Cyanide-free alkaline copper plating solution and preparation method thereof
Technical field
The present invention relates to the electroplating technology field, particularly can replace the cyanide-free alkaline copper plating solution of cyanide copper fully.The invention still further relates to the preparation method of this cyanide-free alkaline copper plating solution.
Background technology
Plating plays a part indispensable in Chinese national economy, and many products of industry all need to electroplate processing, and traditional decorative electroplating liquid all must use the sodium cyanide of severe toxicity, and environment and social stability are had huge harm.
Since country issued that " promotion law on cleaner production " and State Council issue 32 commands, galvanizer author was doing a lot of researchs aspect " eliminate and contain the backward production technique of cyanogen plating ".Domestic in recent years cyanide-free alkaline copper plating technology obtains large development, and there also have corresponding product to enter abroad to be domestic, is progressively used at the electroplating enterprise that some environmental requirements are high.Years of practice proves: cyanide-free alkaline copper plating is as iron, copper, and brass, zinc alloy, the bottoming coating of base materials such as aluminium and alloy zinc-impregnating layer is feasible.Existing cyanide-free copper electroplating technology mainly contains pyrophosphate method of electro-plating copper, vitriol electro-coppering, quadrol electro-coppering, fluoroborate plating copper, citric acid-tartrate electro-coppering, HEDP (hydroxy ethylidene-diphosphate) electro-coppering and thionamic acid electro-coppering system etc.Wherein, pyrophosphate copper plating system large-scale application is handled but generally also need to carry out cyanide pre-plating copper in production, and the plating solution maintenance complexity, and cost is higher.Citric acid-tartrate electro-coppering system also has and is used on a small quantity producing, but bonding force is not ideal enough, and the plating bath cost is also higher, and long-term the placement is easy to mildew.Bonding force extreme difference during vitriol electro-coppering system Direct Electroplating.HEDP electro-coppering system almost can compare favourably with cyanide electroplating, but the sewage disposal expense is still higher.Other several technologies are to rest on the experimental study stage also because of all there being different defectives basically, also are not used for industrial production fully.The crystallization of cyanide electroplating copper layer is careful, bonding force good, all platings of plating bath, leveling property, stability are also very good, can be on iron and steel, zinc and zinc alloy matrix part Direct Electroplating.But contain cyanide ion in the cyanide electroplating copper liquid, toxicity is big, and waste water and waste liquid are difficult, and contaminate environment is serious, and is detrimental to health.Therefore, people are seeking the cyanide-free copper electroplating liquid that can substitute cyanide copper always.
China galvanizer author is since nineteen seventies, be engaged in the research and development of cyanideless electro-plating always, as cyanide-free alkaline copper plating solution patents such as pyrophosphate salt, citric acid, HEDP, tartrate, fluoroborate, propylhomoserin acetate, organic amine occur at the cyanide-free copper electroplating process aspect, but each liquid all has the deficiency of self, for example, potassium pyrophosphate is made complexing agent, and its form complexed is:
Two phosphorus of pyrophosphate connect by oxygen, pyrophosphate facile hydrolysis when pH value is low and produce the ortho-phosphoric acid root and in plating bath, tie and tire out, to cause sedimentation velocity significantly to descend. again because many metals have been understood replacement(metathesis)reaction in pyrophosphate plating solution, produce displacement copper layer, influence the bonding force between coating, so must also will carry out preplating before the plating.Such plating bath cost height, the operational condition harshness, the plating bath instability, liquid waste disposal difficulty etc., particularly binding force of cladding material is bad, has hindered and has applied.
Therefore develop a kind of requirement that meets cleaner production, do not contain objectionable impuritiess such as prussiate, heavy metal, be suitable for steel part, brass, copper, zinc alloy diecasting, the preplating of aluminium and aluminium alloy zinc-impregnating layer; Plating bath has fabulous dispersion and covering performance, and coating is careful, and level and smooth, softness has certain luminance brightness; Plating bath is simple to operate, and control is easy, and solution dispersibility and covering power are good, and the coating crystallization is careful, has good ductility, and the coating overall quality can become a urgent and important job with the copper facing that cyanide copper plating matches in excellence or beauty.
Summary of the invention
The objective of the invention is to overcome above-mentioned existing disadvantages of background technology part, and a kind of cyanide-free alkaline copper plating solution is provided.
Another object of the present invention provides the preparation method of this cyanide-free alkaline copper plating solution.
Cyanide-free alkaline copper plating solution of the present invention, employing be the basal liquid of bivalent cupric ion, can with the complexing agent of metal copper ion complexing.Itself and cupric ion form complexed may for:
Wherein, R1 is an aromatic alcohol compound, and R2 is the carboxyl aromatic compounds, and R3 is the aliphatic alcohols compound, and R4 is the fat carboxyl compounds.
The objective of the invention is to reach: cyanide-free alkaline copper plating solution by following measure, it is characterized in that copper plating bath is by metal copper ion, complexing agent, conducting salt is formed, described complexing agent is 10-(2, the 5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound, the content of complexing agent is 200-300g/L, described conducting salt comprises potassium hydroxide and salt of wormwood, the content of conducting salt is 50-75g/L, the content of metal copper ion is 8-12g/L, and electro-coppering groove cathode current density is 0.5-1.5A/dm during plating
2, the plating bath pH value is 9-10, bath temperature is 40-60 ℃.
In technique scheme, the source of described metal copper ion is one or more in ventilation breather, copper sulfate, the cupric nitrate.
In technique scheme, consisting of of described plating bath: 10-(2, the 5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound, the content of complexing agent is 250g/L, potassium hydroxide 30g/L, salt of wormwood 35g/L, the content of metal copper ion is 10g/L in the ventilation breather, electro-coppering groove cathode current density is 1.0A/dm during plating
2, the plating bath pH value is 9.5, bath temperature is 55 ℃.
The preparation method of cyanide-free alkaline copper plating solution of the present invention is characterized in that it comprises the steps:
1., ventilation breather is modulated into pasty state, the content that makes its metal copper ion is 8-12g/L with distilled water;
2., with distilled water 10-(2, the 5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide dissolution, the content of complexing agent is 200-300g/L, adds potassium hydroxide or sodium hydroxide again, and pH is adjusted between the 8.0-9.0;
3., under agitation condition, with solution 1. slowly join solution 2. in, make it fully by complexing;
4., with the salt of wormwood dissolved in distilled water, and join successively solution 3. in;
5., with potassium hydroxide or sodium hydroxide bath pH value is adjusted between the 9-10 once more
6., with using behind the distilled water constant volume;
Electro-coppering groove cathode current density is 0.5-1.5A/dm during plating
2, bath temperature is 40-60 ℃.
In technique scheme, described ventilation breather can be replaced by copper sulfate or cupric nitrate.
In technique scheme, described potassium hydroxide or sodium hydroxide and salt of wormwood are conducting salt, and the content of described conducting salt is 50-75g/L.
Adopt novel organic phosphine as main complexing agent in the non-cyanide alkaline copper plating bath of the present invention, addition is 200-300g/L.Addition is low excessively, and cathodic polarization reduces, and electroconductibility is relatively poor, and bath voltage is higher, and liberation of hydrogen is serious, and anode dissolution is bad, and coating is coarse, and bright range is narrower.Addition is too high, and coating performance improves not obvious, also can increase cost.
Cyanide-free alkaline copper plating solution of the present invention is by metal copper ion, complexing agent, and conducting salt is formed.Metal copper ion concentration is relevant with the dispersive ability that allows current density, in order to make the current density of permission, performance such as dispersive ability and sedimentation velocity all reaches practical requirement, be advisable in the 8-12g/L scope through test copper content, metal copper ion concentration is low excessively in the plating bath, and specific conductivity descends, bath voltage is higher, liberation of hydrogen is serious, and the coating bright range dwindles, and allows current density to descend.The metal copper ion excessive concentration, dispersive ability reduces, and the coating crystallization is coarse.
Complexing agent adopts the novel organic phosphine that a plurality of substituted radicals are arranged, and is of coupled connections by organic group between the phosphorus atom, and this organophosphorus is not easy to be hydrolyzed, and has guaranteed the stability of plating bath.Addition 200--300g/L is advisable, and adds lowly, and the coating bright range dwindles, and dispersive ability reduces and influence bonding force, the also easy passivation of anode.Add too highly, the plating bath cathode efficiency is low, also can increase cost.
Salt of wormwood and potassium hydroxide are conducting salts, can improve plating bath electric conductivity and dispersive ability, and the content of conducting salt is that the coating bright range is dwindled in the too high meeting of 50-75g/L content.
The source of metal copper ion can be a copper carbonate, copper sulfate, and cupric nitrates etc. are through entering plating bath after the complexing agent complexing.In electroplating process, the supply of cupric ion is mainly dissolved from anodic in the plating bath.
The cyanide-free alkaline copper plating pH value of this solution requires to be controlled at the 9-10 scope and is advisable.PH value is low excessively, easily produces replacement coating, causes its bonding force to descend the dispersive ability variation.PH value is too high, and the coating bright range dwindles, the color and luster deepening, and coating is coarse, and burr appears in high district.
The cyanide-free alkaline copper plating plating bath use temperature wide ranges of this solution, the current efficiency height, the coating crystallization is careful, and appearance luster is good, bath stability, all plating and hiding power are strong, and cost is low, and wastewater treatment is easy.Can replace containing the cyanide electroplating copper liquid of severe toxicity, use as pre-copper facing or Direct Electroplating copper.
Compared with prior art, cyanide-free alkaline copper plating solution of the present invention has following advantage:
1, this solution is cyanide-free alkaline copper plating solution, has protected environment, has reduced public hazards, and its solution can be in steel part, and brass spare is directly electroplated on the zine pressure casting (or through soaking the aluminum component of zinc), has superpower bonding force between coating and the matrix metal.But this solution rack plating, but also barrel plating; Pre-plating layer be can make, middle or overlay coating also can be used as.
2, this solution solution composition is stable, and operation is convenient, and solution dispersibility and covering power are good, and the coating crystallization is careful, has good ductility, and the coating overall quality can match in excellence or beauty with cyanide copper plating.
3, the complexing agent in this solution cyanide-free alkaline copper plating solution, adopt the oxygen between two phosphorus to replace with organic group, make it become organophosphorus, this organophosphorus acid is the organic phosphoric acid that connects two phosphates on the carbon atom, metal ion there is stronger sequestering action, has guaranteed bonding force superpower between coating and the base material.
4, electroplate the copper that concentrated solution can provide matrix necessity in this solution, sedimentary copper can be replenished by the dissolving of antianode.
5, this solution can be worked at normal temperatures, and sedimentation velocity can be slower, is not suitable for demand of practical production.Improve temperature and help improving the dispersive ability of plating bath and the bonding force of coating.Consider the volatilization of high temperature tank liquor and the consumption of the energy, temperature should be controlled between 40~60 ℃.The current efficiency height, the coating crystallization is careful, and appearance luster is good, bath stability, covering power and covering power are strong, and cost is low, and wastewater treatment is easy.The real cyanide electroplating liquid that contains severe toxicity that can substitute fully.
Embodiment
Describe performance of the present invention in detail below by enforcement, but they do not constitute limitation of the invention, only do for example.Simultaneously by illustrating that advantage of the present invention will become clear more and understanding easily.
The chemistry of complexing agent is by name: 10-(2, the 5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound, abbreviate ODOPB as, and be for CAS number: 99208-50-1, molecular formula is: C
18H
9PO
4Outward appearance is white or little yellow, purity: 〉=98%, fusing point: 245-255 ℃, be commercially available product.Its molecular structural formula is:
Embodiment 1
Plating bath is formed:
10-(2, the 5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound
200g/L
Cupric ion 8g/L in the ventilation breather
Potassium hydroxide 20g/L
Salt of wormwood 30g/L
The preparation method:
1., with distilled water ventilation breather is modulated into pasty state; 2., complexing agent is dissolved, add potassium hydroxide or sodium hydroxide solution again, PH is adjusted between the 8.0-9.0 with distilled water; 3., under agitation condition, with solution 1. slowly join solution 2. in, make it fully by complexing; 4., with the salt of wormwood dissolved in distilled water, and join successively solution 3. in; 5., with potassium hydroxide or sodium hydroxide bath pH value is adjusted between the 9-10 once more; 6., with using behind the distilled water constant volume.
Electro-coppering groove cathode current density is 0.5A/dm during plating
2, bath pH value is 9.0, bath temperature is 50 ℃.
Embodiment 2:
Plating bath is formed:
10-(2, the 5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound
250g/L
Cupric ion 10g/L in the ventilation breather
Potassium hydroxide 30g/L
Salt of wormwood 35g/L
The preparation method:
1. with distilled water ventilation breather is modulated into pasty state; 2. with distilled water complexing agent is dissolved, add potassium hydroxide or sodium hydroxide solution again, pH is adjusted between the 8.0-9.0; 3. under agitation condition, with solution 1. slowly join solution 2. in, make it fully by complexing; 4. with the salt of wormwood dissolved in distilled water, and join successively solution 3. in; 5. with potassium hydroxide or sodium hydroxide bath pH value is adjusted between the 9-10 once more; 6. with using behind the distilled water constant volume.
Electro-coppering groove cathode current density 1.0A/dm during plating
2, bath pH value is 9.5, bath temperature is 55 ℃.
Embodiment 3
Plating bath is formed:
10-(2, the 5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound
300g/L
Cupric ion 12g/L in the cupric nitrate
Potassium hydroxide 30g/L
Salt of wormwood 40g/L
Method for making:
1. with distilled water ventilation breather is modulated into pasty state; 2. use distilled water 10-(2, the 5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide dissolution, add potassium hydroxide or sodium hydroxide solution again, pH is adjusted between the 8.0-9.0; 3. under agitation condition, with solution 1. slowly join solution 2. in, make it fully by complexing; 4. with the salt of wormwood dissolved in distilled water, and join successively solution 3. in; 5. with potassium hydroxide or sodium hydroxide bath pH value is adjusted between the 9-10 once more; 6. with using behind the distilled water constant volume.
Electro-coppering groove cathode current density 1.5A/dm during plating
2, bath pH value is 10.0, bath temperature is 60 ℃.
Embodiment 4
Plating bath is formed:
10-(2, the 5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide compound
280g/L
Cupric ion 9g/L in the copper sulfate
Potassium hydroxide 30g/L
Salt of wormwood 45g/L
Method for making:
1. with distilled water ventilation breather is modulated into pasty state; 2. use distilled water 10-(2, the 5-dihydroxy phenyl)-10-hydrogen-9-oxa--10-phospho hetero phenanthrene-10-oxide dissolution, add potassium hydroxide or sodium hydroxide solution again, pH is adjusted between the 8.0-9.0; 3. under agitation condition, with solution 1. slowly join solution 2. in, make it fully by complexing; 4. with the salt of wormwood dissolved in distilled water, and join successively solution 3. in; 5. with potassium hydroxide or sodium hydroxide bath pH value is adjusted between the 9-10 once more; 6. with using behind the distilled water constant volume.
Electro-coppering groove cathode current density 1.5A/dm during plating
2, bath pH value is 10.0, bath temperature is 60 ℃.
The invention will be further described below by simultaneous test.
One. the comparison of this cyanide-free alkaline copper plating solution and cyanide electroplating liquid coating performance:
1, both all can be at iron and steel, brass, zinc-aluminium die casting and aluminum component Direct Electroplating after soaking zinc.
2, both all have good covering power and covering power.
3, this technology has better ductility and toughness than cyanide copper plating.
4, this technology cyanide-free copper electroplating coating has good weldability.
5, this technology is lower than the hardness of cyanide copper plating.Cyanide electroplating 1500N/mm
2This liquid 500N/mm
2
6, this solution does not contain the prussiate of severe toxicity, for the operator provides a good working environment.
7, the operational condition broadness of this technology (temperature, pH value etc.)
8, this technology does not have prussiate to electroplate the worry of carbonate accumulation for a long time.
9, this technology will reach identical thickness than cyanide copper plating and need plate slightly long time and bigger current density.(because Cu
2+++ 2e-Cu and Cu
1++ e----Cu power consumption is bigger), but the liquor ratio prussiate current efficiency height that is somebody's turn to do.(cyanide-free copper electroplating is up to 95%, and cyanide copper plating is about 75%)
10, wastewater treatment is simple, the waste water of this solution is easier than cyanide electroplating: only need to add the vitriol oil in the waste water, pH value is transferred to about 3.5, the hydrogen peroxide that adds 30-50ml/L again, and inflate 2-3 hour continuously to destroy the complexing agent in the plating bath, add the resolvent and the cupric ion of the complexing agent after calcium hydroxide decomposes with precipitation, add the flocculation agent flocculation again, precipitation separation.Handling the back plating bath is colourless liquid, is lower than 0.3ppm through surveying content of copper ion, can carry out safety dumping.
The technology of two these solution of .. and cyanide copper plating processing performance are relatively
This technology cyanide copper plating process
Embodiment 2 plating baths are formed cuprous cyanide 60g/L
Metallic copper 42.5g/L
Sodium cyanide (dissociating) 12g/L
Sodium hydroxide 10-20g/L
60 ℃ of temperature
PH 9.2-10.0 PH 10-12
Cathode current density 0.2-1.5A/dm
20.2-1.5A/dm
2
Anode: negative electrode 1.5: 1 1.5: 1
Anode OHFC (the high electricity of anaerobic is led copper) electrolysis copper coin
Stir strong pneumatic blending and large vol circulating filtration
In the experiment, be numbered that metallic copper content is 9.5g/L in this electroplate liquid of 1; Be numbered that metallic copper content is 6.5g/L in this electroplate liquid of 2; The numbering 3 be cyanide electroplating liquid, metallic copper content is 42g/L in the electroplate liquid.The plating bath of these 3 numberings and the performance of coating are carried out following comparison:
2.1.1 Hull Cell test piece outward appearance
In temperature is under 50 ℃, and above 3 kinds of plating baths are carried out Hull groove experiment, and the outward appearance of observing test piece the results are shown in Table 1.When total current was 0.5A, the test piece of 3 kinds of plating baths was half light; When total current was 1A and 1.5A, numbering 2,3 the high Current Zone coating of test piece the crystallization coarse or scope of burning was greater than numbering 1.But be numbered slightly wide than numbering 3 of scope that 2 solution obtains test piece half light.
Show 1:3 numbering Hull groove experiment, the outward appearance of test piece relatively
2.1.2 sedimentation velocity
Adopt iron plate in coating bath, to test the sedimentation velocity V and the current efficiency η of plating bath.Test soln and ampere-minute meter polyphone write down the actual electric weight that passes through, and calculate sedimentation velocity and current efficiency by the weightening finish of iron plate, the results are shown in Table 2.
The current density of the different plating baths of table 2 and sedimentation velocity
As seen from Table 2, improve the current density sedimentation velocity and accelerate, current efficiency descends; This increases the back liberation of hydrogen by current density and causes.In addition, current efficiency is big in the big plating bath of metal copper ion concentration, and sedimentation velocity is also fast.Generally speaking, current density is 1.5A/dm
2When following, the current efficiency of these 3 kinds of plating baths is all more than 90%, and it is slightly fast to be numbered the sedimentation velocity of 1 solution.
2.1.3 dispersive ability
Adopt the Hull groove to measure the dispersive ability of plating bath, 50 ℃ of temperature, electric current 1.0A electroplates 30min, and test piece is an iron plate.Cladding portion in the test piece is divided into 10 equal portions, gets the mid-way, adopt X-fluorescence thickness tester to measure the thickness of coating in 1~8 each mid-way, position, calculate the dispersive ability T.P of plating bath according to formula as measurement point
T.P=∑δi/7δ1×100%(i=2~8)
The thickness of coating (μ m) of δ 1-1 grid position in the formula, the thickness of coating of δ i-2~No. 8 arbitrary grid (μ m).
The dispersive ability that measures 1,2, No. 3 plating bath is respectively 68.7%, 64.2%, 61.3%, shows that numbering 2 dispersive ability is better than the summary of numbering 3 for the dispersive ability that is numbered 1 good than numbering 2.
2.1.4 binding force of cladding material
The bonding force of coating is closely related with body material.By different matrix being carried out cyanide-free alkaline copper plating, back nickel plating, adopt reverse bending test and thermal shock test to detect the bonding force of coating.
Steel part electroplate liquid flow process: oil removing → pickling → activation → cyanide-free alkaline copper plating (J=1~1.5A/dm
2, t=20~40min, thickness of coating 4~12 μ m) → plating acid bright copper plating (J=2A/dm
2, t=10min, about 13~17 μ m of thickness of coating) → bright nickel plating (J=2A/dm
2, t=10min, the about 4 μ m of thickness of coating).
Zinc alloy matrix electroplate liquid: oil removing → activation → cyanide-free alkaline copper plating (ρ (Cu)=6.5g/L, J=1~1.5A/dm
2, t=20~40min, thickness of coating 4~12 μ m) → plating acid bright copper plating (J=2A/dm
2, t=10min, about 13~17 μ m of thickness of coating) → bright nickel plating (J=2A/dm
2, t=10min, the about 4 μ m of thickness of coating).
Above 2 kinds of matrixes are electroplated, obtained the copper layer and the bright nickel coating of different thickness, coating does not have foaming and decortication phenomenon.Coating until base fracture, does not all have the peeling obscission through alternating bending.The electrolytic coating of steel part, aluminium and aluminum alloy base material is put into the cold water quenching through 250 ℃, zinc alloy base material behind 150 ℃ of baking 1h, being numbered 1,2,3 does not all have and bubble and the phenomenon of peeling, and illustrates that the bonding force of this liquid coating and cyanide electroplating liquid is suitable.
Above-mentioned test contrast shows this solution binding force of cladding material, sedimentation velocity, dispersive ability, covering power and bath stability are good, fully can be as iron and steel, brass, the pre-copper plate of zinc-aluminium die casting matrix also can be used for the up-to-standard zinc alloy matrix pre-plating layer of die casting.Be the liquid that can really replace cyanide electroplating fully. this solution does not contain the prussiate of severe toxicity, for the operator provides nontoxic, as to clean a works fine environment.Simultaneously, electroplating wastewater processing is easier than cyanide copper plating, has really accomplished to stop to pollute from the source.