CN101974769B - Alkaline non-cyanide copper plating solution taking amino methylene diphosphonic acid as main coordinating agent - Google Patents
Alkaline non-cyanide copper plating solution taking amino methylene diphosphonic acid as main coordinating agent Download PDFInfo
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- CN101974769B CN101974769B CN2010101368614A CN201010136861A CN101974769B CN 101974769 B CN101974769 B CN 101974769B CN 2010101368614 A CN2010101368614 A CN 2010101368614A CN 201010136861 A CN201010136861 A CN 201010136861A CN 101974769 B CN101974769 B CN 101974769B
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- cyanide
- copper
- phosphonic acid
- ethylhexyl phosphonic
- amino methane
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Abstract
The invention provides alkaline copper plating solution taking amino methylene diphosphonic acid as main coordinating agent, relating to the field of non-cyanide plating. Plating solution is composed of the following components: amino methylene diphosphonic acid (AMDP) with the concentration of 30-120g/L, Cu2+ with the concentration of 3-25g/L, CO32- with the concentration of 10-80g/L and sodium hydroxide of potassium hydroxide used for regulating pH value of solution to be 7.5-13.5. The invention has the advantages that formula of plating solution is simple, no cyanide pollution is produced, covering power is high, cathode current efficiency is high, concentration polarization produced in plating process is small, allowable current density range is wide, copper plating can be directly carried out on ferric matrix, zinc or zinc alloy matrix and zinc dipped aluminium material, and copper coating having excellent bonding force with 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 amino methane di 2 ethylhexyl phosphonic acid (AMDP) 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 salt is to the strong inadequately (stability constant lgK[Cu (P of coordination ability of cupric ion
2O
7)
2 6-] ≈ 9), copper coordination ion generation reduction reaction current potential is negative inadequately
[1], and pyrophosphate copper plating solution is to pH value control very strict (general 8.13-8.19), and this is because two phosphorus of pyrophosphate connect by oxygen, and 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.If pyrophosphate salt P-O-P key is replaced with P-C-P, because the C-P bond polarity is very little, highly stable in solution, therefore with the P-C-P key constitute together with diphosphonic acids, as 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP), Amino Trimethylene Phosphonic Acid (ATMP), ethylene diamine tetra methylene phosphonic acid (EDTMP), amino methane di 2 ethylhexyl phosphonic acids (AMDP) etc. not only have the surfactivity of pyrophosphate salt, have stronger cupric coordination ability than pyrophosphate salt simultaneously, will improve the processing performance of plating bath greatly.As far back as the seventies in 20th century Nanjing University's coordination chemistry institute systematically to propose the earliest with 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) be the alkaline non-cyanide copper plating bath of main coordination agent by tackling key problem, and the cyanide-free copper electroplating commodity of selling on the present market are main coordination agent with HEDP all, as the SurTec of German Surtec company (Hangzhou) 864 alkaline non-cyanogen copper facing, the BH-580 of Guangzhou Etsing Plating Industry Science Technology Research Institute cyanide-free alkaline copper plating etc.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 with organic phospho acid such as HEDP, ATMP and the directly electro-coppering on the zinc alloy diecasting matrix of EDTMP formation electroplate liquid.The molecular weight of HEDP is 206, molecular structural formula as shown in Figure 1, link to each other with centre-C group-the OH group and-the CH3 group is very little for the contribution that improves HEDP and Cu (II) coordination ability, it is opposite because the existence of these two groups makes the HEDP molecular weight relatively large, when HEDP and cupric coordination, will reduce the velocity of diffusion of coordination product in solution because of space steric effect, in electroplating process, can produce concentration polarization, the close scope of crossing of electric current that causes negative electrode to allow is narrow partially, and the suitable cathode current density of Fang Jingli suggestion is 1.0-1.5A/dm
2(Fang Jingli. the direct copper-plating technique exploitation of steel part HEDP was looked back first part-exploitation course and the improvement [J] over nearly 30 years in 30 years. electroplates and covering with paint, 2009,28 (9): 6-9).With respect to CN
-(stability constant 1gK[Cu (CN)
4- 3-] ≈ 30), HEDP is to Cu
2+Strong not enough (the stability constant 1gK[Cu (HL) of coordination ability
2 6-] ≈ 12.48), the deposition potential of copper coordination ion is negative not enough, on higher and mushy matrix such as sintered NdFeB, the zinc alloy replacement(metathesis)reaction takes place easily still in electronegativity, causes binding force of cladding material not good.
(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, and defective such as prussiate plating bath cathode efficiency is low, and covering power is less than normal.Problems such as the plating bath that does not conform to prussiate causes coating and basal body binding force not good, and the current density range that the HEDP plating bath negative electrode of existing industrial applications allows is narrow partially, and HEDP and cupric coordination ability are strong inadequately.
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 amino methane di 2 ethylhexyl phosphonic acid (AMDP), it is characterized in that this electroplate liquid mainly contains: amino methane di 2 ethylhexyl phosphonic acid (AMDP) concentration 30-100g/L, bivalent cupric ion (Cu
2+) 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 amino methane di 2 ethylhexyl phosphonic acid 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 0.5-4A/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) amino methane di 2 ethylhexyl phosphonic acid (AMDP) with the amino methane di 2 ethylhexyl phosphonic acid.The molecular structural formula of HEDP relatively, AMDP has reduced molecular weight, remove in the structure link to each other with middle carbon potential-CH
3, this will reduce and cupric ion (Cu
2+) steric effect during coordination; Simultaneously will with copper constitute coordination stable-NH
2Be incorporated in the structure, should-NH
2In hydrogen easier with vicinal hydroxyl groups in O associate by intramolecular hydrogen bond, make H easily ionizable in the hydroxyl, and the easier Cu that enters into of the lone-pair electron of O
2+Unoccupied orbital in.These 2 are all impelled the coordination reaction between AMDP and the copper to be easier to carry out, constitute more stable coordination compound.According to coordination compound titration principle: stable more as coordination compound, then the hydrogen ion of Shi Fanging is many more, and the pH value of solution value rises slow more when splashing into same volume of hydrogen potassium oxide (KOH).We with KOH respectively titration contain the Cu of same molar weight
2+-HEDP and Cu
2+-AMDP solution, and record pH change curve, as shown in Figure 3.Can judge Cu from Fig. 3
2+More stable with the coordination compound that AMDP constitutes.
(2) amino methane di 2 ethylhexyl phosphonic acid (AMDP) molecular weight is 191, when containing the content of copper ion of same concentrations in the solution, the mol ratio that realizes cupric ion/main coordination agent is identical, obviously the needed quality of AMDP is lacked than HEDP, the velocity of diffusion of coordination compound is faster, can produce littler concentration polarization in electroplating process, the current density range of permission is wider.
(3) compared AMDP cyanide-free copper electroplating system and cyanide copper plating system, found that covering power AMDP cyanide-free copper electroplating system has improved 34% than cyanide copper plating system, the cathode efficiency of AMDP cyanide-free copper electroplating system is 94%, and the cyanide copper plating system is 65%.
(4) be the alkaline non-cyanide copper facing plating bath that main coordination agent constitutes in order to the amino methane di 2 ethylhexyl phosphonic acid, 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 amino methane di 2 ethylhexyl phosphonic acid (AMDP).
Fig. 3 is the pH change curve of KOH volumetric soiutions.
(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 the amino methane di 2 ethylhexyl phosphonic acid.
Load weighted amino methane di 2 ethylhexyl phosphonic acid 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, 25 ℃ of regulator solution temperature are 1.5A/dm with the cathode current density
2The about 6 microns copper coating of plating on Φ 2mm steel wire matrix, 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 the amino methane di 2 ethylhexyl phosphonic acid.
Load weighted amino methane di 2 ethylhexyl phosphonic acid 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.
Through the zine pressure casting of ultrasonic wave oil removing, activation pre-treatment, chargedly in above-mentioned solution go into groove and electroplate, the control solution temperature is that 50 ℃, cathode current density are 3A/dm during plating
2, electroplating time is 10 minutes.By electron trade standard SJ1282-1977, with the zine pressure casting after the plated copper through 200 ℃ of quench treatment coating bubbling not.
Claims (6)
1. one kind is the electroplate liquid that the alkaline non-cyanide copper facing of main coordination agent is used with the amino methane di 2 ethylhexyl phosphonic acid, it is characterized in that this electroplate liquid mainly contains: amino methane di 2 ethylhexyl phosphonic acid (AMDP) concentration 30-120g/L, bivalent cupric ion concentration 3-25g/L.
2. as claimed in claim 1 is the electroplate liquid that the alkaline non-cyanide copper facing of main coordination agent is used with the amino methane di 2 ethylhexyl phosphonic acid, it is characterized in that described bivalent cupric ion is 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 the amino methane di 2 ethylhexyl phosphonic acid, it is characterized in that for the solvability that improves copper anode and obtains the careful copper coating of crystallization, adds carbanion, and content is 10-80g/L.
4. as claimed in claim 1 is the electroplate liquid that the alkaline non-cyanide copper facing of main coordination agent is used with the amino methane di 2 ethylhexyl phosphonic acid, it is characterized in that described this electroplate liquid pH is 7.5～13.5.
One kind as claim 1-4 arbitrary described be the preparation method of the electroplate liquid used of the alkaline non-cyanide copper facing of main coordination agent with the amino methane di 2 ethylhexyl phosphonic acid, it is characterized in that earlier respectively amino methane di 2 ethylhexyl phosphonic acid 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.
Among application such as the claim 1-4 arbitrary claim described be the plating method of the electroplate liquid used of the alkaline non-cyanide copper facing of main coordination agent with the amino methane di 2 ethylhexyl phosphonic acid, it is characterized in that controlling solution temperature 15-70 ℃, cathode current density 0.5-4A/dm
2
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Cited By (1)
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| CN106521574A (en) * | 2016-12-05 | 2017-03-22 | 浙江工业大学 | Cyanide-free copper-plated electroplating solution suitable for wide pH range and wide current density range and preparation method for cyanide-free copper-plated electroplating solution |
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| CN102242381A (en) * | 2011-06-29 | 2011-11-16 | 杭州阿玛尔科技有限公司 | Alkaline non-cyanide copper plating solution with main coordination agent of methylenediphosphonate |
| CN105177644A (en) * | 2015-07-21 | 2015-12-23 | 安徽江威精密制造有限公司 | Copper plating method for aluminum pieces |
| CN106757195B (en) * | 2016-12-05 | 2019-05-03 | 浙江工业大学 | A kind of process for protecting surface of the porous class material of high activity |
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| US6406675B1 (en) * | 2000-09-13 | 2002-06-18 | Hercules Incorporated | Method for reducing cyanide consumption during processing of gold and silver ores to remove base metals |
| JP4799887B2 (en) * | 2005-03-24 | 2011-10-26 | 石原薬品株式会社 | Electro copper plating bath and copper plating method |
| CN101348927B (en) * | 2008-09-05 | 2010-10-06 | 江南机器（集团）有限公司 | Non-cyanide copper plating solution |
| CN101550569A (en) * | 2009-04-13 | 2009-10-07 | 昆明理工大学 | Non-cyanide alkaline copper plating bath, preparation and use method thereof |
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| CN106521574A (en) * | 2016-12-05 | 2017-03-22 | 浙江工业大学 | Cyanide-free copper-plated electroplating solution suitable for wide pH range and wide current density range and preparation method for cyanide-free copper-plated electroplating solution |
| CN106521574B (en) * | 2016-12-05 | 2018-10-26 | 浙江工业大学 | A kind of non-cyanide plating solution for copper-plating used and preparation method thereof suitable for width pH and wide current density range |
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