CN102242381A - Alkaline non-cyanide copper plating solution with main coordination agent of methylenediphosphonate - Google Patents
Alkaline non-cyanide copper plating solution with main coordination agent of methylenediphosphonate Download PDFInfo
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- CN102242381A CN102242381A CN2011101795055A CN201110179505A CN102242381A CN 102242381 A CN102242381 A CN 102242381A CN 2011101795055 A CN2011101795055 A CN 2011101795055A CN 201110179505 A CN201110179505 A CN 201110179505A CN 102242381 A CN102242381 A CN 102242381A
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- methylenediphosphonate
- mdp
- cyanide
- copper
- electroplate liquid
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Abstract
The invention provides an alkaline copper plating solution with a main coordination agent of methylenediphosphonate, and relates to non-cyanide electroplating field. The plating solution comprises the following components: methylenediphosphonate (MDP) with concentration of 30-100 g/L, cupric ion with concentration of 3-25 g/L, and carbonate ion with concentration of 10-80 g/L. By using sodium hydroxide or potassium hydroxide, pH value of the solution is adjusted to 7.5-13.5. The plating solution in the invention has the characteristics of simple formula, no cyanide pollution, small concentration polarization generated in an electroplating process, good stability of the plating solution, and wide allowable current density range. By using the plating solution to plate copper on iron matrix, zinc matrix, zinc alloy matrix or aluminium zinc galvanizing directly, a copper plating layer with good bonding force with the matrix is obtained.
Description
(1) technical field
The present invention relates to a kind of new alkaline non-cyanide plating solution for copper-plating used, particularly using methylenediphosphonate (MDP) (MDP) is the alkaline non-cyanide plating solution for copper-plating used of main coordination agent, be used for iron, zinc or zinc alloy, soak the direct copper facing of metallic matrixes such as aluminium behind the zinc, also can be used for the copper coating thickening, belong to technical field of surface.
(2) background technology
Because of the acid copper sulfate electroplate liquid in iron, zinc or the direct copper facing of metallic matrix meeting generation replacement(metathesis)reactions such as zinc alloy, aluminium, cause the bonding force of matrix and copper coating very poor.In order to obtain high-bond, now industrial widely used be the alkaline cyanide electroplate liquid.But, can produce great environment and social safety accident potential because prussiate has very large bio-toxicity.The 28 scope of electroplating enterprise having been listed in " forcing the cleaner production audit " of the Law of the People's Republic of China on Promoting Clean Production.The former State Economic and Trade Commission of China is in issue on June 2nd, 2002 the 32nd command, and clearly proposition will be eliminated and contain the cyanogen plating.National Development and Reform Committee issued the 40th command again " catalogue (basis in 2005) was instructed in industry restructuring, reaffirms to eliminate to contain the galvanized industry policy of cyanogen on December 2nd, 2005.Therefore the exploitation of cyanide-free copper electroplating technology is very urgent, but also is a technology.The relatively more typical cyanide-free copper electroplating system of research report has alkaline pyrophosphate copper plating, sulfamate copper facing, citrate copper-plating, organic phosphonate copper facing, organic carboxylate copper facing etc. at present.(patent No.: 85103672) disclose a kind of alkaline non-cyanide electrolytic copper plating liquor, the proposition spent glycol is a coordination agent to Chinese invention patent.With phosphorated compound in the structure is that the copper plating bath of main coordination agent is the technology that the industrialization future is arranged in the cyanide-free copper electroplating most.On some steel matrix, use as pyrophosphate copper plating liquid, but pyrophosphate copper plating solution is to the control of pH value very strict (general 8.13-8.19), this is because two phosphorus of pyrophosphate connect by oxygen, the pyrophosphate facile hydrolysis generated the ortho-phosphoric acid root when pH value of solution value was low, thereby copper plating solution was lost efficacy.Two phosphorus of pyrophosphate are connected to change into to connect by carbon by oxygen be formed with the machine phosphonic acid thing, will improve the processing performance of plating bath greatly.The Chinese invention patent of the method for a kind of direct copper non-cyanide plating of zinc alloy casting die by name (patent No.: 200610151222.9), propose to constitute directly electro-coppering on the zinc alloy diecasting matrix of electroplate liquid with organic phospho acid such as 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP), Amino Trimethylene Phosphonic Acid (ATMP) and ethylenediamine tetramethylene phosphonic acid (EDTMP).And with 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) be the alkaline non-cyanide copper plating bath chemical property of main coordination agent in research paper, also repeatedly mention (Fang Jingli, Ma Xinmao, Lu Weizhen. SCI, 1981,2 (3): 285-293.The smart military Jiang Mei swallow Qiao Liang of Zheng, etc., CO
3 2-To the influence research of 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid copper plating bath, Acta PhySico-Chimica Sinica, 2008,24 (9): 1733-1738).The molecular weight of HEDP is 206, molecular structural formula as shown in Figure 1, between two phosphorus-the C group because have-the OH group and-CH
3Group links to each other, make the HEDP molecular weight relatively large, when HEDP and copper complexing, will reduce the velocity of diffusion of complexing product in solution because of the volume steric effect, in electroplating process, can produce concentration polarization, this causes along with the continuity work plating bath of electroplating time is very unstable, causes binding force of cladding material not good in the copper facing meeting that powers on of the higher matrix of activity such as zinc alloy matrix.
(3) summary of the invention
The invention provides a kind of alkaline non-cyanide copper plating solution that does not contain prussiate, solved that to contain the environmental pollution that the prussiate plating bath brings in the prior art serious, do not contain the prussiate plating bath and cause coating and basal body binding force not good, problems such as HEDP plating bath long-time running instability.
For reaching goal of the invention the technical solution used in the present invention be:
A kind of is the electroplate liquid that the alkaline non-cyanide copper facing of main coordination agent is used with methylenediphosphonate (MDP) (MDP), it is characterized in that this electroplate liquid mainly contains: methylenediphosphonate (MDP) (MDP) concentration 30-100 grams per liter (g/L), bivalent cupric ion concentration 3-25g/L.The salt that bivalent cupric ion is provided can be copper sulfate or cupric nitrate or cupric chloride or ventilation breather.With alkaline matter regulator solution pH to 7.5～13.5 such as sodium hydroxide or potassium hydroxide,, add the carbanion of 10-80g/L in the solution for solvability and the careful copper layer of acquisition crystallization that improves copper anode.The collocation method of this cyanide-free copper electroplating solution is: respectively methylenediphosphonate (MDP) and bivalent cupric ion salt are mixed after with water dissolution earlier, add sodium hydroxide then or more than the potassium hydroxide regulator solution pH to 7, add carbanion at last, stirring and dissolving promptly gets described cyanide-free copper electroplating solution.Main processing parameter is during the plating of this cyanide-free copper electroplating solution: 15-70 ℃ of control solution temperature, cathode current density 0.5-4 ampere/square decimeter (A/dm
2).
Of the present invention is that the beneficial effect of the alkaline non-cyanide plating solution for copper-plating used of main coordination agent is mainly reflected in: molecular structural formula such as Fig. 2 of (1) MDP with methylenediphosphonate (MDP), molecular weight is 176, the content of copper ion that contains in solution is identical, the mol ratio that realizes cupric ion/main coordination agent is identical, obviously the needed quality of MDP is lacked than HEDP, little because of the volume steric effect simultaneously, the complex reaction between MDP and the copper is easier to carry out.(2) be that alkaline non-cyanide copper facing that main coordination agent constitutes is carried out the cathodic polarization curve contrast with plating bath (as Fig. 3, the polarization curve testing apparatus is the CHI650 electrochemical workstations that Shanghai occasion China produces with HEDP and methylenediphosphonate (MDP) respectively; Test condition: 20 ℃ of solution temperatures, sweep velocity are 2 millivolts/second (mV/s), and stainless steel electrode is the research electrode, and mercurous chloride electrode is made reference electrode, and platinum electrode is made supporting electrode; Cupric ion (the Cu of two solution
2+) content is identical, HEDP:Cu
2+With MDP:Cu
2+Mol ratio identical), discovery is that the plating bath of main coordination agent is wider and limit current density is bigger than being that the plating bath of main coordination agent has a copper reduction reaction potential interval with methylenediphosphonate (MDP) with 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, this shows with methylenediphosphonate (MDP) to be plating bath littler concentration polarization of meeting generation in electroplating process of main coordination agent, the current density range that allows is wider, the good stability of plating bath.
(3) be the alkaline non-cyanide copper facing plating bath that main coordination agent constitutes in order to methylenediphosphonate (MDP), prescription is simple, and is nontoxic, do not have cyanide pollution, directly copper facing on the aluminium at iron-based body, zinc or zinc alloy matrix, after soaking zinc obtains the bonding force excellence of copper coating and matrix.
(4) description of drawings
Fig. 1 is the molecular structure of 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP).
Fig. 2 is the molecular structure of methylenediphosphonate (MDP) (MDP).
Fig. 3 is to be the cathodic polarization curve comparison diagram of the alkaline non-cyanide copper facing of main coordination agent formation with plating bath with HEDP and methylenediphosphonate (MDP) respectively.
(5) embodiment
The present invention is described further below in conjunction with specific embodiment, but method related in the scheme and technical parameter can not be interpreted as limitation of the present invention.
Embodiment 1:
Is the alkaline non-cyanide copper plating solution that main coordination agent constitutes by following proportioning preparation with methylenediphosphonate (MDP).
Load weighted methylenediphosphonate (MDP) and cupric sulfate pentahydrate are mixed with deionized water dissolving respectively, in stirring, add potassium hydroxide solution, add quantitative salt of wormwood at last and be stirred to dissolving fully.
In the gained solution, 30 ℃ of regulator solution temperature are 1A/dm with the cathode current density
2The about 5 microns copper coating of plating on 2 millimeters steel wire matrixes of diameter of phi, electroplating time is 15 minutes, it is intact with winding method test bonding force to press ASTM B452-2002.
Embodiment 2:
Is the alkaline non-cyanide copper plating solution that main coordination agent constitutes by following proportioning preparation with methylenediphosphonate (MDP).
Load weighted methylenediphosphonate (MDP) and copper chloride dihydrate are mixed with deionized water dissolving respectively, in stirring, add sodium hydroxide solution, add quantitative yellow soda ash at last and be stirred to dissolving fully.
In the gained solution, 40 ℃ of regulator solution temperature are 2A/dm with the cathode current density
2The about 5 microns copper coating of plating on 2 millimeters steel wire matrixes of diameter of phi, electroplating time is 7 minutes, it is intact with winding method test bonding force to press ASTMB452-2002.
Claims (7)
1. one kind is the electroplate liquid that the alkaline non-cyanide copper facing of main coordination agent is used with methylenediphosphonate (MDP), it is characterized in that this electroplate liquid mainly contains: methylenediphosphonate (MDP) (MDP) concentration 30-100 grams per liter (g/L), bivalent cupric ion concentration 3-25 grams per liter.
2. as claimed in claim 1 is the electroplate liquid that the alkaline non-cyanide copper facing of main coordination agent is used with methylenediphosphonate (MDP), it is characterized in that described bivalent cupric ion can derive from the one or more combination in copper sulfate, cupric chloride, ventilation breather, the cupric nitrate.
3. as claimed in claim 1 is the electroplate liquid that the alkaline non-cyanide copper facing of main coordination agent is used with methylenediphosphonate (MDP), it is characterized in that for the solvability that improves copper anode and obtains the careful copper coating of crystallization, can add carbanion, and content is the 10-80 grams per liter.
4. as claimed in claim 1 is the electroplate liquid that the alkaline non-cyanide copper facing of main coordination agent is used with methylenediphosphonate (MDP), it is characterized in that described this electroplate liquid pH is 7.5～13.5.
As claim 1 and 4 described be the electroplate liquid that the alkaline non-cyanide copper facing of main coordination agent is used with methylenediphosphonate (MDP), it is characterized in that adding in sodium hydroxide and the potassium hydroxide one or both and make up the pH that adjusts electroplate liquid.
6. the preparation method of an above-mentioned cyanide-free copper electroplating solution, it is characterized in that earlier respectively methylenediphosphonate (MDP) and bivalent cupric ion salt are mixed after with water dissolution, add sodium hydroxide then or more than the potassium hydroxide regulator solution pH to 7, add carbanion at last, stirring and dissolving promptly gets described cyanide-free copper electroplating solution.
7. the plating main technologic parameters of an above-mentioned cyanide-free copper electroplating solution is characterized in that controlling solution temperature 15-70 ℃, cathode current density 0.5-4 ampere/square decimeter (A/dm
2).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102995074A (en) * | 2012-10-30 | 2013-03-27 | 南通汇丰电子科技有限公司 | Cyanide-free alkaline copper plating solution |
| CN105113775A (en) * | 2015-09-18 | 2015-12-02 | 中建七局(上海)有限公司 | Basic structure of cantilever scaffold |
| CN106498457A (en) * | 2016-12-24 | 2017-03-15 | 苏州锆钒电子科技有限公司 | A kind of new cyanide-free copper electroplating technique |
| CN112941513A (en) * | 2021-01-29 | 2021-06-11 | 广西隆林利通线缆科技有限公司 | Production method of cyanide-free electroplating copper-clad aluminum wire |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102995074A (en) * | 2012-10-30 | 2013-03-27 | 南通汇丰电子科技有限公司 | Cyanide-free alkaline copper plating solution |
| CN105113775A (en) * | 2015-09-18 | 2015-12-02 | 中建七局(上海)有限公司 | Basic structure of cantilever scaffold |
| CN106498457A (en) * | 2016-12-24 | 2017-03-15 | 苏州锆钒电子科技有限公司 | A kind of new cyanide-free copper electroplating technique |
| CN112941513A (en) * | 2021-01-29 | 2021-06-11 | 广西隆林利通线缆科技有限公司 | Production method of cyanide-free electroplating copper-clad aluminum wire |
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Application publication date: 20111116 |