argon shield, makes TiO
2-WO
3mixture electrode, processing parameter is in Table 2.Electrode weight 30g left and right, after boring, weight is about 28g.
Table 2 technology for preparing electrode parameter
Technique with embodiment 2 is carried out electrolysis, the electrode of 56g left and right is after 14h electrolysis altogether, the reduction process of oxide compound completes, Ti and W metal have formed TiW alloy (sosoloid), its outward appearance is similar to embodiment 1 with microtexture etc., made Ti-58%W(wt.%) alloy, approach with theoretical composition Ti-57%W.In the TiW alloy making, oxygen level is 0.39%, and purity is higher, and the current efficiency in electrolytic process is 56% left and right.
embodiment 4:
Mean particle size is to 0.9
μthe TiO of m
2and WO
3powder in mass ratio 6:4 mixes, and adds carbon dust and more distilled water, and the formation slip that stirs pours into cylindrical electrode in gypsum mold, and after placement 72h, the demoulding is taken out.After drying at room temperature 48h, in vacuum oven, under argon shield environment, carry out high temperature sintering, make TiO
2-WO
3mixture electrode, porosity approximately 38%, electrode weight 30g left and right, after boring, weight is about 28g.Technology for preparing electrode is in Table 3.
Table 3 technology for preparing electrode parameter
With the technique electrolysis of embodiment 1, altogether the electrode of 56g left and right is after 16h electrolysis, and the reduction process of oxide compound completes, and has made Ti-49wt%W alloy (sosoloid), approaches with theoretical composition Ti-47%W, and its outward appearance and microtexture etc. are similar to embodiment 1.
embodiment 5:
Mean particle size is respectively to 1.0
μm and 0.9
μthe TiO of m
2and WO
3powder in mass ratio 4:6 mixes, and after interpolation PVA solution and carbon dust mix, compression molding is plate-shaped electrode.At room temperature, after dry 48h, at 1100 ℃ of sintering, make TiO
2-WO
3mixture electrode, electrode weight 30g left and right, after boring, weight is about 28g.Technology for preparing electrode parameter is in Table 4.
Table 4 technology for preparing electrode parameter
With the technique electrolysis of embodiment 1, the electrode of 56g left and right is after 16h electrolysis altogether, and the reduction process of oxide compound completes.After electrolysate cleaning, drying polishing, have metalluster, have higher-strength, become alloy, particle is sintered together each other, and porosity obviously reduces.Electrolysate is carried out to XRD analysis, and it is mainly comprised of single-phase Ti-W alloy (sosoloid).After electrolysis, made Ti-64%W(wt.%) alloy, approach with theoretical composition Ti-66%W, in the TiW alloy making, oxygen level is 0.37%, purity is higher.
Claims (6)
1. a method for preparation of titanium-tungsten alloy through molten salt electrolysis, is characterized in that: the method for preparation of titanium-tungsten alloy through molten salt electrolysis comprises:
(1), by mean particle size 2
μthe TiO that m is following, purity is greater than 98%
2and WO
3powder mixes in the ratio of 9:1～3:7, add that to be equivalent to the carbon dust of two kinds of powder gross weights 5～10% or carbon dust and titanium hydride powder ratio be 10:(1-10) mixture make pore-forming material, add again total weight of solids 6～12% polyvinyl alcohol solutions or distilled water to make tackiness agent, use mechanical method to mix, make mixed powder;
(2), mixed powder prepared by (1) carries out mold pressing, pressure 3～15MPa, pressurize 1～3min, makes biscuit; Or in the mixed powder of preparation, continue to add distilled water to make the slurry of 60～80% concentration, injection forming in mould, makes molding blank; The electrode base substrate of making is that diameter is not less than 60mm, is highly the cylindrical of 3～10mm, or the length of side 50～150mm, height 3～10mm's is lamellar;
(3), to the at room temperature seasoning of base substrate of (2) moulding or at 150 ℃, be dried to below moisture not higher than 5%,, at 900～1200 ℃ of sintering 3～10h, make TiO
2-WO
3mixture electrode is done negative electrode, take high purity graphite as anode, under argon gas atmosphere protection, with CaCl
2for fused salt carries out electrolysis, 800～1100 ℃ of electrolysis temperatures; Electrolysis adopts compound intermittent pulsed current, pulsewidth 5～10
μs, between arteries and veins 10～30
μs, pulsed current 0～20A; Before electrolysis, be first evacuated to and be better than 10Pa, be then filled with argon gas, argon shield in experiment whole process; After electrolysis finishes, the solid electrolytic product on negative electrode is proposed to fused salt, be cooled to room temperature; Cooling rear electrolysate is cleaned and removes fused salt, make titanium-tungsten alloy.
2. the method for preparation of titanium-tungsten alloy through molten salt electrolysis according to claim 1, it is characterized in that: the method that described cooling rear electrolysate washes away electrolysis fused salt is: first use distilled water flushing, 1～2% hydrochloric acid soln washing, ultrasonic cleaning, wash again, finally in the temperature below 100 ℃, dry, the product of acquisition is titanium-tungsten alloy.
3. the method for preparation of titanium-tungsten alloy through molten salt electrolysis according to claim 1, is characterized in that: described TiO
2-WO
3mixture electrode is that diameter is not less than 60mm, is highly the cylindrical of 3～10mm, more than substance 25g; Or the length of side 50～150mm, be highly the lamellar sample of 3～10mm, more than substance 25g.
4. the method for preparation of titanium-tungsten alloy through molten salt electrolysis according to claim 1, is characterized in that: described TiO
2and WO
3powder is analytically pure TiO
2and WO
3powder, TiO
2powder is Detitanium-ore-type, WO
3powder is close-packed hexagonal structure.
5. the method for preparation of titanium-tungsten alloy through molten salt electrolysis according to claim 1, is characterized in that: described polyvinyl alcohol and titanium hydride analytical pure, carbon dust are chemical pure product.
6. the method for preparation of titanium-tungsten alloy through molten salt electrolysis according to claim 1, is characterized in that: electrolysis temperature-rise period is: be first evacuated to and be better than 10Pa, be filled with argon gas, be warming up to 350 ℃ and be incubated 2h more than, make CaCl
2fused salt is fully dry, is then warmed up to electrolysis temperature and starts electrolysis; After electrolysis finishes, stop heating, make stove naturally cooling, during be filled with continuously argon gas.
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| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| Direct electrochemical production of Ti–10W alloys from mixed oxide preform precursors;K. Dring etal;《Journal of Alloys and Compounds》;20061231;103–109 * |
| K. Dring etal.Direct electrochemical production of Ti–10W alloys from mixed oxide preform precursors.《Journal of Alloys and Compounds》.2006, |
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