CN104120468B - A kind of without cyanogen cuprous electro-coppering zinc alloy solution - Google Patents
A kind of without cyanogen cuprous electro-coppering zinc alloy solution Download PDFInfo
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- CN104120468B CN104120468B CN201410286768.XA CN201410286768A CN104120468B CN 104120468 B CN104120468 B CN 104120468B CN 201410286768 A CN201410286768 A CN 201410286768A CN 104120468 B CN104120468 B CN 104120468B
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Abstract
A kind of without cyanogen cuprous electro-coppering zinc alloy solution, the present invention relates to a kind of preparation without cyanogen cuprous electro-coppering zinc alloy solution and using method.The controlledization problem that the present invention is to solve Coating composition during electro-coppering kirsite and the high power consumption problem caused without employing cupric in cyanogen technology at present.A kind of formulated, at 30 ~ 75 DEG C, 0.1 ~ 3.0A/dm without cyanogen cuprous electro-coppering zinc alloy solution employing cuprous compound, zinc chloride, cuprous non-cyanogen chelating agent, auxiliary complex-former, bath stability agent, brightener and sodium acetate2Under conditions of use, and use ruthenium-titanium anode or ormolu anode.The a kind of of the present invention can pass through to control the copper zinc ratio in coating for the selective complexation of cuprous ion without cyanogen cuprous electro-coppering zinc alloy solution, and plating solution uses cuprous ion can reduce the economized of power consumption, the beneficially energy.
Description
Technical field
The invention belongs to electro-coppering kirsite field, relate to a kind of preparation without cyanogen cuprous electro-coppering zinc alloy solution and using method.
Background technology
Ormolu is also referred to as pyrite, receives extensive concern owing to appearing similar to the color of gold.Therefore ormolu coating obtains large-scale application as imitation gold deposit, especially as the decorative coating of the products such as artware, light fixture and clock and watch.At the standard conditions, it is 0.521V (vsSHE) that cuprous ion is reduced to the current potential of metallic copper, it is 0.337V (vsSHE) that copper ion is reduced to the current potential of metallic copper, and the current potential that zinc ion is reduced to metallic zinc is-0.76V (vsSHE).Owing under mark state, the sedimentation potential of two kinds of metals differs greatly, it is achieved the top priority of copper zinc codeposition is to drag down the reduction potential of cuprous ion or copper ion, most effective of which method is exactly to add cuprous ion or the chelating agent of copper ion in the plating solution.The sedimentation potential of copper and zinc can be made by adding cyanide in the plating solution close as the chelating agent of cuprous ion.When in plating solution, the concentration of cyanide improves, cuprous ion can form with cyanide ion that ligancy is higher, the more negative complex ion of discharge potential, but without forming the complex ion of high coordination with zinc ion, thus obtains that composition is stable, crystallize careful coating.Therefore, cyanide copper kirsite obtains a wide range of applications.
But, owing to cyanide exists severe toxicity, cyanide copper kirsite technology does not only exist serious potential safety hazard, and the processing cost of electroplating wastewater is the most of a relatively high.Along with the raising of people's environmental consciousness, the exploitation of cyanideless electro-plating ormolu technology becomes a vital task of field of electroplating already.Under this background, the multiple cyanideless electro-plating ormolu system such as pyrophosphate system, tartrate system and ethylenediamine system is developed.Complexing power yet with non-cyanogen chelating agent is more weak relative to cyanide, current the most undesirable in terms of the control of Coating composition without cyanogen technology, not yet obtains large-scale commercial Application.Therefore, find effect more preferably chelating agent and replace cyanide, thus control the sedimentation potential of copper and zinc, it is thus achieved that composition rational ormolu coating has become the matter of utmost importance that cyanideless electro-plating ormolu needs to solve.It addition, various systems without cyanogen all use cupric, it will be greatly improved the energy consumption of electroplating process, it is unfavorable for the energy conservation of production process.
Find the selectivity strong chelating agent of non-cyanogen of cuprous ion, exploitation, without cyanogen cuprous electro-coppering zinc alloy solution, is possible not only to effectively control the relation between copper zinc sedimentation potential, it is thus achieved that the ormolu coating that composition is controlled, and the consumption of electric energy can be substantially reduced, create huge economic benefit.
Summary of the invention
The present invention is intended to realize controlledization of electro-coppering zn alloy coating composition, and solves at present without the high energy consumption problem using cupric to cause in cyanogen technology, and provides a kind of preparation without cyanogen cuprous electro-coppering zinc alloy solution and using method.
The one of the present invention is prepared according to following steps without cyanogen cuprous electro-coppering zinc alloy solution:
(1) according to the concentration of cuprous compound be 0.5 ~ 40.0g/L, the concentration of stabilizer be 0.2 ~ 25g/L, the concentration of cuprous non-cyanogen chelating agent be 10 ~ 160g/L, the concentration of auxiliary complex-former be that 5 ~ 80g/L weighs cuprous compound, stabilizer, cuprous non-cyanogen chelating agent and auxiliary complex-former respectively；(2) stabilizer step (1) weighed, cuprous non-cyanogen chelating agent and auxiliary complex-former are dissolved in the hydrochloric acid solution of 20mL/L successively, and heated and stirred obtains solution A to dissolving；(3) cuprous compound weighed in step (1) is joined in solution A, stirring to dissolving, obtained solution B after placing 12 hours；(4) according to chlorination zinc concentration be 5 ~ 50g/L, the concentration of brightener be 0.02 ~ 2.00g/L, the concentration of sodium acetate be that 10 ~ 40g/L weighs zinc chloride, brightener and sodium acetate respectively；(5) zinc chloride, brightener and the sodium acetate that weigh in step (4) are joined in solution B stirring to dissolving, adjust pH value to 1.0 ~ 6.0 with hydrochloric acid or ammonia after filtration, join without cyanogen cuprous electro-coppering zinc alloy solution.
Cuprous compound described in step (1) and (3) is the one in Red copper oxide, Cu-lyt. or cuprous bromide；Stabilizer described in step (1) and (2) is a kind of or the most several combination in vitamin C, sodium hypophosphite, DL-alpha-tocopherol, hydroquinone, catechol or resorcinol, described cuprous non-cyanogen chelating agent is the one in N-methylthiourea, tetramethyl thiourea, thiourea or ethylene thiourea, and described auxiliary complex-former is the one in disodiumedetate, trisodium citrate, sodium gluconate, adipic acid, sodium potassium tartrate tetrahydrate or sodium glutamate；Brightener described in step (4) and (5) is the combination of a kind of or two of which in ammonium molybdate, peptone, cresol sulfonic acid or nickel acetate.
A kind of temperature normally worked without cyanogen cuprous electro-coppering zinc alloy solution of the present invention is 30 ~ 75 DEG C, and the electric current density of normal work is 0.1 ~ 3.0A/dm2, and galvanic anode uses ruthenium-titanium anode or ormolu anode.
The one of the present invention without cyanogen cuprous electro-coppering zinc alloy solution by add cuprous non-cyanogen chelating agent, the discharge potential of cuprous ion can be significantly reduced with selectivity, it is allowed to close with the discharge potential of zinc ion, therefore can obtain stable components by the method for electrochemical reduction, crystallize careful ormolu coating.The present invention can be by controlling cuprous non-cyanogen chelating agent and the content of auxiliary complex-former in plating solution, it is thus achieved that copper content arbitrary target coating between 5.00% ~ 95.00%.By this carry out acid copper kirsite without cyanogen cuprous electro-coppering zinc alloy solution time, can reduce electroplating process consume electricity, be of value to the energy conservation of production process.
Accompanying drawing explanation
Fig. 1 be test one preparation without cyanogen cuprous electro-coppering zinc alloy solution；
Fig. 2 be test one preparation without the cuprous copper electroplating solution of cyanogen temperature be 40 DEG C, electric current density be 1.0A/dm2Under conditions of after plating 2 hours the electron scanning micrograph of gained ormolu coating；
Fig. 3 be test one preparation without the cuprous copper electroplating solution of cyanogen temperature be 40 DEG C, electric current density be 1.0A/dm2Under conditions of after plating 2 hours, the EDX of gained ormolu coating can spectrogram；
Fig. 4 be test one preparation without the cuprous copper electroplating solution of cyanogen temperature be 40 DEG C, electric current density be 1.0A/dm2Under conditions of after plating 2 hours the distribution diagram of element of gained ormolu coating, (a) copper, (b) zinc element.
Detailed description of the invention
Detailed description of the invention one: the one of present embodiment is prepared according to following steps without cyanogen cuprous electro-coppering zinc alloy solution:
(1) according to the concentration of cuprous compound be 0.5 ~ 40.0g/L, the concentration of stabilizer be 0.2 ~ 25g/L, the concentration of cuprous non-cyanogen chelating agent be 10 ~ 160g/L, the concentration of auxiliary complex-former be that 5 ~ 80g/L weighs cuprous compound, stabilizer, cuprous non-cyanogen chelating agent and auxiliary complex-former respectively；(2) stabilizer step (1) weighed, cuprous non-cyanogen chelating agent and auxiliary complex-former are dissolved in the hydrochloric acid solution of 20mL/L successively, and heated and stirred obtains solution A to dissolving；(3) cuprous compound weighed in step (1) is joined in solution A, stirring to dissolving, obtained solution B after placing 12 hours；(4) according to chlorination zinc concentration be 5 ~ 50g/L, the concentration of brightener be 0.02 ~ 2.00g/L, the concentration of sodium acetate be that 10 ~ 40g/L weighs zinc chloride, brightener and sodium acetate respectively；(5) zinc chloride, brightener and the sodium acetate that weigh in step (4) are joined in solution B stirring to dissolving, adjust pH value to 1.0 ~ 6.0 with hydrochloric acid or ammonia after filtration, join without cyanogen cuprous electro-coppering zinc alloy solution.
A kind of temperature normally worked without cyanogen cuprous electro-coppering zinc alloy solution of present embodiment is 30 ~ 75 DEG C, and the electric current density of normal work is 0.1 ~ 3.0A/dm2And use ruthenium-titanium anode or ormolu anode as galvanic anode, gained copper coating stable components, crystallize careful, can be by controlling cuprous non-cyanogen chelating agent and the content of auxiliary complex-former in plating solution, it is thus achieved that copper content arbitrary target coating between 5.00% ~ 95.00%.By this carry out acid copper kirsite without cyanogen cuprous electro-coppering zinc alloy solution time, can reduce electroplating process consume electricity, be of value to the energy conservation of production process.
Detailed description of the invention two: present embodiment cuprous compound described in step step (1) and (3) unlike detailed description of the invention one is the one in Red copper oxide, Cu-lyt. or cuprous bromide, and concentration is 1.0 ~ 30.0g/L.Other is identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment stabilizer described in step (1) and (2) unlike detailed description of the invention one or two is a kind of or the most several combination in vitamin C, sodium hypophosphite, DL-alpha-tocopherol, hydroquinone, catechol or resorcinol, and concentration is 0.5 ~ 20g/L.Other is identical with detailed description of the invention one or two.
When the stabilizer of present embodiment is compositions, any combination pressed by various stabilizers.
Detailed description of the invention four: present embodiment cuprous non-cyanogen chelating agent described in step (1) and (2) unlike one of detailed description of the invention one to three is the one in N-methylthiourea, tetramethyl thiourea, thiourea or ethylene thiourea, and concentration is 15 ~ 150g/L.Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention five: present embodiment auxiliary complex-former described in step (1) and (2) unlike one of detailed description of the invention one to four is the one in disodiumedetate, trisodium citrate, sodium gluconate, adipic acid, sodium potassium tartrate tetrahydrate or sodium glutamate, and concentration is 8 ~ 70g/L.Other is identical with one of detailed description of the invention one to four.
Detailed description of the invention six: present embodiment is the combination that brightener is a kind of or two of which in ammonium molybdate, peptone, cresol sulfonic acid or nickel acetate described in step (4) and (5) unlike one of detailed description of the invention one to five, and concentration is 0.05 ~ 1.80g/L.Other is identical with one of detailed description of the invention one to five.
When the brightener of present embodiment is compositions, two kinds of brighteners are by any combination.
Detailed description of the invention seven: present embodiment described temperature normally worked without cyanogen cuprous electro-coppering zinc alloy solution unlike one of detailed description of the invention one to six is 30 ~ 75 DEG C, and the electric current density normally worked is 0.1 ~ 3.0A/dm2, and use ruthenium-titanium anode or ormolu anode as galvanic anode.Other is identical with one of detailed description of the invention one to six.
By following verification experimental verification beneficial effects of the present invention:
Test one: the one of this test is prepared according to the following steps without cyanogen cuprous electro-coppering zinc alloy solution:
(1) according to the concentration of Cu-lyt. be 10.0g/L, the concentration of hydroquinone be 1.0g/L, the concentration of catechol be 2.0g/L, the concentration of tetramethyl thiourea be 40g/L, the concentration of disodiumedetate be that 20g/L weighs Cu-lyt., hydroquinone, catechol, tetramethyl thiourea and disodiumedetate respectively；(2) hydroquinone, catechol, tetramethyl thiourea and disodiumedetate that step (1) weighs being dissolved in successively in the hydrochloric acid solution of 20mL/L, heated and stirred obtains solution A to dissolving；(3) Cu-lyt. weighed in step (1) is joined in solution A, stirring to dissolving, obtained solution B after placing 12 hours；(4) according to chlorination zinc concentration be 30g/L, the concentration of ammonium molybdate be 0.2g/L, the concentration of peptone be 1.00g/L, the concentration of sodium acetate be that 30g/L weighs zinc chloride, ammonium molybdate, peptone and sodium acetate respectively；(5) zinc chloride, ammonium molybdate, peptone and the sodium acetate that weigh in step (4) are joined in solution B stirring to dissolving, adjust pH value to 3.5 with hydrochloric acid or ammonia after filtration, join without cyanogen cuprous electro-coppering zinc alloy solution.
This test preparation one without cyanogen cuprous electro-coppering zinc alloy solution as it is shown in figure 1, be lavender clear solution.The one of this test preparation without cyanogen cuprous electro-coppering zinc alloy solution temperature be 50 DEG C, electric current density be 1.0A/dm2And use ruthenium-titanium anode be under conditions of galvanic anode after plating 2 hours the electron scanning micrograph of gained ormolu coating as in figure 2 it is shown, ormolu coating is smooth as can be seen from Figure 2, it is careful to crystallize；The EDX spectrogram of gained ormolu coating contains copper and zinc element as it is shown on figure 3, coating is central as can be seen from Figure 3, and analyzing the mass percent of copper in display coating is 62.5%, and in coating, the mass percent of zinc element is 37.5%；As shown in Figure 4, as can be seen from Figure 4, in the middle of coating, copper and zinc element are evenly distributed the distribution diagram of element of gained ormolu coating.
A kind of current efficiency without cyanogen cuprous electro-coppering zinc alloy solution recording this test preparation according to mass method is 79.3%, owing to using Cu-lyt. as electroplating main salt, therefore can be of value to the energy conservation of production process with the consumption of saves energy.
Test two: the one of this test is prepared according to the following steps without cyanogen cuprous electro-coppering zinc alloy solution:
(1) according to the concentration of Cu-lyt. be 10.0g/L, the concentration of resorcinol be 2.0g/L, the concentration of thiourea be 35g/L, the concentration of trisodium citrate be that 25g/L weighs Cu-lyt., resorcinol, thiourea and trisodium citrate respectively；(2) resorcinol, thiourea and trisodium citrate that step (1) weighs being dissolved in successively in the hydrochloric acid solution of 20mL/L, heated and stirred obtains solution A to dissolving；(3) Cu-lyt. weighed in step (1) is joined in solution A, stirring to dissolving, obtained solution B after placing 12 hours；(4) according to chlorination zinc concentration be 25g/L, the concentration of ammonium molybdate be 0.2g/L, the concentration of peptone be 1.00g/L, the concentration of sodium acetate be that 30g/L weighs zinc chloride, ammonium molybdate, peptone and sodium acetate respectively；(5) zinc chloride, ammonium molybdate, peptone and the sodium acetate that weigh in step (4) are joined in solution B stirring to dissolving, adjust pH value to 3.5 with hydrochloric acid or ammonia after filtration, join without cyanogen cuprous electro-coppering zinc alloy solution.
The one of this test preparation without cyanogen cuprous electro-coppering zinc alloy solution temperature be 50 DEG C, electric current density be 1.0A/dm2And use ruthenium-titanium anode be under conditions of galvanic anode after plating 2 hours in gained ormolu coating the mass percent of copper be 68.6%, in coating, the mass percent of zinc element is 31.4%.
A kind of current efficiency without cyanogen cuprous electro-coppering zinc alloy solution recording this test preparation according to mass method is 81.6%.
Test three: the one of this test is prepared according to the following steps without cyanogen cuprous electro-coppering zinc alloy solution:
(1) according to the concentration of Cu-lyt. be 15.0g/L, ascorbic concentration be 3.0g/L, the concentration of thiourea be 85g/L, the concentration of sodium potassium tartrate tetrahydrate be that 60g/L weighs Cu-lyt., vitamin C, thiourea and sodium potassium tartrate tetrahydrate respectively；(2) vitamin C, thiourea and sodium potassium tartrate tetrahydrate that step (1) weighs being dissolved in successively in the hydrochloric acid solution of 20mL/L, heated and stirred obtains solution A to dissolving；(3) Cu-lyt. weighed in step (1) is joined in solution A, stirring to dissolving, obtained solution B after placing 12 hours；(4) according to chlorination zinc concentration be 40g/L, the concentration of cresol sulfonic acid be 0.8g/L, the concentration of nickel acetate be 0.1g/L, the concentration of sodium acetate be that 30g/L weighs zinc chloride, cresol sulfonic acid, nickel acetate and sodium acetate respectively；(5) zinc chloride, cresol sulfonic acid, nickel acetate and the sodium acetate that weigh in step (4) are joined in solution B stirring to dissolving, adjust pH value to 3.0 with hydrochloric acid or ammonia after filtration, join without cyanogen cuprous electro-coppering zinc alloy solution.
The one of this test preparation without cyanogen cuprous electro-coppering zinc alloy solution temperature be 50 DEG C, electric current density be 1.0A/dm2And use ruthenium-titanium anode be under conditions of galvanic anode after plating 2 hours in gained ormolu coating the mass percent of copper be 50.8%, in coating, the mass percent of zinc element is 49.2%.
A kind of current efficiency without cyanogen cuprous electro-coppering zinc alloy solution recording this test preparation according to mass method is 72.8%.
Claims (6)
1. one kind without cyanogen cuprous electro-coppering zinc alloy solution, it is characterised in that the compound method of this electro-coppering zinc alloy solution sequentially includes the following steps:
(1) according to the concentration of cuprous compound be 0.5 ~ 40.0g/L, the concentration of stabilizer be 0.2 ~ 25g/L, the concentration of cuprous non-cyanogen chelating agent be 15 ~ 150g/L, the concentration of auxiliary complex-former be that 5 ~ 80g/L weighs cuprous compound, stabilizer, cuprous non-cyanogen chelating agent and auxiliary complex-former respectively；(2) stabilizer step (1) weighed, cuprous non-cyanogen chelating agent and auxiliary complex-former are dissolved in the hydrochloric acid solution of 20mL/L successively, and heated and stirred obtains solution A to dissolving；(3) cuprous compound weighed in step (1) is joined in solution A, stirring to dissolving, obtained solution B after placing 12 hours；(4) according to chlorination zinc concentration be 5 ~ 50g/L, the concentration of brightener be 0.02 ~ 2.00g/L, the concentration of sodium acetate be that 10 ~ 40g/L weighs zinc chloride, brightener and sodium acetate respectively；(5) zinc chloride, brightener and the sodium acetate that weigh in step (4) are joined in solution B stirring to dissolving, adjust pH value to 1.0 ~ 3.0 with hydrochloric acid or ammonia after filtration, join without cyanogen cuprous electro-coppering zinc alloy solution；
Cuprous non-cyanogen chelating agent described in step (1) and (2) is the one in N-methylthiourea, tetramethyl thiourea, thiourea or ethylene thiourea；
Described can be by controlling cuprous non-cyanogen chelating agent and the content of auxiliary complex-former in plating solution without cyanogen cuprous electro-coppering zinc alloy solution, it is thus achieved that copper content arbitrary target coating between 5.00% ~ 95.00%.
The most according to claim 1 a kind of without cyanogen cuprous electro-coppering zinc alloy solution, it is characterized in that the cuprous compound described in step (1) and (3) is the one in Red copper oxide, Cu-lyt. or cuprous bromide, concentration is 1.0 ~ 30.0g/L.
The most according to claim 1 a kind of without cyanogen cuprous electro-coppering zinc alloy solution, it is characterized in that the stabilizer described in step (1) and (2) is a kind of or the most several combination in vitamin C, sodium hypophosphite, DL-alpha-tocopherol, hydroquinone, catechol or resorcinol, concentration is 0.5 ~ 20g/L.
The most according to claim 1 a kind of without cyanogen cuprous electro-coppering zinc alloy solution, it is characterized in that the auxiliary complex-former described in step (1) and (2) is the one in disodiumedetate, trisodium citrate, sodium gluconate, adipic acid, sodium potassium tartrate tetrahydrate or sodium glutamate, concentration is 8 ~ 70g/L.
The most according to claim 1 a kind of without cyanogen cuprous electro-coppering zinc alloy solution, it is characterized in that the combination that the brightener described in step (4) and (5) is a kind of or two of which in ammonium molybdate, peptone, cresol sulfonic acid or nickel acetate, concentration is 0.05 ~ 1.80g/L.
6., according to the one described in aforementioned any one claim without cyanogen cuprous electro-coppering zinc alloy solution, it is characterised in that the described temperature normally worked without cyanogen cuprous electro-coppering zinc alloy solution is 30 ~ 75 DEG C, the electric current density of normal work is 0.1 ~ 3.0A/dm2, and use ruthenium-titanium anode or ormolu anode as galvanic anode.
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| CN113466304A (en) * | 2021-06-24 | 2021-10-01 | 青岛科技大学 | PEDOT (PEDOT-PSS) hydrogel modified electrode as well as preparation method and application thereof |
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| CN101545123B (en) * | 2009-03-30 | 2010-12-01 | 哈尔滨汽轮机厂有限责任公司 | Method for non-cyanide copper electroplating of steel parts |
| CN101624714B (en) * | 2009-08-18 | 2010-12-29 | 杜强 | Cu-Sn-Zn plating solution containing organic addition agent and electroplating technique utilizing same |
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| GB1181964A (en) * | 1966-05-14 | 1970-02-18 | English Electric Co Ltd | Improvements in or relating to the Electrodeposition of Copper |
| US4005174A (en) * | 1974-06-17 | 1977-01-25 | Fernand Jacques Joseph Bodson | Process for the elimination of chloride from zinc sulphate solutions |
| US5302278A (en) * | 1993-02-19 | 1994-04-12 | Learonal, Inc. | Cyanide-free plating solutions for monovalent metals |
| CN1170963C (en) * | 1997-03-18 | 2004-10-13 | 利罗纳尔公司 | Cyanide-free monovalent copper eletroplating solutions |
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| CN102011157A (en) * | 2009-09-04 | 2011-04-13 | 耿香珍 | Electroplated zinc and copper alloy |
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