CN101054698A - Method of pre-electrodepositing copper on zinc surface by ion liquid - Google Patents
Method of pre-electrodepositing copper on zinc surface by ion liquid Download PDFInfo
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- CN101054698A CN101054698A CN 200710037409 CN200710037409A CN101054698A CN 101054698 A CN101054698 A CN 101054698A CN 200710037409 CN200710037409 CN 200710037409 CN 200710037409 A CN200710037409 A CN 200710037409A CN 101054698 A CN101054698 A CN 101054698A
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Abstract
The present invention relates to a process for pre-electrodeposition of copper at zincium surface by adopting ion liquid. Said method in accordance with the present invention comprises the following steps: selectively synthesizing intermediate of chlorinated 1-methyl-3-butyl-imidazole (BMIM-Cl), preparing BMIBF4 ionic liquid from the BMIM-Cl together with NH4BF4, adding the intermediate of 10%(BMIM-Cl ) and dissolving it in BMIBF4 ionic liquid, and adding waterless copper chloride into the ionic liquid mentioned above finally, stirring them uniformly to form an ionic liquid electrolyte for electroplate copper, wherein said ionic liquid can be used for electric plating zincium surface with one layer of cuprum because that the ionic liquid will substantially not erode surfaces of zincium substrate and will not be involved in a metatheticalreaction with the cupric ions in the ionic liquid at the same time. The electrical current efficiency of the ionic liquid for pre-electrodeposition of copper in accordance with the present invention may achieve 100%. The pin-holing phenomena in plating and hydrogen separation in aqueous solution electrodeposition of copper will not occur for the ionic liquid for electrodeposition of copper. Said ionic liquid for electrodeposition of copper will not pollute the environments.
Description
Technical field
The present invention relates to a kind of method of zinc surface pre-electrodepositing copper, particularly a kind of method that adopts ionic liquid at the zinc surface pre-electrodepositing copper.
Background technology
Zinc alloy diecasting is cheap, production efficiency is high, working accuracy is high, has certain mechanical strength, can be cast into shape complexity, the higher various component of precision, be applied on haberdashery and hardware, light industry household electrical appliances, mechano-electronic, the imitative artwork through galvanized zine pressure casting ornamental, corrosion stability good and characteristics such as inexpensive with it.For this reason, domestic galvanizer author has carried out a large amount of research to the electroplating technology of zine pressure casting in recent years.
The surface chemical property of zinc casting is more active, corrosion resistance is poor, therefore need be at the stronger metal of zinc casting electroplating surface one deck corrosion resistance, general industry all is the technology that adopts electronickelling and chromium, because the chemical property of zinc is more active, electroplating solution take place easily the dissolved corrosion phenomenon and with solution in other metal ion (nickel) replacement(metathesis)reaction takes place, can influence the bonding force between electrolytic coating and the zinc-base body like this, thereby influence electrolytic coating, therefore in the technical process of prior art, use pre-plating of copper cyanide technology, because prussiate has good complex ability, after it and copper complexing, can reduce in the solution metal copper ion freely, can avoid the replacement(metathesis)reaction between the copper zinc effectively, thereby can improve the bonding force between copper and the matrix zinc, still, the national environmental protection method has stipulated clearly and will progressively eliminate the prussiate electroplating technology that it is extremely urgent to seek the new pre-copper plating process of no cyanogen like this.
Summary of the invention
The object of the present invention is to provide a kind of method that adopts ionic liquid at the zinc surface pre-electrodepositing copper, to solve the environmental issue that the technology that adopts the pre-electro-coppering of cyaniding in existing zinc casting electroplating nickel on surface and the chromium process exists.
Design of the present invention is:
Because ion liquid physicochemical property, as the specific conductivity height, at high temperature still have very low vapour pressure, electrochemical stability good (broad electrochemical window is promptly arranged), dissolving power to organism and inorganics is strong, thermostability and good flame resistance, acid-basicity such as can regulate at characteristics, wherein Tetrafluoroboric acid 1-methyl-3-butyl imidazole (BMIBF
4) have a good characteristic that exists stable in the air.The inventive method is selected synthesizing chlorinated 1-methyl-3-butyl-imidazoles (BMIM-Cl) intermediate, again with NH
4BF
4Preparation BMIBF
4Ionic liquid, and then add 10% (BMIM-Cl) intermediate and be dissolved in BMIBF
4In the ionic liquid, at last in the above-mentioned ionic liquid of the cuprous adding of anhydrous chlorides of rase, be stirred into the ionic liquid electrolyte of preparing electro-coppering after mutually, this ionic liquid go up substantially not can the corrosion zinc matrix the surface, simultaneously it also not can with cupric ion generation replacement(metathesis)reaction in the ionic liquid, therefore can electroplate layer of copper at zinc surface.
According to above-mentioned design, the present invention adopts following technical proposals:
A kind of method that adopts ionic liquid at the zinc surface pre-electrodepositing copper is characterized in that the concrete steps of this method are:
A) be n-propylcarbinyl chloride and 1-methyl-imidazoles that 1: 1 ratio is dissolved in the mixed solvent of toluene and water in molar ratio, wherein the volume ratio of toluene and water is 1: 1, refluxes after 72 hours, obtains chloridization 1-methyl-3-butyl imidazole ionic liquid intermediate; Use Rotary Evaporators 80～82 ℃ of following vacuum removal of impurity 5～6 hours in this ionic liquid intermediate again;
B) 1.1: 1 in molar ratio mixed of ionic liquid intermediate that above-mentioned steps a is synthesized and ammonium borofluoride becomes mixed solution, adding acetone as reaction medium, wherein the volume ratio of acetone and mixed solution is 1: 1, after the back flow reaction 72 hours, filtering separation ammonium chloride, filtrate rotary evaporation in vacuo 18～24 hours under 80～82 ℃ of conditions,, obtain BMIBF to remove acetone, other side reaction organic impurity and moisture
4Ionic liquid;
C) stir down, the cuprous BMIBF that obtains through step b that joins of anhydrous chlorides of rase
4In the ionic liquid, till saturated;
D) will be through pretreated zinc casting as negative electrode, as anode, the ionic liquid that obtains with step c is an electrolytic solution with fine copper, and temperature is controlled to be 45～55 ℃, and voltage control is in 1.5V, and current density is 0.5～1.0A/dm
2, electroplated 30～60 minutes;
E) at last plating piece is cleaned, dries.
The present invention has following conspicuous outstanding substantive distinguishing features and remarkable advantage compared with prior art:
(1) current efficiency of the pre-electro-coppering of ionic liquid can reach 100%.
(2) the ionic liquid electro-coppering does not have in the aqueous solution electro-coppering and to produce liberation of hydrogen and coating has the pin hole phenomenon.
(3) the ionic liquid electro-coppering can not produce environment and pollute.
Embodiment
Is n-propylcarbinyl chloride and 1-methyl-imidazoles that 1: 1 ratio is dissolved in the mixed solvent of toluene and water in molar ratio, and wherein the volume ratio of toluene and water is 1: 1, and reflux obtained chloridization 1-methyl-3-butyl imidazole ionic liquid intermediate after 72 hours; Use Rotary Evaporators 80～82 ℃ of following vacuum removal of impurity 5～6 hours in this ionic liquid intermediate again; 1.1: 1 in molar ratio mixed of this ionic liquid intermediate and ammonium borofluoride is become mixed solution, add acetone again as reaction medium, wherein the volume ratio of acetone and mixed solution is 1: 1, after the back flow reaction 72 hours, filtering separation ammonium chloride, filtrate rotary evaporation in vacuo 18～24 hours under 80～82 ℃ of conditions,, obtain BMIBF to remove acetone, other side reaction organic impurity and moisture
4Ionic liquid; Stir down, cuprous this BMIBF that joins of anhydrous chlorides of rase
4In the ionic liquid, till saturated; Will be through pretreated zinc casting as negative electrode, as anode, the ionic liquid that obtains with step c is an electrolytic solution with fine copper, and temperature is controlled to be 45～55 ℃, and voltage control is in 1.5V, and current density is 0.5～1.0A/dm
2, electroplated 30～60 minutes; At last plating piece is cleaned, dries.Concrete processing parameter sees also table 1.
The technology of table 1 ionic liquid electro-coppering
| Negative electrode | Volts DS (V) | Current density (A/dm 2) | Electroplating temperature ℃ | Stir (rpm) | The effect of zinc metal sheet surface electrical copper facing | |
| Bonding force | Quality of coating | |||||
| Zinc metal sheet | 1.0 | 0.5 | 25 | 200 | Better | Smooth careful |
| Zinc metal sheet | 1.2 | 1.0 | 50 | 200 | Good | Smooth careful |
| Zinc metal sheet | 1.5 | 2.0 | 80 | 200 | Better | More smooth careful |
Claims (1)
1. method that adopts ionic liquid at the zinc surface pre-electrodepositing copper is characterized in that the concrete steps of this method are:
A. be n-propylcarbinyl chloride and 1-methyl-imidazoles that 1: 1 ratio is dissolved in the mixed solvent of toluene and water in molar ratio, wherein the volume ratio of toluene and water is 1: 1, refluxes after 72 hours, obtains chloridization 1-methyl-3-butyl imidazole ionic liquid intermediate; Use Rotary Evaporators 80～82 ℃ of following vacuum removal of impurity 5～6 hours in this ionic liquid intermediate again;
B. 1.1: 1 in molar ratio mixed of ionic liquid intermediate that above-mentioned steps a is synthesized and ammonium borofluoride becomes mixed solution, add acetone again as reaction medium, wherein the volume ratio of acetone and mixed solution is 1: 1, after the back flow reaction 72 hours, filtering separation ammonium chloride, filtrate rotary evaporation in vacuo 18～24 hours under 80～82 ℃ of conditions,, obtain BMIBF to remove acetone, other side reaction organic impurity and moisture
4Ionic liquid;
C. stir down, the cuprous BMIBF that obtains through step b that joins of anhydrous chlorides of rase
4In the ionic liquid, till saturated;
D. will be through pretreated zinc casting as negative electrode, as anode, the ionic liquid that obtains with step c is an electrolytic solution with fine copper, and temperature is controlled to be 45～55 ℃, and voltage control is in 1.5V, and current density is 0.5～1.0A/dm
2, electroplated 30～60 minutes;
E. at last plating piece is cleaned, dries.
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|---|---|---|---|
| CN 200710037409 CN101054698A (en) | 2007-02-09 | 2007-02-09 | Method of pre-electrodepositing copper on zinc surface by ion liquid |
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|---|---|---|---|
| CN 200710037409 CN101054698A (en) | 2007-02-09 | 2007-02-09 | Method of pre-electrodepositing copper on zinc surface by ion liquid |
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| CN101230148B (en) * | 2007-12-25 | 2010-12-01 | 浙江大学 | Method for preparing chitosan-ionic liquid-copper nanoparticles composite membrane on electrode negative surface by one-step electic synthesis |
| CN102061492A (en) * | 2010-12-09 | 2011-05-18 | 沈阳师范大学 | Electroplate liquid based on room temperature ion liquid indium chloride/fluoboric acid 1-methyl-3-butylimidazole system |
| CN102191517A (en) * | 2010-03-10 | 2011-09-21 | 中国科学院过程工程研究所 | Method of electroplating zinc, nickel, molybdenum and their alloys by using ionic liquid |
| CN102191545A (en) * | 2010-03-08 | 2011-09-21 | 宁波大学 | Method for growing cuprous bromide crystals |
| CN102517608A (en) * | 2011-12-23 | 2012-06-27 | 彩虹集团公司 | Method for electrodepositing zinc and zinc alloy at low temperature by ionic liquor |
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| CN104499002A (en) * | 2014-12-10 | 2015-04-08 | 上海大学 | Method for preparing copper-iron nano plated layer from low-grade sulfide ore through direct electro-deposition |
| CN105088287A (en) * | 2015-08-13 | 2015-11-25 | 斌源材料科技（上海）有限公司 | Electrolyte prepared based on deep eutetic ion liquid and water and electroplating method thereof |
| CN106591897A (en) * | 2016-11-24 | 2017-04-26 | 浙江大学 | Cyanide-free ionic-liquid copper-plating solution and copper plating process |
| CN106661753A (en) * | 2014-04-15 | 2017-05-10 | 尼奥工业有限责任公司 | Ionic liquid electrolyte and method to electrodeposit metals |
| CN108149285A (en) * | 2017-12-28 | 2018-06-12 | 广东达志环保科技股份有限公司 | Non-cyanide plating solution for copper-plating used and electro-plating method |
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| CN102191545A (en) * | 2010-03-08 | 2011-09-21 | 宁波大学 | Method for growing cuprous bromide crystals |
| CN102191517A (en) * | 2010-03-10 | 2011-09-21 | 中国科学院过程工程研究所 | Method of electroplating zinc, nickel, molybdenum and their alloys by using ionic liquid |
| CN102191517B (en) * | 2010-03-10 | 2014-04-30 | 中国科学院过程工程研究所 | Method of electroplating zinc, nickel, molybdenum and their alloys by using ionic liquid |
| CN102061492A (en) * | 2010-12-09 | 2011-05-18 | 沈阳师范大学 | Electroplate liquid based on room temperature ion liquid indium chloride/fluoboric acid 1-methyl-3-butylimidazole system |
| CN102061492B (en) * | 2010-12-09 | 2013-03-20 | 沈阳师范大学 | Electroplate liquid based on room temperature ion liquid indium chloride/fluoboric acid 1-methyl-3-butylimidazole system |
| CN102517608A (en) * | 2011-12-23 | 2012-06-27 | 彩虹集团公司 | Method for electrodepositing zinc and zinc alloy at low temperature by ionic liquor |
| CN102912384A (en) * | 2012-10-31 | 2013-02-06 | 南京工业大学 | Method for preparing porous copper powder by electrodepositing Cu-Al-Mg-Li alloy |
| CN102912384B (en) * | 2012-10-31 | 2015-03-04 | 南京工业大学 | Method for preparing porous copper powder by electrodepositing Cu-Al-Mg-Li alloy |
| CN106661753A (en) * | 2014-04-15 | 2017-05-10 | 尼奥工业有限责任公司 | Ionic liquid electrolyte and method to electrodeposit metals |
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| CN104499002A (en) * | 2014-12-10 | 2015-04-08 | 上海大学 | Method for preparing copper-iron nano plated layer from low-grade sulfide ore through direct electro-deposition |
| CN105088287A (en) * | 2015-08-13 | 2015-11-25 | 斌源材料科技（上海）有限公司 | Electrolyte prepared based on deep eutetic ion liquid and water and electroplating method thereof |
| CN106591897B (en) * | 2016-11-24 | 2019-05-03 | 浙江大学 | A kind of no cryanide ion liquid copper plating solution and copper-plating technique |
| CN106591897A (en) * | 2016-11-24 | 2017-04-26 | 浙江大学 | Cyanide-free ionic-liquid copper-plating solution and copper plating process |
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