CN103305880A - Citrate-tartrate dual-complexing non-cyanide alkaline copper-plating electrolyte on steel substrate - Google Patents

Citrate-tartrate dual-complexing non-cyanide alkaline copper-plating electrolyte on steel substrate Download PDF

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CN103305880A
CN103305880A CN201310142637XA CN201310142637A CN103305880A CN 103305880 A CN103305880 A CN 103305880A CN 201310142637X A CN201310142637X A CN 201310142637XA CN 201310142637 A CN201310142637 A CN 201310142637A CN 103305880 A CN103305880 A CN 103305880A
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China
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electrolytic solution
copper
coating
citrate
plating
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CN201310142637XA
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Chinese (zh)
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陈小兵
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湖北恒鑫金属表面处理有限公司
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Publication of CN103305880A publication Critical patent/CN103305880A/en

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Abstract

The invention discloses a citrate-tartrate dual-complexing non-cyanide alkaline copper-plating electrolyte on a steel substrate. The electrolyte per liter is prepared from the following raw materials by weight: 29-32g of copper sulfate, 110-147g of sodium citrate, 40-50g of sodium potassium tartrate, 6-8g of potassium nitrate, 8-12g of sodium bicarbonate, 0.5-1.5g of nicotinic acid, 0.1-0.2g of polyethylene glycol, 1-1.5ml of polyethyleneimine, 0.84-1.32mg of 2-mercapto benzimidazole and the balance of water. The electrolyte disclosed by the invention is good in dispersion capability, strong in coverage capability, high in stability, clean and environmentally-friendly in formula and suitable for wide working current density range; a plating coat of a plated part electroplated by the electrolyte is excellent in binding force, uniform in distribution and suitable for preparing a basic layer or a copper-plating layer in a medium thickness on a complex steel part.

Description

The two complexing alkaline cyanide-free copper plating electrolytic solution of Citrate trianion-tartrate on the steel substrate
Technical field
The present invention relates to the cyanideless electro-plating copper technology, specifically the two complexing alkaline cyanide-free copper plating electrolytic solution of Citrate trianion-tartrate on a kind of steel substrate.
Background technology
Cyanide electroplating dispersive ability and covering power are good, and bath composition is simple, and easy care be applicable to the bottoming of steel part and zinc, Al-alloy products etc., but its electrolytic solution contains the prussiate of a large amount of severe toxicity, electroplate the waste water, the waste gas harm operator ' s health that produce.China had put into effect the regulations that the cancellation prussiate is electroplated in recent years, European Union and Norway have also worked out respectively RoHS (about ban use of some objectionable impurities instruction in electronic and electrical equipment) and PoHS (forbidding special harmful substance in the consumer products) rules, and a nearly step uses poisonous additive restriction in the electrolytic solution.
The primary work that replaces cyanide electroplating electrolytic solution is exactly to seek non-cyanogen complexing agent to prevent replacement proble, and can guarantee that good bonding force is arranged between copper coating and matrix.Chinese scholars has been carried out many research to copper-plating technique, and 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid copper facing has been used for producing in enormous quantities report abroad, and the cyanide-free alkaline copper plating that Plaschem and Cupral company produce all adopts organic phosphonate as prescription; Before domestic current pyrophosphate copper plating was used for the copper facing of zinc alloy matrix plating hydrosulphate, oneself was widely used in tubulose and the complex part copper facing process for upsetting; China Patent Publication No. is that the invention of CN101550569A is take hydroxy ethylene diphosphonic acid as main complexing agent, and Citrate trianion is auxiliary complex-former, and the alkaline copper plating process current density scope of formation is at 0.5-3A/dm 2, temperature controlling range is wider, and the coating crystallization is careful, and electrolytic solution is stable, pollutes but these processing methodes easily produce phosphorus in waste water.And the EDTA of report also can be used for Alkali CyanideFree Copper Electroplating Technology as main complexing agent, but because the effect of boiling together of EDTA and cupric ion is too strong, is not easy to wastewater treatment.China Patent Publication No. is that the invention of CN101665962A is to make complexing agent with Citrate trianion, tartrate, organic amine, brightening agent preferably is selected from least a in butter of antimony, nitric acid antimony, antimony trisulfate, tin anhydride, nitrate, the nitrite etc., the test piece light that obtains, but the cathode current density scope is at 0.5-2A/dm 2, current density is narrower, is not easy to process than complex parts.China Patent Publication No. is that the invention of CN102080241A is with a kind of lower concentration weakly alkaline cyanide-free copper electroplating and tank liquor compound method, main complexing agent has used tartrate, Citrate trianion, Amino Trimethylene Phosphonic Acid salt, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid salt, ethylenediamine tetraacetic methyl fork phosphonate, auxiliary complex-former is the mixture of salicylic acid, succimide and derivative thereof, T10, has preferably bonding force, the electrolytic solution stability is splendid, has again good dispersive ability and covering power and process maintenance simple.But organism is too many, exists chemical oxygen demand too high, is not easy to wastewater treatment.
From the research of existing report and the element task of carrying out, the citrate system alkaline copper plating is most possible as the substitute products without the cyanogen environment-protection electroplating, industrial method such as my company's Citrate trianion alkaline cyanide-free copper plating on the patent 201010164782.4-steel substrate of in April, 2010 application, a kind of good stability is provided, economic environmental protection, the electroplate liquid formulation that life cycle is long, but along with further production and research are found, this plating bath exists electroplating time short for the copper plate of the wide current density range of complex part, the problems such as binding force of cladding material is poor, and the plating bath dispersing property is limited.We after deliberation and think that the most key link is to want one group of choice for use simply but the good additive of over-all properties, make the copper plate of cyanide-free copper electroplating technique preparation except satisfying good combination power and leveling property, also should possess wider current density range, be fit to the bottoming needs than complex part.
Summary of the invention
Purpose of the present invention is exactly the deficiency that exists for existing cyanide-free alkaline copper plating technology, provide that a kind of dispersive ability is good, covering power is strong, stability is high, the prescription clean environment firendly, the two complexing alkaline cyanide-free copper plating electrolytic solution of Citrate trianion-tartrate on the steel substrate that binding force of cladding material is good, planarization is good that can adapt to the working current density wide ranges, forms after electroplating.
The two complexing alkaline cyanide-free copper plating electrolytic solution of Citrate trianion-tartrate on the steel substrate of the present invention is characterized in that every liter of electrolytic solution is comprised of the raw material of following dosage:
Copper sulfate 29~32g Trisodium Citrate 110~147g
Seignette salt 40~50g saltpetre 6~8g
Sodium bicarbonate 8~12g nicotinic acid 0.5~1.5g
Polyoxyethylene glycol 0.1~0.2g
Polymine 1~1.5ml
2-mercaptobenzimidazole 0.84~1.32mg
Water surplus.
During preparation, according to the volume of required electrolytic solution, take by weighing above-mentioned each raw material by proportioning, be dissolved in volume required 2/3 the water, stirring and dissolving, and be 7~8 with sodium hydroxide or potassium hydroxide regulator solution pH, add water to again volume required, fine setting pH to 9.
Screening formulation of the present invention is, every liter of electrolytic solution is comprised of the raw material of following dosage:
Copper sulfate 30g Trisodium Citrate 147g
Seignette salt 45g saltpetre 8g
Sodium bicarbonate 10g nicotinic acid 0.5~1g
Polyoxyethylene glycol 0.1~0.2g
Polymine 1~1.5ml
2-mercaptobenzimidazole 0.9~1.2mg
Water surplus.
Main improvement of the present invention is to have added nicotinic acid, polymine on the basis of original additive.Wherein nicotinic acid has another name called Nicotinicum Acidum, is white crystals or crystalline powder, odorless or have little smelly, little acid of distinguishing the flavor of, the aqueous solution shows acid-reaction.Used nicotinic acid is the agent of a kind of pharmaceutical grade environment-protection brightening among the present invention, can produce certain mating reaction with cupric ion, is conducive to improve the cathodic polarization performance of copper plating solution.Can reduce in the present invention the pit in current density district, coating middle part, improve the phenomenon of burning in low current density district, its content is 0.5~1.5g/L, too high levels, and coating can roughen.Polymine claims again polyethylene imine, it is a kind of high molecular weight water soluble polymer, colourless or faint yellow sticky shape liquid, water absorbability is arranged, and water-soluble, ethanol is insoluble to benzene, it is a kind of tensio-active agent of macromolecule, can be adsorbed on matrix surface, produce stronger mating capability with cupric ion, improve the cathodic polarization performance of electrolytic solution.Be that to select molecular weight be 10000 polymine in the present invention, can improve the high current density scope of bright coating, be conducive to refinement coating crystal grain, its content is 1~1.5ml/L, too high levels, and coating easily shades, peeling.
Copper content is about 8g/L in the cyanide-free alkaline copper plating electrolytic solution of the present invention, can select copper sulfate, ventilation breather, cupric nitrate is main salt, but consider operation, cost and Properties Control, preferentially select copper sulfate (cupric sulfate pentahydrate) as main salt, its content is 29~32g/L.
Still select Trisodium Citrate as main complexing agent among the present invention, the mol ratio of copper sulfate and Citrate trianion is controlled at 1: 3~and 4, formed stable mixed-ligand complex in electrolytic solution, the cathodic polarization effect strengthens, and helps to form the careful coating of crystallization at wider current density range.Can not form stable Cuprocitrol complex compound in the electrolytic solution when citrate content is low, replacement(metathesis)reaction easily occurs; Too high levels, free citrate ion increases, and current efficiency reduces, and the slack-off rear coating of sedimentation velocity easily burns.
Used Seignette salt is auxiliary complex-former (also can select sodium tartrate), and its content is controlled at 40~50g/L.Seignette salt can improve the whole jaundice of coating color and luster, the problem of high district current density peeling.When the Seignette salt too high levels, the coating color and luster turns to be yellow again, and produces many pits at medium current density place, and cathode efficiency reduces.
Used polyoxyethylene glycol is conducive to improve electrolytic solution cathodic polarization performance, promotes grain refining, reduces the coating pit, and its content is 0.1~0.2g/L, too high levels, and coating easily produces evolving hydrogen reaction, affects the coating effect.
Used 2-dredges basic benzoglyoxaline and is white crystalline powder, and is nontoxic, and bitter taste is arranged.As copper brightener, can make the coating light, and smooth effect is arranged, also can improve working current density, its content is 0.84~1.32mg/L, and content is excessively low, and uneven coating is even, too high levels, easily burn at coating high current density place.
Used saltpetre is as conducting salt, and its content is 6~8g/L.Add saltpetre, can improve the half bright coating current density upper limit to 10A/dm 2When potassium nitrate content is lower, the electrolytic solution dispersive ability is perfect not, can only obtain 5A/dm 2With second bright coating; When content was higher, the electroconductibility of electrolytic solution increased, and high current density region easily produces rough surface, and the existence meeting of nitrate ion significantly reduces the cathodic polarization effect, nickel plating on the copper coating after being not suitable for.
Used sodium bicarbonate is as buffer reagent, and its content is 8~12g/L, is conducive to control stability, pH value and the coating performance of electrolytic solution.
The method that the two complexing alkaline cyanide-free copper plating electrolytic solution of Citrate trianion-tartrate prepare wide current density range coating on the steel substrate of the present invention may further comprise the steps:
(1) preparation electrolytic solution: take by weighing the mantoquita of aequum, main complex compound, auxiliary complex, conducting salt and various additive, be dissolved in the tap water that accounts for cumulative volume about 2/3, and pH value of solution is transferred to 7~8.Constantly stir make all substances dissolving after, add again tap water to volume required, and add sodium hydroxide or potassium hydroxide fine setting pH to 9, electrolytic solution be heated to 40~50 ℃ for subsequent use;
(2) prepare chemical degreasing fluid: preparation contains the degreasing fluid of sodium hydroxide 20~40g/L, yellow soda ash 20~30 g/L, tertiary sodium phosphate 5~10g/L, water glass 5~15 g/L, OP emulsifying agent 1~3g/L, be heated to 80~90 ℃ for subsequent use;
The condition of surface of metal parts before plating almost is inevitably will stick greasy dirt.During oil removing plating piece directly immersed in the degreaser and get final product about 5min;
(3) preparating acid washing lotion: select hydrochloric acid as pickling agent, during use concentrated hydrochloric acid (massfraction is 36.5%) and the water volume ratio by 1: 5~3: 5 is mixed, during processing plating piece embathed about 2min and get final product;
(4) with the test piece of A3 iron and steel after electrochemical deoiling is processed, respectively with hot water wash with wash from the beginning, again after cleanup acid treatment, with the tap water flushing, then be placed in the Hull groove that contains electrolytic solution of the present invention and electroplate, the electric current of setting is 1~3A, under bubbling stirred, electroplating time was 5~20 minutes;
(5) sample with preparation washes and the distilled water rinsing with tap water respectively, dries up and just can.
Improve the plating piece that the electrolytic solution after filling a prescription is made through above-mentioned processing step, compare with the prepared plating piece of electrolytic solution that does not add nicotinic acid and polymine, its advantage and effect are as follows:
(1) adopt Hull groove template method to detect the dispersive ability of electrolytic solution, plated sample as stated above after, calculate the dispersed T=90% of plating bath, (the dispersed T=73.6% of the plating bath of prior art) illustrates that electrolytic solution dispersive ability of the present invention is good.Detect the covering power of electrolytic solution according to the negative pole of right angle method, the result shows coating area coverage 100%, illustrates that electrolytic solution covering power of the present invention is good.Above-mentioned processing method work still kept good electrolytic solution and coating performance in 6 days, illustrated that electrolytic solution has good stability;
(2) under above-mentioned processing method, working current density is controlled at 1~10 A/dm 2, electroplate 10min, thickness of coating is 1~3 μ m, the coating growth rate is relatively steady, is fit to plating bottoming copper layer; Electroplate 20min, thickness of coating is 2~7 μ m, and the coating growth rate is relatively very fast, is fit to plating intermediate gauge copper layer; Electroplated 10 minutes under the processing condition of prior art (patent 201010164782.4), coating can reach 2~8 μ m, although its coating growth rate is fast, formed binding force of cladding material is poor, peeling and pit easily occur;
(3) way of taking pliability test, scratch test and thermal shock test to combine detects the coating bonding properties.Under above-mentioned processing method, the sample of 10min is electroplated in preparation.Be respectively 1A/dm with hawkbill in current density during pliability test 2, 4A/dm 2And 10A/dm 2Three places are doubling coating repeatedly, until the coating fracture is observed three place's tomographies and do not found copper coating peeling situation; Use steel knife during scratch test, draw two parallel lines at a distance of the 2mm place on the plating piece surface, line will be scratched copper coating and be reached matrix, and discovery coating is scratched but do not have peeling, crowfoot cracks situation; During thermal shock test sample is placed on and is heated to 300 ℃ in the vacuum drying oven, insulation 1h.After the heating, sampling is placed on quenching in the water, the copper layer that find to cover bubbles, peels off etc. and the Matrix separation phenomenon, (electroplate 10 minutes sample under the processing condition of prior art after above-mentioned pliability test, scratch test and thermal shock test, coating all has in various degree peeling, peel off etc. and the Matrix separation situation).Comprehensive explanation electrolytic solution of the present invention is good through the binding force of cladding material that above-mentioned processing method obtains;
(4) adopt scanning electronic microscope and atomic force microscope to observe respectively under the above-mentioned processing method and electroplate 10min, be respectively 1 A/dm in current density 2, 4A/dm 2, 10A/dm 2Place's sample micromorphology all shows as relatively consistent, the in a row distribution of copper crystallite size comparatively even;
(5) electrolyte prescription clean environment firendly of the present invention, technological operation is simple and control is convenient, and the working current density wide ranges satisfies the copper plate than preparation bottoming or intermediate gauge on the Complicated Steel ironware.
Description of drawings
Fig. 1 is the electrolytic solution cathodic polarization curve figure that draws under the different add-ons of polyoxyethylene glycol in the embodiment of the invention 1;
Fig. 2 is the electrolytic solution cathodic polarization curve figure that draws under the different add-ons of 2-mercaptobenzimidazole in the embodiment of the invention 2;
Fig. 3 is the electrolytic solution cathodic polarization curve figure that draws under the different add-ons of nicotinic acid in the embodiment of the invention 3;
Fig. 4 is the electrolytic solution cathodic polarization curve figure that draws under the different add-ons of polymine in the embodiment of the invention 4;
Fig. 5 electroplates when the polyoxyethylene glycol addition is 0.1g/L in the embodiment of the invention 1 after 10 minutes with sem observation gained picture;
Fig. 6 electroplates when the 2-mercaptobenzimidazole addition is 0.9mg/L in the embodiment of the invention 2 after 10 minutes with sem observation gained picture;
Fig. 7 electroplates when the nicotinic acid addition is 0.5g/L in the embodiment of the invention 3 after 10 minutes with sem observation gained picture;
Fig. 8 electroplates when the polymine addition is 1.5ml/L in the embodiment of the invention 4 after 10 minutes with sem observation gained picture.
Embodiment
Embodiment 1
Preparation 250ml sulfur acid copper 30 g/L, Trisodium Citrate 147 g/L, Seignette salt 45 g/L, saltpetre 8 g/L, sodium bicarbonate 10 g/L, nicotinic acid 1g/L, polymine 1 ml/L, polyoxyethylene glycol 0.1 g/L, the electrolytic solution of 2-mercaptobenzimidazole 1.2mg/L: take by weighing copper sulfate 7.5g, Trisodium Citrate 36.75g, Seignette salt 11.25g, saltpetre 2g, sodium bicarbonate 2.5g, nicotinic acid 0.25g, polymine 0.25ml, polyoxyethylene glycol 0.0250g, 2-mercaptobenzimidazole 0.3mg adds in the 160ml tap water, stirring and dissolving, regulate pH value to 7~8, adding tap water to liquor capacity is 250ml again, regulates pH value to 9.Electrolytic solution be heated to 50 ℃ for subsequent use.
Prepare chemical degreasing fluid: preparation contains the degreasing fluid of sodium hydroxide 20~40g/L, yellow soda ash 20~30 g/L, tertiary sodium phosphate 5~10g/L, water glass 5~15 g/L, OP emulsifying agent 1~3g/L as stated above, be heated to 80~90 ℃ for subsequent use.
The preparating acid washing lotion: being 36.5% concentrated hydrochloric acid and water with massfraction mixes by 1: 5~3: 5 volume ratio, is mixed with pickle solution.
Through electrochemical deoiling 5 minutes, clean with hot water and cold water respectively, pickling with the tap water flushing, then was placed in the Hull groove that above-mentioned electrolytic solution is housed and electroplates after 2 minutes again with the test piece of A3 iron and steel, and it is 4A/dm that cathodic current is set 2, under bubbling stirs, electroplated 10 minutes.With sem observation coating microscopic appearance, the copper crystallite size is relatively consistent, in a row distributes comparatively even, referring to Fig. 5.
In the present embodiment, other component concentrations are constant in the maintenance electrolytic solution, regulate polyethyleneglycol content and are respectively 0.2g/L, 0.3g/L, do not contain polyoxyethylene glycol, and the polarization curve that detection electrolytic solution cathodic polarization performance is painted is seen Fig. 1.As shown in Figure 1, owing to having added polyoxyethylene glycol, strengthened the cathodic polarization performance of electrolytic solution in the electrolytic solution, when polyethyleneglycol content was 0.2g/L, electrolytic solution cathodic polarization performance was best.
Embodiment 2
Press the electrolytic solution of embodiment 1 described method preparation 250ml sulfur acid copper 30 g/L, Trisodium Citrate 147 g/L, Seignette salt 45 g/L, saltpetre 8 g/L, sodium bicarbonate 10 g/L, nicotinic acid 1g/L, polymine 1 ml/L, polyoxyethylene glycol 0.2 g/L, 2-mercaptobenzimidazole 0.9 mg/L, be preheated to 50 ℃.
The scheme of pressing embodiment 1 after pickling, oil removing, washing, is placed on the iron and steel test piece in the Hull groove that above-mentioned electrolytic solution is housed, and the cathode current density size is set is 4A/ dm 2, under bubbling stirs, electroplated 10 minutes, with sem observation coating microscopic appearance, the copper crystallite size is relatively consistent, in a row distributes comparatively even, referring to Fig. 6.
In the present embodiment, other component concentrations are constant in the maintenance electrolytic solution, and the content of regulating 2-mercaptobenzimidazole is respectively 1.5mg/L, 2.1mg/L, does not contain 2-mercaptobenzimidazole, and the polarization curve that detection electrolytic solution cathodic polarization performance is painted is seen Fig. 2.As shown in Figure 2, owing to having added 2-mercaptobenzimidazole, strengthened the cathodic polarization performance of plating bath in the electrolytic solution, when 2-mercaptobenzimidazole content was 1.5mg/L, the cathodic polarization performance was best.
Embodiment 3
Press the electrolytic solution of embodiment 1 described method preparation 250ml sulfur acid copper 30 g/L, Trisodium Citrate 147 g/L, Seignette salt 45 g/L, saltpetre 8 g/L, sodium bicarbonate 10 g/L, nicotinic acid 0.5g/L, polymine 1 ml/L, polyoxyethylene glycol 0.2 g/L, 2-mercaptobenzimidazole 1.2mg/L, be preheated to 50 ℃.
The scheme of pressing embodiment 1 after pickling, oil removing, washing, is placed on the iron and steel test piece in the Hull groove that above-mentioned electrolytic solution is housed, and the cathode current density size is set is 4A/ dm 2, under bubbling stirs, electroplated 10 minutes, with sem observation coating microscopic appearance, the copper crystallite size is relatively consistent, in a row distributes comparatively even, referring to Fig. 7.
In the present embodiment, other component concentrations are constant in the maintenance electrolytic solution, and the content of regulating nicotinic acid is respectively 1.0g/L, 1.5g/L, does not contain nicotinic acid, and the polarization curve that detection electrolytic solution cathodic polarization performance is painted is seen Fig. 3.As shown in Figure 3, owing to having added nicotinic acid, strengthened the cathodic polarization performance of electrolytic solution in the electrolytic solution, when Nicotinic Acid Content was 1.0g/L, electrolytic solution cathodic polarization performance was best.
Embodiment 4
Press the electrolytic solution of embodiment 1 described method preparation 250ml sulfur acid copper 30 g/L, Trisodium Citrate 147 g/L, Seignette salt 45 g/L, saltpetre 8 g/L, sodium bicarbonate 10 g/L, nicotinic acid 1g/L, polymine 1.5ml/L, polyoxyethylene glycol 0.2 g/L, 2-mercaptobenzimidazole 1.2mg/L, be preheated to 50 ℃.
The scheme of pressing embodiment 1 after pickling, oil removing, washing, is placed on the iron and steel test piece in the Hull groove that above-mentioned electrolytic solution is housed, and the cathode current density size is set is 4A/ dm 2, under bubbling stirs, electroplated 10 minutes, with sem observation coating microscopic appearance, the copper crystallite size is relatively consistent, in a row distributes comparatively even, referring to Fig. 8.
In the present embodiment, other component concentrations are constant in the maintenance electrolytic solution, and the content of regulating polymine is respectively 0.5ml/L, 1.0 ml/L, does not contain polymine, and the polarization curve that detection electrolytic solution cathodic polarization performance is painted is seen Fig. 4.As shown in Figure 4, owing to having added polymine, strengthened the cathodic polarization performance of electrolytic solution in the electrolytic solution, when the polyethyleneimine: amine content was 1.0ml/L, electrolytic solution cathodic polarization performance was best.
Embodiment 5
Press the electrolytic solution of embodiment 1 described method preparation 250ml sulfur acid copper 29 g/L, Trisodium Citrate 110 g/L, Seignette salt 40 g/L, saltpetre 7 g/L, sodium bicarbonate 12 g/L, nicotinic acid 1.5g/L, polymine 1.5ml/L, polyoxyethylene glycol 0.2 g/L, 2-mercaptobenzimidazole 0.84mg/L.
The scheme of pressing embodiment 1 after pickling, oil removing, washing, is placed on the iron and steel test piece in the Hull groove that above-mentioned electrolytic solution is housed, and the cathode current density size is set is 4A/ dm 2, under bubbling stirs, electroplated 10 minutes, with sem observation coating microscopic appearance, the copper crystallite size is relatively consistent, in a row distributes comparatively even.
Embodiment 6
Press the electrolytic solution of embodiment 1 described method preparation 250ml sulfur acid copper 32 g/L, Trisodium Citrate 126 g/L, Seignette salt 50g/L, saltpetre 6 g/L, sodium bicarbonate 8 g/L, nicotinic acid 0.5g/L, polymine 1.5ml/L, polyoxyethylene glycol 0.1 g/L, 2-mercaptobenzimidazole 1.32mg/L.
The scheme of pressing embodiment 1 after pickling, oil removing, washing, is placed on the iron and steel test piece in the Hull groove that above-mentioned electrolytic solution is housed, and the cathode current density size is set is 4A/ dm 2, under bubbling stirs, electroplated 10 minutes, with sem observation coating microscopic appearance, the copper crystallite size is relatively consistent, in a row distributes comparatively even.
Can find out from above-described embodiment, owing to having added nicotinic acid, polymine, polyoxyethylene glycol, four kinds of additives of 2-mercaptobenzimidazole in the electrolytic solution, strengthened the cathodic polarization performance of electrolytic solution, this is conducive to the copper crystallization and produces stable settled layer in the iron and steel test piece, the copper coating topographic profile that obtains is more consistent, does not have open defect.
Comparing embodiment 1
This embodiment is all identical with preparation process, the method for embodiment 1, just preparation electrolytic solution the time do not add nicotinic acid and polymine.
Comparing embodiment 2
This embodiment is all identical with preparation process, the method for embodiment 2, just preparation electrolytic solution the time do not add nicotinic acid and polymine.
Comparing embodiment 3
This embodiment is all identical with preparation process, the method for embodiment 3, just preparation electrolytic solution the time do not add nicotinic acid and polymine.
Comparing embodiment 4
This embodiment is all identical with preparation process, the method for embodiment 4, just preparation electrolytic solution the time do not add nicotinic acid and polymine.
Following table has provided the test-results of the plating piece that embodiment 1~4 and comparing embodiment 1~4 make.
Table 1
Can find out by upper table, in the embodiment of the invention 1,2,3,4 the electrolytic solution owing to having added nicotinic acid and polymine, the copper coating crystallization that obtains is careful, smooth and without peeling, pit, the phenomenon of burning, and the phenomenon that peeling, crowfoot cracks, copper layer bubble, peel off also do not occur through combining power test coating; And in the comparing embodiment 1,2,3,4 electrolytic solution owing to not adding nicotinic acid and polymine, prepared copper coating all has in various degree pit, burns, peeling or coating surface obfuscation, irregular problem, the phenomenon that peeling, crowfoot cracks all occur, peel off through combining power test coating.
Take coating after pliability test, scratch test, the thermal shock test phenomenon that peeling, crowfoot cracks, copper layer bubble, peel off all not occur the plating piece that makes under embodiment 1,2,3,4,5,6 processing condition, electrolytic solution of the present invention is described owing to having added nicotinic acid and polymine, in wide current density range, keeping good bonding force, the copper coating pattern does not have open defect, the plating bath dispersing property reaches 90%, satisfies the wide current density range bottoming of complex part copper facing needs fully.
Above-mentioned embodiment of the present invention only is can not limit the present invention to explanation of the present invention, anyone makes any change in the principle identical with claims of the present invention and scope, zoom in or out in proportion, all should think to be included within the scope of claims.

Claims (2)

1. two complexing alkaline cyanide-free copper plating electrolytic solution of Citrate trianion-tartrate on the steel substrate is characterized in that every liter of electrolytic solution is comprised of the raw material of following dosage:
Copper sulfate 29~32g Trisodium Citrate 110~147g
Seignette salt 40~50g saltpetre 6~8g
Sodium bicarbonate 8~12g nicotinic acid 0.5~1.5g
Polyoxyethylene glycol 0.1~0.2g
Polymine 1~1.5ml
2-mercaptobenzimidazole 0.84~1.32mg
Water surplus
During preparation, according to the volume of required electrolytic solution, take by weighing above-mentioned each raw material by proportioning, be dissolved in volume required 2/3 the water, stirring and dissolving, and be 7~8 with sodium hydroxide or potassium hydroxide regulator solution pH, add water to again volume required, fine setting pH to 9.
2. two complexing alkaline cyanide-free copper plating electrolytic solution of Citrate trianion-tartrate on the steel substrate according to claim 1 is characterized in that every liter of electrolytic solution is comprised of the raw material of following dosage:
Copper sulfate 30g Trisodium Citrate 147g
Seignette salt 45g saltpetre 8g
Sodium bicarbonate 10g nicotinic acid 0.5~1g
Polyoxyethylene glycol 0.1~0.2g
Polymine 1~1.5ml
2-mercaptobenzimidazole 0.9~1.2mg
Water surplus.
CN201310142637XA 2013-04-24 2013-04-24 Citrate-tartrate dual-complexing non-cyanide alkaline copper-plating electrolyte on steel substrate CN103305880A (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103668374A (en) * 2013-12-19 2014-03-26 株洲永盛电池材料有限公司 Method for carrying out one-side copper plating on wide stainless steel band and electroplating bath
CN103668357A (en) * 2013-12-19 2014-03-26 株洲永盛电池材料有限公司 Alkaline cyanide-free high-speed copper plating solution
CN103726081A (en) * 2014-01-22 2014-04-16 哈尔滨辰能工大环保科技股份有限公司 Cyanide-free alkaline copper plating method for improving impermeable carbon copper film
CN105154928A (en) * 2015-09-07 2015-12-16 湖州方明环保科技有限公司 Novel cyanide-free alkaline copper plating solution and preparation method thereof
CN105401181A (en) * 2015-12-23 2016-03-16 苏州市金星工艺镀饰有限公司 Electroplating method of environmentally-friendly cyanide-free gold-plating electroplating fluid
CN105401180A (en) * 2015-12-23 2016-03-16 苏州市金星工艺镀饰有限公司 Electroplating liquid of wear-resistant gold-plated film and electroplating method thereof
CN105525319A (en) * 2016-01-18 2016-04-27 苏州市华婷特种电镀有限公司 Method for treatment in electroplating process
CN105586616A (en) * 2016-01-18 2016-05-18 苏州市华婷特种电镀有限公司 Process for pretreating part to be plated in electroplating process
CN106065486A (en) * 2016-06-10 2016-11-02 太原工业学院 A kind of non-cyanide copper electroplating compound additive and production technology thereof
CN106498454A (en) * 2016-10-14 2017-03-15 吴迪 A kind of preparation method of biomass cyanideless electro-plating liquid
CN107059073A (en) * 2017-06-02 2017-08-18 华北理工大学 A kind of copper-iron alloy low-carbon steel composite material and preparation method thereof
CN110284162A (en) * 2019-07-22 2019-09-27 广州三孚新材料科技股份有限公司 A kind of photovoltaic conflux welding cyanide-free alkaline copper plating solution and preparation method thereof

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Cited By (13)

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Publication number Priority date Publication date Assignee Title
CN103668357B (en) * 2013-12-19 2016-08-17 湖南永盛新材料股份有限公司 A kind of alkaline non-cyanide high-speed plating copper electrolyte
CN103668357A (en) * 2013-12-19 2014-03-26 株洲永盛电池材料有限公司 Alkaline cyanide-free high-speed copper plating solution
CN103668374A (en) * 2013-12-19 2014-03-26 株洲永盛电池材料有限公司 Method for carrying out one-side copper plating on wide stainless steel band and electroplating bath
CN103726081A (en) * 2014-01-22 2014-04-16 哈尔滨辰能工大环保科技股份有限公司 Cyanide-free alkaline copper plating method for improving impermeable carbon copper film
CN105154928A (en) * 2015-09-07 2015-12-16 湖州方明环保科技有限公司 Novel cyanide-free alkaline copper plating solution and preparation method thereof
CN105401181A (en) * 2015-12-23 2016-03-16 苏州市金星工艺镀饰有限公司 Electroplating method of environmentally-friendly cyanide-free gold-plating electroplating fluid
CN105401180A (en) * 2015-12-23 2016-03-16 苏州市金星工艺镀饰有限公司 Electroplating liquid of wear-resistant gold-plated film and electroplating method thereof
CN105525319A (en) * 2016-01-18 2016-04-27 苏州市华婷特种电镀有限公司 Method for treatment in electroplating process
CN105586616A (en) * 2016-01-18 2016-05-18 苏州市华婷特种电镀有限公司 Process for pretreating part to be plated in electroplating process
CN106065486A (en) * 2016-06-10 2016-11-02 太原工业学院 A kind of non-cyanide copper electroplating compound additive and production technology thereof
CN106498454A (en) * 2016-10-14 2017-03-15 吴迪 A kind of preparation method of biomass cyanideless electro-plating liquid
CN107059073A (en) * 2017-06-02 2017-08-18 华北理工大学 A kind of copper-iron alloy low-carbon steel composite material and preparation method thereof
CN110284162A (en) * 2019-07-22 2019-09-27 广州三孚新材料科技股份有限公司 A kind of photovoltaic conflux welding cyanide-free alkaline copper plating solution and preparation method thereof

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