CN101949044B - Niobium electro-osmosis method for steel surface in ionic liquid - Google Patents
Niobium electro-osmosis method for steel surface in ionic liquid Download PDFInfo
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- CN101949044B CN101949044B CN2010102913976A CN201010291397A CN101949044B CN 101949044 B CN101949044 B CN 101949044B CN 2010102913976 A CN2010102913976 A CN 2010102913976A CN 201010291397 A CN201010291397 A CN 201010291397A CN 101949044 B CN101949044 B CN 101949044B
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Abstract
The invention discloses a niobium electro-osmosis method for steel surface in ionic liquid, which comprises the following steps of: adding aluminum powder and NbCl5 into ethyl ether in a molar ratio of 3:1-1:3; adding the obtained solution into 1-ethyl-3-methylimidazole trifluoromethanesulfonate ionic liquid; adding 1 to 3 percent NaCl solution into the solution to prepare ionic liquid electro-osmosis solution; putting the pretreated steel matrix into the ionic liquid electro-osmosis solution, and performing electro-deposition by adopting a direct-current constant voltage mode, wherein the steel matrix is used as a cathode, a pure niobium plate or a pure aluminum plate is used as an anode, the voltage range is 12 to 30V, the distance between the cathode and the anode is 1 to 3 centimeters, the deposition time is 10 minutes to 12 hours and the temperature of the ionic liquid electro-osmosis solution is 70 to 160 DEG C; and taking out the matrix after the deposition is finished, and flushing the matrix by using deionized water to obtain light black or grey blue niobium osmosis steel. The method solves the problem that a niobium plating layer cannot be obtained in aqueous solution, is environment-friendly, and has simple process and easy operation.
Description
Technical field
The present invention relates to the method for steel surface electroosmosis niobium in the ionic liquid.By ionic liquid, the mode that adopts dc electrodeposition to improve the solidity to corrosion of steel, is expanded its range of application in an amount of metal niobium of depositing on surface of steel.
Background technology
Heavy transition element niobium (Nb), it is a kind of strong ferrite former, be again strong carbon, nitride forming element, it is essential that the compatibility of it and other element is used for the different steel grade of exploitation performance, especially in the heat-resistance stainless steel in high temperature field, niobium even the expensive molybdenum of replacement that can part, thereby it is more and more extensive to contain the application of niobium steel.Owing to can not obtain the coating of pure niobium by the method for aqueous solution electric osmose, how the production that contains the niobium steel usually is by metallurgical method, utilizes a series of aftertreatment control niobium having form and obtain the steel grade of different application performance in steel again.The metallurgical production process is relatively complicated and need large-scale production unit, and application process has certain limitation.
Ionic liquid is meant fully under the room temperature of being made up of negative ions and is the salt of liquid, and positive ion is generally relatively large, the asymmetric organic cation of volume, and negatively charged ion is the less relatively inorganic anion of volume.Plurality of advantages such as ionic liquid is low owing to the tool fusing point, volatility is low, of a great variety become a kind of novel, eco-friendly green medium, be used widely in fields such as life science, solar cell, electroluminescent material, metal electrodepositions, disclose the method for galvanic deposit Co in a kind of ionic liquid as (CN1884622A) such as Yang Peixia.Because metal niobium is a kind of inert metal, can not be at aqueous solution deposition, and the many metallurgical industry by complexity of the steel grade that contains niobium obtain, under this background, the mode that the present invention adopts dc electrodeposition in ionic liquid to the surface electroosmosis niobium of matrix steel, obtain the steel of different content of niobium by control process parameters, thereby improve the performance of steel, enlarge its range of application.
Summary of the invention
The method that the purpose of this invention is to provide steel substrate surface electric osmose niobium in a kind of ionic liquid, niobium can not deposit in the aqueous solution thereby solve, and the problem of the technological process relative complex of metallurgical method.
The present invention adopts following technical scheme:
The method of steel surface electroosmosis niobium in the ionic liquid may further comprise the steps:
(1) in ether, adds aluminium powder and NbCl
5, aluminium powder and NbCl
5Mol ratio be 3: 1～1: 3, with NbCl
5Be reduced to Nb
3Cl
8, and obtain oxidation products AlCl
3
(2) step (1) gained solution is joined in 1-ethyl-3-Methylimidazole fluoroform sulphonate ionic liquid control aluminium powder, NbCl
5With 1-ethyl-3-Methylimidazole fluoroform sulphonate three's ratio be (3～1): (1～3): (1～10); Adding concentration is the NaCl solution of 1%～3% massfraction, is configured to ionic liquid electric osmose liquid;
(3) will put into above-mentioned ionic liquid through pretreated steel matrix, steel matrix is a negative electrode, and pure niobium plate or pure aluminum plate are anode, adopts the mode of direct current constant voltage to carry out galvanic deposit; Voltage range is 12V～30V, and cathode and anode spacing is 1cm～3cm, depositing time 10min～12h, and ion liquid temperature is controlled at 70 ℃～160 ℃;
(4) take out matrix after deposition finishes, use deionized water rinsing, obtain light/dark balance or the caeseous niobium steel that oozes.
Aluminium powder and NbCl in the described step (1)
5Mol ratio be 3: 1,3: 2,1: 3,2: 1 or 2.4: 1; The reagent that uses in the reduction process is analytical reagent.
The method of described step (3) substrate pretreated is that matrix is carried out mechanical grinding, and deionized water rinsing is used in the polishing back, uses alcohol degreasing again, and last cold wind dries up.
Can finish in a step when mode of employing direct current constant voltage is carried out galvanic deposit in the described step (3), the voltage range during at this moment described the deposition is 12V～30V, depositing time 10min～12h.
Adopting in the described step (3) mode of direct current constant voltage to carry out galvanic deposit was divided into for two steps and carries out: promptly earlier carry out galvanic deposit under a direct current constant voltage, raise after deposition for some time or reduce voltage, deposit when voltage reaches constant again; Voltage range during described the deposition is 12V～30V, and cathode and anode spacing is 1cm～3cm, depositing time 10min～12h, and ion liquid temperature is controlled at 70 ℃～160 ℃.
The present invention has outstanding technique effect than prior art:
(1) the present invention has solved the problem that can't obtain niobium coating in the aqueous solution with the method for ionic liquid electrodeposition niobium;
(2) according to implementation condition of the present invention, the content that oozes niobium in the niobium steel can be controlled by processing condition.
(3) deposit fluid that uses in the deposition process of the present invention is the ionic liquid of environmental protection, can not cause environmental pollution.
(4) enforcement of the present invention does not need large-scale production unit, and technological process is simple, easy to operate.
Embodiment
Get the steel plate of thick 1mm, be machined to the rectangular sheet of 10mm * 30mm.
Embodiment 1
(1) configuration ionic liquid electric osmose liquid:
In ether, add aluminium powder and NbCl
5, gained solution is joined in 1-ethyl-3-Methylimidazole fluoroform sulphonate ionic liquid, the ratio of control electric osmose fluid component is Al: NbCl
5: emimOTf=3.6: 1.2: 1.3, while interpolation massfraction in solution was 2.7% NaCl.
(2) matrix surface electric osmose niobium:
To put into above-mentioned ionic liquid electric osmose liquid through pretreated steel matrix, stainless steel is a negative electrode, aluminium flake is an anode, cathode and anode spacing is 1cm, control electric osmose liquid temp is 100 ℃, and constant voltage deposition 12h takes out stainless steel after deposition finishes under 28.3V voltage, use deionized water rinsing, obtain containing Nb and be 0.30% stainless steel.
Embodiment 2
(1) configuration ionic liquid electric osmose liquid:
In ether, add aluminium powder and NbCl
5, gained solution is joined in 1-ethyl-3-Methylimidazole fluoroform sulphonate ionic liquid, the ratio of control electric osmose fluid component is Al: NbCl
5: emimOTf=2.4: 1.2: 1.3, while interpolation massfraction in solution was 1% NaCl.
(2) matrix surface electric osmose niobium:
To put into above-mentioned ionic liquid electric osmose liquid through pretreated steel matrix, stainless steel is a negative electrode, aluminium flake is an anode, cathode and anode spacing is 3cm, and control electric osmose liquid temp is 100 ℃, constant voltage deposition 15min under 17.0V voltage, boost to 28.7V deposition 45min again, stainless steel is taken out in the deposition back that finishes, and uses deionized water rinsing, obtains containing Nb and be 0.88% stainless steel.
Embodiment 3
(1) configuration ionic liquid electric osmose liquid:
In ether, add aluminium powder and NbCl
5, gained solution is joined in 1-ethyl-3-Methylimidazole fluoroform sulphonate ionic liquid, the ratio of control electric osmose fluid component is Al: NbCl
5: emimOTf=2.4: 1: 1.3, while interpolation massfraction in solution was 3% NaCl.
(2) matrix surface electric osmose niobium:
To put into above-mentioned ionic liquid electric osmose liquid through pretreated steel matrix, stainless steel is a negative electrode, aluminium flake is an anode, cathode and anode spacing is 2cm, and control electric osmose liquid temp is 70 ℃, constant voltage deposition 30min under 28.7V voltage, be depressurized to 19.6V deposition 10h again, stainless steel is taken out in the deposition back that finishes, and uses deionized water rinsing, obtains containing Nb and be 1.29% stainless steel.
Embodiment 4
(1) configuration ionic liquid electric osmose liquid:
In ether, add aluminium powder and NbCl
5, gained solution is joined in 1-ethyl-3-Methylimidazole fluoroform sulphonate ionic liquid, the ratio of control electric osmose fluid component is Al: NbCl
5: emimOTf=3: 2: 4, while interpolation massfraction in solution was 2.7% NaCl.
(2) matrix surface electric osmose niobium:
To put into above-mentioned ionic liquid electric osmose liquid through pretreated steel matrix, stainless steel is a negative electrode, aluminium flake is an anode, cathode and anode spacing is 1cm～3cm, and control electric osmose liquid temp is 130 ℃, constant voltage deposition 20min under 28.7V voltage, be depressurized to 18.0V deposition 13min again, stainless steel is taken out in the deposition back that finishes, and uses deionized water rinsing, obtains containing Nb and be 3.55% stainless steel.
Embodiment 5
(1) configuration ionic liquid electric osmose liquid:
In ether, add aluminium powder and NbCl
5, gained solution is joined in 1-ethyl-3-Methylimidazole fluoroform sulphonate ionic liquid, the ratio of control electric osmose fluid component is Al: NbCl
5: emimOTf=1: 3: 10, while interpolation massfraction in solution was 2% NaCl.
(2) matrix surface electric osmose niobium:
To put into above-mentioned ionic liquid electric osmose liquid through pretreated steel matrix, stainless steel is a negative electrode, pure niobium sheet is an anode, cathode and anode spacing is 2cm, and control electric osmose liquid temp is 155 ℃, constant voltage deposition 12min under 15.9V voltage, boosted to the 21.8V deposition again 1 hour 20 minutes, stainless steel is taken out in the deposition back that finishes, and uses deionized water rinsing, obtains containing Nb and be 8.28% stainless steel.
Embodiment 6
(1) configuration ionic liquid electric osmose liquid:
In ether, add aluminium powder and NbCl
5, gained solution is joined in 1-ethyl-3-Methylimidazole fluoroform sulphonate ionic liquid, the ratio of control electric osmose fluid component is Al: NbCl
5: emimOTf=3: 1: 4, while interpolation massfraction in solution was 2.7% NaCl.
(2) matrix surface electric osmose niobium:
To put into above-mentioned ionic liquid electric osmose liquid through pretreated steel matrix, stainless steel is a negative electrode, pure niobium sheet is an anode, cathode and anode spacing is 1cm～3cm, control electric osmose liquid temp is 70 ℃, and constant voltage deposition 20min takes out stainless steel after deposition finishes under 28.7V voltage, use deionized water rinsing, obtain containing Nb and be 0.35% stainless steel.
Embodiment 7
(1) configuration ionic liquid electric osmose liquid:
In ether, add aluminium powder and NbCl
5, gained solution is joined in 1-ethyl-3-Methylimidazole fluoroform sulphonate ionic liquid, the ratio of control electric osmose fluid component is Al: NbCl
5: emimOTf=2: 3: 10, while interpolation massfraction in solution was 1.5% NaCl.
(2) matrix surface electric osmose niobium:
To put into above-mentioned ionic liquid electric osmose liquid through pretreated steel matrix, stainless steel is a negative electrode, pure niobium sheet is an anode, cathode and anode spacing is 2cm, and control electric osmose liquid temp is 155 ℃, constant voltage deposition 15min under 28.9V voltage, be depressurized to 21.8V deposition 1 hour 20 minutes again, stainless steel is taken out in the deposition back that finishes, and uses deionized water rinsing, obtains containing Nb and be 0.52% stainless steel.
Claims (4)
1. the method for steel surface electroosmosis niobium in the ionic liquid may further comprise the steps:
(1) in ether, adds aluminium powder and NbCl
5, aluminium powder and NbCl
5Mol ratio be 3: 1～1: 3, with NbCl
5Be reduced to Nb
3Cl
8, and obtain oxidation products AlCl
3
(2) step (1) gained solution is joined in 1-ethyl-3-Methylimidazole fluoroform sulphonate ionic liquid control aluminium powder, NbCl
5With 1-ethyl-3-Methylimidazole fluoroform sulphonate three's ratio be (3～1): (1～3): (1～10); Adding concentration is the NaCl solution of 1%～3% massfraction, is configured to ionic liquid electric osmose liquid;
(3) will put into step (2) ionic liquid electric osmose liquid through pretreated steel matrix, steel matrix is a negative electrode, and pure niobium plate or pure aluminum plate are anode, adopts the mode of direct current constant voltage to carry out galvanic deposit; Voltage range is 12V～30V, and cathode and anode spacing is 1cm～3cm, depositing time 10min～12h, and the temperature of ionic liquid electric osmose liquid is controlled at 70 ℃～160 ℃;
(4) take out matrix after deposition finishes, use deionized water rinsing, obtain light/dark balance or the caeseous niobium steel that oozes.
2. the method for steel surface electroosmosis niobium in the ionic liquid according to claim 1 is characterized in that aluminium powder and NbCl in the step (1)
5Mol ratio be 3: 1,3: 2,1: 3,2: 1 or 2.4: 1; The reagent that uses in the reduction process is analytical reagent.
3. the method for steel surface electroosmosis niobium in the ionic liquid according to claim 1, the method that it is characterized in that step (3) substrate pretreated are that polishing back is with alcohol degreasing and dry up.
4. according to the method for steel surface electroosmosis niobium in the described ionic liquid of each claim in the claim 1～3, it is characterized in that adopting in the step (3) direct current constant voltage mode to carry out galvanic deposit and carry out in two steps: respectively two different direct current constant voltage deposit; Described sedimentary voltage range is 12V～30V, depositing time 10min～12h, and ion liquid temperature is controlled at 70 ℃～160 ℃.
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| CN103343373A (en) * | 2013-07-06 | 2013-10-09 | 哈尔滨工业大学 | Preparation method of ionic liquid electrodeposition copper/indium/gallium/selenium CIGS thin-film materials |
| CN113913881A (en) * | 2021-10-29 | 2022-01-11 | 苏州新中能源科技有限公司 | Method for electroplating copper on steel surface in ionic liquid |
| CN114855231A (en) * | 2022-05-27 | 2022-08-05 | 江西思远再生资源有限公司 | Method for plating niobium on magnesium and magnesium alloy |
Citations (4)
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| WO2006053362A2 (en) * | 2004-11-19 | 2006-05-26 | Plansee Se | Method for depositing layers from ionic liquids |
| CN1884622A (en) * | 2006-05-19 | 2006-12-27 | 哈尔滨工业大学 | Metal cobalt electrodeposition method by ion liquid |
| EP1983078A1 (en) * | 2007-04-17 | 2008-10-22 | Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO | Electrodeposition |
| CN101538725A (en) * | 2009-03-31 | 2009-09-23 | 哈尔滨工业大学 | Method for preparing Tb-Co alloy layer by utilizing ionic liquid electrodeposition technology |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006053362A2 (en) * | 2004-11-19 | 2006-05-26 | Plansee Se | Method for depositing layers from ionic liquids |
| CN1884622A (en) * | 2006-05-19 | 2006-12-27 | 哈尔滨工业大学 | Metal cobalt electrodeposition method by ion liquid |
| EP1983078A1 (en) * | 2007-04-17 | 2008-10-22 | Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO | Electrodeposition |
| CN101538725A (en) * | 2009-03-31 | 2009-09-23 | 哈尔滨工业大学 | Method for preparing Tb-Co alloy layer by utilizing ionic liquid electrodeposition technology |
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