CN105401178A - Electroplating and chemical plating combined plating solution used for zinc die cast alloy - Google Patents

Electroplating and chemical plating combined plating solution used for zinc die cast alloy Download PDF

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Publication number
CN105401178A
CN105401178A CN201510937216.5A CN201510937216A CN105401178A CN 105401178 A CN105401178 A CN 105401178A CN 201510937216 A CN201510937216 A CN 201510937216A CN 105401178 A CN105401178 A CN 105401178A
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China
Prior art keywords
plating
chemical nickel
cyanide
plating solution
electroplating
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CN201510937216.5A
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Chinese (zh)
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张颖
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Individual
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites

Abstract

The invention discloses an electroplating and chemical plating combined plating solution used for zinc die cast alloy. The combined plating solution comprises a cyanide-free pre-electroplated copper electroplating solution and a chemical nickel-plating electroplating solution. The cyanide-free pre-electroplated copper electroplating solution comprises 100-120 g/L of cupric pyrophosphate, 40-50 g/L of sodium pyrophosphate, 280-300 g/L of trisodium citrate, 26-30 g/L of sodium potassium tartrate tetrahydrate, 30-50 g/L of HEDP, 260-280 g/L of ethidene diamine, 2-3 g/L of ammonium hydrogen difluoride, 2-3 g/L of sodium fluoride and 6-8 g/L of lithium fluoride, wherein the pH value of ammonium hydroxide is adjusted to be 8.5-9.5. The chemical nickel-plating electroplating solution comprises 30-40 g/L of NiSO4.6H2O, 2-4 g/L of C6H8O7.H2O, 3-5 g/L of lactic acid, 0.5-1.5 g/L of propionic acid, 16-20 mL/L of HF(40%), 14-16 g/L of NH4HF2, 14-16 g/L of NaH2PO2.H2O, 20-22 mL/L of NH3.H2O and 2-4 mg/L of thiourea, and the pH value is 4.5-5.5. The two electroplating solutions are matched and stored independently, during using, the cyanide-free pre-electroplated copper electroplating solution is used for carrying out cyanide-free electroplated copper bottoming firstly, and then the chemical nickel-plating electroplating solution is used for carrying out chemical nickel plating.

Description

A kind of plating for zinc die casting alloys and electroless plating associating plating solution
Technical field
The present invention relates to field of surface treatment, particularly a kind of plating for zinc die casting alloys and electroless plating associating plating solution.
Background technology
Because zinc alloy low price, fusing point are low, particularly extrusion process performance is good, has been widely used in and has manufactured hardware accessory, also can be used for manufacturing ornamental practical metalwork.As the badge etc. of various slide fastener, belt hook, case and bag accessory, vehicle nameplate and soldier.
Zinc alloy diecasting appearance is greyish white, and there is various defect on surface, as: slag inclusion, shrinkage cavity etc., therefore, in not surface treated situation, its usability and ornamental all non-constant.Common surface treatment method is plating.According to difference that is ornamental, Functional Requirement, electroplating technology has certain difference.As, have that appearance is gold-plated, silver-plated, chromium plating, plating rifle look etc. point.But regardless of the coating of appearance, the pre-electroplating method of zinc alloy diecasting is identical.So-called preplating, refers to the coating directly contacted with zinc alloy.Plating after preplating, will adopt diverse ways according to different demand.
The electroplating technology that zinc alloy diecasting is conventional is: 1. treatment before plating-cyanide electroplating preplating-tetra-sodium copper facing-acid copper-plating-bright nickel plating-gold-plated (silver-plated); 2. treatment before plating-neutral nickel plating preplating-tetra-sodium copper facing-acid copper-plating-bright nickel plating-gold-plated (silver-plated).
Cyanide electroplating pre-metallization solution is containing cuprous cyanide 30g/L, sodium cyanide 33g/L.Cyanide copper plating process stable performance, easy and simple to handle, but owing to employing a large amount of prussiate, all there is very strict requirement to the process of the plating three wastes, explained hereafter management.Again due in recent years; the zinc alloy diecasting surface-treated development relevant to cyanide copper plating process is very rapid; make to electroplate containing cyanogen the environmental pollution brought in rising trend, therefore, existing cyanide copper plating process can not meet the requirement of industrial development and environment protection.Particularly State Economic and Trade Commission promulgated the 32nd command last year, included one of backward technique must forcing for 2003 to eliminate in by containing cyanogen plating.The alternative techniques finding cyanide electroplating has been not only a technical problem.
Neutral nickel preplating is mainly used in the rack plating process of zinc alloy diecasting, and the main component of plating solution is NiSO 4, Trisodium Citrate etc., containing prussiate, but the bonding force of nickel layer and matrix can not show a candle to the performance of cyanide electroplating preplating, and conforming product rate is low.And due to the activation capacity of neutral nickel-plating liquid to zinc alloy diecasting poor, also have higher requirement to its pre-treatment.Neutral nickel plating technology generally can not be used for the barrel plating of zinc alloy diecasting, and therefore, range of application is not industrially very extensive.In addition, the solution cost of neutral nickel plating is higher, and wastewater treatment difficulty, limits its large-scale application industrially.
Other zinc alloy diecasting pre-plating process also have electroless copper, HEDP copper facing, gunmetal plating etc., all fail to obtain practical application in the industry because of problems such as bonding force, cost, wastewater treatments.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of plating for zinc die casting alloys and electroless plating associating plating solution, and this plating solution environmental pollution is few, and the bonding force between base material and coating is high, and corrosion resistance of coating is high, and plating piece surfacing is attractive in appearance.
For achieving the above object, the technical solution used in the present invention is as follows:
For plating and the electroless plating associating plating solution of zinc die casting alloys, described associating plating solution comprises without cyanogen pre-galvanized copper electroplate liquid and chemical nickel-plating plating solution two portions, and wherein non-cyanide pre-plating copper solution composition is cupric pyrophosphate 100-120g/L; Trisodium phosphate 40-50g/L, trisodium citrate 280-300g/L, Seignette salt 26-30g/L, HEDP30-50g/L, quadrol 260-280g/L; Bifluoride hydrogen ammonium 2-3g/L; Sodium Fluoride 2-3g/L, lithium fluoride 6-8g/L; Ammoniacal liquor adjust ph 8.5-9.5; Chemical nickel-plating plating solution composition is: NiSO46H 2o30-40g/L, C 6h 8o 7h 2o2-4g/L, lactic acid 3-5g/L, propionic acid 0.5-1.5g/L, HF (40%) 16-20mL/L, NH 4hF 214-16g/L, NaH 2pO 2h 2o14-16g/L, NH 3h 2o20-22mL/L, thiocarbamide 2-4mg/L, pH value 4.5-5.5; Two kinds of plating solutions configure respectively to be deposited, and during use, first uses and carries out non-cyanide copper electroplating bottoming without cyanogen pre-galvanized copper electroplate liquid, then use chemical nickel-plating plating solution to carry out chemical nickel plating.
When using the present invention to combine plating solution, need carry out oil removing grease removal, acid pickling and rust removing, activation treatment to the surface of zinc die casting alloys part, processing mode can adopt ordinary method to carry out.
After adopting associating plating solution of the present invention to carry out Nickel Plating Treatment, best effects on surface carries out passivation and sealing pores, and two kinds of methods adopt ordinary method equally.
Plating solution of the present invention is applicable to the plating nickel on surface process of 2#, 3#, 5# and 7# zinc alloy diecasting product.
Two kinds of plating solutions of the present invention are a kind of products, need conbined usage just can reach the desirable technique effect of the present invention, are used alone or coordinate other plating solutions to use to solve technical problem of the present invention, and reach corresponding technique effect.
The present invention has following beneficial effect:
1) the present invention is first on the basis of a large amount of orthogonal test, determine the composition of the pre-plating solution of non-cyanide pre-plating copper, and in conjunction with the feature of non-cyanide pre-plating copper, have adjusted the composition of chemical nickel-plating plating solution, the coating layer adopting plating solution of the present invention to prepare is made to have the strong metallic coating of bonding force, coating film thickness is even, and solidity to corrosion is high.Metallic coating has good static conductive, rub resistance, heat conduction and anti-electromagnetic interference capability, avoids the consequence that cyanide electroplating bottoming causes environment to be heavily polluted, and is a kind of environmentfriendly products; The raw material used in the present invention, low price, low production cost, economic benefit significantly improves.
2) adjustment is optimized for the solution composition of service requirements to non-cyanide pre-plating copper and chemical nickel plating of slide fastener especially, above-mentioned two kinds of bath compositions are need according to plating the functional component selected, lack wherein any one component in two kinds of plating solutions and will cause plating effect deteriorate, and add other component again and will cause cost up, and do not have clear improvement effect, even deleterious.On the basis of the component determined, and then determine the content of each component, test proves, when only having the content when each component to be in the scope of such scheme restriction, could obtain that sticking power chamber, solidity to corrosion are high, the coating of appearance looks elegant, the above-mentioned scope of any one component deviation, all will cause the deterioration of plating outcome, therefore, can think that each function ingredients reaches synergistic action effect in the compositional range that such scheme limits.And only have when two kinds of plating solution conbined usage, effect is just more remarkable.
Embodiment
Embodiment one
For plating and the electroless plating associating plating solution of zinc die casting alloys, described associating plating solution comprises without cyanogen pre-galvanized copper electroplate liquid and chemical nickel-plating plating solution two portions, and wherein non-cyanide pre-plating copper solution composition is cupric pyrophosphate 100g/L; Trisodium phosphate 50g/L, trisodium citrate 280g/L, Seignette salt 30g/L, HEDP30g/L, quadrol 280g/L; Bifluoride hydrogen ammonium 2g/L; Sodium Fluoride 3g/L, lithium fluoride 6g/L; Ammoniacal liquor adjust ph 9.5; Chemical nickel-plating plating solution composition is: NiSO 46H 2o30g/L, C 6h 8o 7h 2o4g/L, lactic acid 3g/L, propionic acid 1.5g/L, HF (40%) 16mL/L, NH 4hF 216g/L, NaH 2pO 2h 2o14g/L, NH 3h 2o22mL/L, thiocarbamide 2mg/L, pH value 5.5, two kinds of plating solutions configure respectively to be deposited, and during use, first uses and carries out non-cyanide copper electroplating bottoming without cyanogen pre-galvanized copper electroplate liquid, then use chemical nickel-plating plating solution to carry out chemical nickel plating.
Embodiment two
For plating and the electroless plating associating plating solution of zinc die casting alloys, described associating plating solution comprises without cyanogen pre-galvanized copper electroplate liquid and chemical nickel-plating plating solution two portions, and wherein non-cyanide pre-plating copper solution composition is cupric pyrophosphate 120g/L; Trisodium phosphate 40g/L, trisodium citrate 300g/L, Seignette salt 26g/L, HEDP50g/L, quadrol 260g/L; Bifluoride hydrogen ammonium 3g/L; Sodium Fluoride 2g/L, lithium fluoride 8g/L; Ammoniacal liquor adjust ph 8.5; Chemical nickel-plating plating solution composition is: NiSO 46H 2o40g/L, C 6h 8o 7h 2o2g/L, lactic acid 5g/L, propionic acid 0.5g/L, HF (40%) 20mL/L, NH 4hF 214g/L, NaH 2pO 2h 2o16g/L, NH 3h 2o20mL/L, thiocarbamide 4mg/L, pH value 4.5, two kinds of plating solutions configure respectively to be deposited, and during use, first uses and carries out non-cyanide copper electroplating bottoming without cyanogen pre-galvanized copper electroplate liquid, then use chemical nickel-plating plating solution to carry out chemical nickel plating.
Embodiment three
For plating and the electroless plating associating plating solution of zinc die casting alloys, described associating plating solution comprises without cyanogen pre-galvanized copper electroplate liquid and chemical nickel-plating plating solution two portions, and wherein non-cyanide pre-plating copper solution composition is cupric pyrophosphate 110g/L; Trisodium phosphate 45g/L, trisodium citrate 290g/L, Seignette salt 28g/L, HEDP40g/L, quadrol 270g/L; Bifluoride hydrogen ammonium 2.5g/L; Sodium Fluoride 2.5g/L, lithium fluoride 7g/L; Ammoniacal liquor adjust ph 9; Chemical nickel-plating plating solution composition is: NiSO 46H 2o35g/L, C 6h 8o 7h 2o3g/L, lactic acid 4g/L, propionic acid 1.0g/L, HF (40%) 18mL/L, NH 4hF 215g/L, NaH 2pO 2h 2o15g/L, NH 3h 2o21mL/L, thiocarbamide 3mg/L, pH value 5.0; Two kinds of plating solutions configure respectively to be deposited, and during use, first uses and carries out non-cyanide copper electroplating bottoming without cyanogen pre-galvanized copper electroplate liquid, then use chemical nickel-plating plating solution to carry out chemical nickel plating.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.

Claims (1)

1., for plating and the electroless plating associating plating solution of zinc die casting alloys, described associating plating solution comprises without cyanogen pre-galvanized copper electroplate liquid and chemical nickel-plating plating solution two portions, it is characterized in that, wherein non-cyanide pre-plating copper solution composition is cupric pyrophosphate 100-120g/L; Trisodium phosphate 40-50g/L, trisodium citrate 280-300g/L, Seignette salt 26-30g/L, HEDP30-50g/L, quadrol 260-280g/L; Bifluoride hydrogen ammonium 2-3g/L; Sodium Fluoride 2-3g/L, lithium fluoride 6-8g/L; Ammoniacal liquor adjust ph 8.5-9.5; Chemical nickel-plating plating solution composition is: NiSO 46H 2o30-40g/L, C 6h 8o 7h 2o2-4g/L, lactic acid 3-5g/L, propionic acid 0.5-1.5g/L, HF (40%) 16-20mL/L, NH 4hF 214-16g/L, NaH 2pO 2h 2o14-16g/L, NH 3h 2o20-22mL/L, thiocarbamide 2-4mg/L, pH value 4.5-5.5; Two kinds of plating solutions configure respectively to be deposited, and during use, first uses and carries out non-cyanide copper electroplating bottoming without cyanogen pre-galvanized copper electroplate liquid, then use chemical nickel-plating plating solution to carry out chemical nickel plating.
CN201510937216.5A 2015-12-16 2015-12-16 Electroplating and chemical plating combined plating solution used for zinc die cast alloy Pending CN105401178A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109261155A (en) * 2018-09-25 2019-01-25 中南大学 A kind of carbon nano tube/copper zinc alloy composites and its preparation method and application

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05222568A (en) * 1992-02-17 1993-08-31 Showa Denko Kk Plating solution composition
CN1598059A (en) * 2004-08-05 2005-03-23 广州杰赛科技股份有限公司 Magnesium alloy non cyanogen plating copper chemical plating nickle and its plating process
CN103898485A (en) * 2013-06-03 2014-07-02 无锡市锡山区鹅湖镇荡口青荡金属制品厂 Chemical nickel-plating process for electroplating nickel on surface of magnesium alloy die-cast piece
CN104694913A (en) * 2015-04-10 2015-06-10 湖南大学 Magnesium alloy fluoride-free chemical nickel-plating solution and nickel plating technology thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05222568A (en) * 1992-02-17 1993-08-31 Showa Denko Kk Plating solution composition
CN1598059A (en) * 2004-08-05 2005-03-23 广州杰赛科技股份有限公司 Magnesium alloy non cyanogen plating copper chemical plating nickle and its plating process
CN103898485A (en) * 2013-06-03 2014-07-02 无锡市锡山区鹅湖镇荡口青荡金属制品厂 Chemical nickel-plating process for electroplating nickel on surface of magnesium alloy die-cast piece
CN104694913A (en) * 2015-04-10 2015-06-10 湖南大学 Magnesium alloy fluoride-free chemical nickel-plating solution and nickel plating technology thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109261155A (en) * 2018-09-25 2019-01-25 中南大学 A kind of carbon nano tube/copper zinc alloy composites and its preparation method and application
CN109261155B (en) * 2018-09-25 2021-05-07 中南大学 Carbon nanotube/copper-zinc alloy composite material and preparation method and application thereof

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Application publication date: 20160316