CN101892498B - Method for preparing iridium layer in ionic liquid electro-deposition solution through electro-deposition - Google Patents
Method for preparing iridium layer in ionic liquid electro-deposition solution through electro-deposition Download PDFInfo
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- CN101892498B CN101892498B CN2010102168600A CN201010216860A CN101892498B CN 101892498 B CN101892498 B CN 101892498B CN 2010102168600 A CN2010102168600 A CN 2010102168600A CN 201010216860 A CN201010216860 A CN 201010216860A CN 101892498 B CN101892498 B CN 101892498B
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Abstract
The invention discloses ionic liquid electro-deposition solution and a method for preparing an iridium layer by electro-deposition with the Ionic liquid electro-deposition solution. The ionic liquid electro-deposition solution is formed by adding 0.001 to 0.20 g of anhydrous trivalent iridium salt into 10 ml of aluminium chloride type ionic liquid, or is formed by adding 0.001 to 0.20 g of anhydrous trivalent iridium salt into 10 ml of non-aluminium chloride type ionic liquid, or is formed by adding 0.001 to 0.20 g of anhydrous trivalent iridium salt and 1 to 20 ml of ethanediol into 10 ml of aluminium chloride type ionic liquid. The technical scheme of the method for preparing the iridium layer through the electro-deposition comprises the following steps of: adding the ionic liquid electro-deposition solution into a electro-deposition tank of a vacuum glove box, wherein an inert material is used as an anode and a to-be-electrodeposited material is used as a cathode; and performing electro-deposition at the temperature of between 70 and 120 DEG C by a constant current mode so as to obtain the iridium layer from the surface of the cathode material.
Description
Technical field
The present invention relates to the ionic liquid solution that a kind of prepared by electrodeposition iridium layer is adopted, also relate to and in ionic liquid solution, adopt the continuous current method to come prepared by electrodeposition iridium layer.
Background technology
Metal iridium has very high fusing point, very high intensity reaches ductility preferably, have other metal can't be obtained unreactiveness and at high temperature have the very strong characteristic that stops oxygen and carbon, therefore usually be plated on the surface of some vital part, need pyritous structural part surface as guided missile cruiser turbine engine, rocket chamber inwall, gas-turbine engine, thermoelectric generator, automotive industry and other, be with a wide range of applications in Aeronautics and Astronautics, navigation and high technology for civilian use field etc.
At present the main method of preparation iridium layer has: aqueous solution electrodeposition prepares that prepared by electrodeposition iridium layer, chemical vapour deposition prepare the iridium layer in iridium layer, the melting salt system, the sputter physical vapor deposition prepares the iridium layer and plasma spraying prepares iridium layer etc.Prepare the iridium layer because there is side reaction in negative electrode at aqueous solution electrodeposition, the iridium layer performance of acquisition is unsatisfactory, has very problems such as big stress.Utilize high-temperature molten salt prepared by electrodeposition iridium layer to have problems such as service temperature is too high, energy consumption big, deep-etching.Chemical vapour deposition prepares iridium layer required equipment costliness, cost height.It is slower that the sputter physical vapor deposition prepares iridium layer sedimentation rate, and be not suitable for being deposited on the complex-shaped parts.The iridium layer porosity that plasma spraying obtained is higher, can not use as supercoat, particularly under hyperthermal environments.
Ionic liquid is meant near the material that is liquid state room temperature, is combined by the relative less inorganic anion with volume of relatively large, the asymmetric organic cation of volume usually, is also referred to as room temperature fused salt sometimes.Ionic liquid has that steam forces down, Heat stability is good, specific conductivity height, electrochemical window are wide, can regulate characteristics such as ion liquid solvability by changing ionic species, and therefore, ionic liquid becomes a kind of brand-new medium in the galvanic deposit.Ionic liquid is as the medium of galvanic deposit, both can deposit and obtain the light metal (being subjected to the restriction of aqueous systems electrochemical window) that can't obtain in the aqueous systems, also can at room temperature obtain the refractory metal that the ability galvanic deposit obtains in high-temperature molten salt, and because side reaction is few, the metallicity that obtains is better, therefore, ionic liquid has broad application prospects aspect metal electrodeposition.
Summary of the invention
One of purpose of the present invention is the composition that proposes a kind of ionic liquid electrodeposition solution that adopts when prepared by electrodeposition iridium layer.
Another object of the present invention is to propose a kind of method of continuous current that adopts to come prepared by electrodeposition iridium layer in ionic liquid solution.
Advantage of the present invention: utilize present method iridium layer of prepared by electrodeposition in ionic liquid to have easy to operate, with low cost, excellent property, and be fit to be deposited on the first-class advantage of complex-shaped component.
The anhydrous trivalent iridium salt that adds 0.001g～0.20g when prepared by electrodeposition iridium layer in the aluminum chloride type ionic liquid of a kind of ionic liquid electrodeposition solution (tank liquor) that adopts of the present invention by 10ml is formed; Or the anhydrous trivalent iridium salt that adds 0.001g～0.20g in the non-aluminum chloride type ionic liquid by 10ml is formed; Or add the anhydrous trivalent iridium salt of 0.001g～0.20g in the aluminum chloride type ionic liquid by 10ml and the ethylene glycol of 1ml～20ml is formed.
Described anhydrous trivalent iridium salt can be IrCl
3, IrF
3And IrBr
3In a kind of;
Described aluminum chloride type ionic liquid is BMIC (chloridization 1-methyl-3-butyl imidazole) or EMIC (chlorination 1-methyl-3-ethyl imidazol(e));
Described non-aluminum chloride type ionic liquid is BMIPF
6(1-methyl-3-butyl imidazole hexafluorophosphate), EMIPF
6(1-methyl-3-ethyl imidazol(e) hexafluorophosphate), BMIBF
4(1-methyl-3-butyl imidazole a tetrafluoro borate) and EMIBF
4A kind of in (1-methyl-3-ethyl imidazol(e) a tetrafluoro borate).
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
The anhydrous trivalent iridium salt that adds 0.001g～0.20g when prepared by electrodeposition iridium layer in the aluminum chloride type ionic liquid of a kind of ionic liquid electrodeposition solution (tank liquor) that adopts of the present invention by 10ml is formed; Or the anhydrous trivalent iridium salt that adds 0.001g～0.20g in the non-aluminum chloride type ionic liquid by 10ml is formed; Or add the anhydrous trivalent iridium salt of 0.001g～0.20g in the aluminum chloride type ionic liquid by 10ml and the ethylene glycol of 1ml～20ml is formed.
Described anhydrous trivalent iridium salt can be IrCl
3, IrF
3And IrBr
3In a kind of;
Described aluminum chloride type ionic liquid is BMIC (chloridization 1-methyl-3-butyl imidazole) or EMIC (chlorination 1-methyl-3-ethyl imidazol(e));
Described non-aluminum chloride type ionic liquid is BMIPF
6(1-methyl-3-butyl imidazole hexafluorophosphate), EMIPF
6(1-methyl-3-ethyl imidazol(e) hexafluorophosphate), BMIBF
4(1-methyl-3-butyl imidazole a tetrafluoro borate) and EMIBF
4A kind of in (1-methyl-3-ethyl imidazol(e) a tetrafluoro borate).
In the present invention, the ionic liquid electrodeposition solution (tank liquor) that is added with ethylene glycol can effectively improve the solubleness of iridium salt.
Use ionic liquid electrodeposition solution of the present invention, under continuous current mode condition, the step of carrying out prepared by electrodeposition iridium layer on negative electrode has:
(A) preparation tank liquor
The anhydrous trivalent iridium salt that adds 0.001g～0.20g in the aluminum chloride type ionic liquid of tank liquor one: 10ml;
Add the anhydrous trivalent iridium salt of 0.001g～0.20g and the ethylene glycol of 1ml～20ml in the aluminum chloride type ionic liquid of tank liquor two: 10ml;
The anhydrous trivalent iridium salt that adds 0.001g～0.20g in the non-aluminum chloride type ionic liquid of tank liquor three: 10ml;
Described anhydrous trivalent iridium salt is IrCl
3, IrF
3And IrBr
3In a kind of;
Described aluminum chloride type ionic liquid is BMIC (chloridization 1-methyl-3-butyl imidazole) or EMIC (chlorination 1-methyl-3-ethyl imidazol(e));
Described non-aluminum chloride type ionic liquid is BMIPF
6(1-methyl-3-butyl imidazole hexafluorophosphate), EMIPF
6(1-methyl-3-ethyl imidazol(e) hexafluorophosphate), BMIBF
4(1-methyl-3-butyl imidazole a tetrafluoro borate) and EMIBF
4A kind of in (1-methyl-3-ethyl imidazol(e) a tetrafluoro borate).
(B) select electrode
Anode: a kind of in graphite, platinum or the iridium;
Negative electrode: the sheet material that negative electrode selects for use its surface to have electroconductibility gets final product, as engine body material Ni
3Al alloy, Mo, W, Re or Nb refractory metal;
(C) galvanostatic conditions galvanic deposit
Cathode current density is 0.01mA/dm
2～0.30mA/dm
2, the voltage between anode and the negative electrode is 0.2V～5.0V;
Low whipping speed is that 800r/min～1500r/min, temperature are under 60 ℃～120 ℃, behind galvanic deposit 0.5h～40h, takes out, and uses dehydrated alcohol, deionized water rinsing successively; Under being 35 ℃～55 ℃, temperature behind dry 5min～30min, promptly made the iridium layer then at the negative electrode plate surface.
Embodiment 1:
In the galvanic deposition cell of 25ml in vacuum glove box, add the anhydrous IrCl of 0.04g
3With the BMIC ionic liquid of 10ml, under the 1000r/min stirring velocity, be warming up to 100 ℃ ± 2 ℃, make iridium salt fully be dissolved in the ionic liquid;
Make anode with graphite (0.5cm * 1.0cm, purity 99%), use Ni
3Al (0.5cm * 1.0cm) make negative electrode, anode surface and cathode surface are arranged parallel to each other, and the distance between anode and the negative electrode is about 20mm;
Logical direct current carries out galvanic deposit, adopts continuous current, and cathode current density is 0.02mA/dm
2, the voltage between anode and the negative electrode is about 1.5V;
In 100 ℃ ± 2 ℃ electrodeposit liquid, take out the cathode base material behind the galvanic deposit 15h, use dehydrated alcohol and deionized water rinsing successively, then after temperature is 35 ℃ of following dry 10min, promptly at Ni
3The Al surface has made the iridium layer.
To at Ni
3The iridium layer that the Al surface obtains utilizes scanning electron microscope (SEM) to observe, and its pattern as shown in Figure 1.Among Fig. 1, at Ni
3The Al matrix surface has smooth, fine and close tectum.
To at Ni
3The tectum that the Al surface obtains carries out the XPS test, as shown in Figure 2.Among Fig. 2, be that the peak has appearred in 63.7eV and 60.7eV place, illustrate that tectal composition is metal Ir at bound energy.
Embodiment 2:
In the galvanic deposition cell of 25ml in vacuum glove box, add the anhydrous IrBr of 0.08g successively
3, 5ml BMIC ionic liquid and 5ml ethylene glycol, under the 1200r/min stirring velocity, be warming up to 80 ℃ ± 2 ℃, make iridium salt fully be dissolved in the ionic liquid;
Make anode with iridium sheet (0.5cm * 1.0cm, purity 99%), make negative electrode with Mo sheet (0.5cm * 1.0cm, purity is 99%); Anode surface and cathode surface are arranged parallel to each other, and the distance between anode and the negative electrode is about 20mm;
Logical direct current carries out galvanic deposit, adopts continuous current, and cathode current density is 0.10mA/dm
2, the voltage between anode and the negative electrode is 1.1V;
In 80 ℃ ± 2 ℃ electrodeposit liquid, take out the cathode base material behind the galvanic deposit 5h, use dehydrated alcohol and deionized water rinsing successively, under temperature is 50 ℃, behind the dry 5min, promptly made the iridium layer then on Mo sheet surface.
Embodiment 3:
In the galvanic deposition cell of 25ml in vacuum glove box, add the anhydrous IrF of 0.15g
3EMIBF with 10ml
4Ionic liquid is warming up to 110 ℃ ± 2 ℃ under the 1500r/min stirring velocity, make iridium salt fully be dissolved in the ionic liquid;
Make anode with iridium sheet (0.5cm * 1.0cm, purity 99%), with Nb (0.5cm * 1.0cm) make negative electrode, anode surface and cathode surface are arranged parallel to each other, and the distance between anode and the negative electrode is about 20mm;
Logical direct current carries out galvanic deposit, adopts continuous current, and cathode current density is 0.2mA/dm
2, the voltage between anode and the negative electrode is about 2V;
In 110 ℃ ± 2 ℃ electrodeposit liquid, take out the cathode base material behind the galvanic deposit 35h, use dehydrated alcohol and deionized water rinsing successively, under temperature is 45 ℃, behind the dry 10min, promptly made the iridium layer then on the Nb surface.
Adopt under the electrodeposition condition identical with embodiment 3, adopt different ionic liquids and anhydrous trivalent iridium salt to deposit the iridium layer, its consumption sees the following form:
| Ionic liquid | Consumption | Anhydrous trivalent iridium salt | Consumption |
| BMIPF 6 | 10ml | IrCl 3 | 0.15g |
| EMIPF 6 | 10ml | IrF 3 | 0.11g |
| BMIBF 4 | 10ml | IrBr 3 | 0.20g |
Claims (6)
1. the method for a prepared by electrodeposition iridium layer in ionic liquid electrodeposition solution is characterized in that including following preparation steps:
(A) preparation tank liquor
The anhydrous trivalent iridium salt that adds 0.001g～0.20g in the aluminum chloride type ionic liquid of tank liquor one: 10ml;
Add the anhydrous trivalent iridium salt of 0.001g～0.20g and the ethylene glycol of 1ml～20ml in the aluminum chloride type ionic liquid of tank liquor two: 10ml;
The anhydrous trivalent iridium salt that adds 0.001g～0.20g in the non-aluminum chloride type ionic liquid of tank liquor three: 10ml;
Anhydrous trivalent iridium salt is IrCl
3, IrF
3And IrBr
3In a kind of;
Aluminum chloride type ionic liquid is BMIC or EMIC;
Non-aluminum chloride type ionic liquid is BMIPF
6, EMIPF
6, BMIBF
4And EMIBF
4In a kind of;
(B) select electrode
Anode: a kind of in graphite, platinum or the iridium;
Negative electrode: the sheet material that negative electrode selects for use its surface to have electroconductibility gets final product;
(C) galvanostatic conditions galvanic deposit
Cathode current density is 0.01mA/dm
2～0.30mA/dm
2, the voltage between anode and the negative electrode is 0.2V～5.0V;
Low whipping speed is that 800r/min～1500r/min, temperature are under 60 ℃～120 ℃, behind galvanic deposit 0.5h～40h, takes out, and uses dehydrated alcohol, deionized water rinsing successively; Under being 35 ℃～55 ℃, temperature behind dry 5min～30min, promptly made the iridium layer then at the negative electrode plate surface.
2. according to claim 1 in ionic liquid electrodeposition solution the method for prepared by electrodeposition iridium layer, it is characterized in that: negative electrode is engine body material Ni in selecting the electrode step
3The Al alloy.
3. according to claim 1 in ionic liquid electrodeposition solution the method for prepared by electrodeposition iridium layer, it is characterized in that: negative electrode is the Mo metal in selecting the electrode step.
4. according to claim 1 in ionic liquid electrodeposition solution the method for prepared by electrodeposition iridium layer, it is characterized in that: negative electrode is the W metal in selecting the electrode step.
5. according to claim 1 in ionic liquid electrodeposition solution the method for prepared by electrodeposition iridium layer, it is characterized in that: negative electrode is the Re metal in selecting the electrode step.
6. according to claim 1 in ionic liquid electrodeposition solution the method for prepared by electrodeposition iridium layer, it is characterized in that: negative electrode is the Nb refractory metal in selecting the electrode step.
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| CN104611744B (en) * | 2014-12-15 | 2017-06-06 | 常州大学 | A kind of method of low-temperature aqueous solution electrochemical co-deposition nickel iridium alloy |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US3639219A (en) * | 1969-12-24 | 1972-02-01 | Int Nickel Co | Iridium plating |
| JP3256912B2 (en) * | 1993-04-30 | 2002-02-18 | 日本エレクトロプレイテイング・エンジニヤース株式会社 | Water-soluble iridium plating bath and plating method |
| JPH0734289A (en) * | 1993-07-22 | 1995-02-03 | Electroplating Eng Of Japan Co | Iridium plating article |
| CN101384752B (en) * | 2006-02-15 | 2013-04-03 | 阿克佐诺贝尔股份有限公司 | Method to electrodeposit metals using ionic liquids |
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