CN103938240A - Combined plating solution for electroplating chromium on surface of magnesium alloy die casting - Google Patents
Combined plating solution for electroplating chromium on surface of magnesium alloy die casting Download PDFInfo
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- CN103938240A CN103938240A CN201310217938.4A CN201310217938A CN103938240A CN 103938240 A CN103938240 A CN 103938240A CN 201310217938 A CN201310217938 A CN 201310217938A CN 103938240 A CN103938240 A CN 103938240A
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Abstract
A combined plating solution for electroplating chromium on the surface of a magnesium alloy die casting is provided. The combined plating solution includes four parts: a zinc dipping solution, a cyanide-free copper-electroplating solution, a chemical nickel-plating solution and a chromium-electroplating solution. Through selection of the plating solutions of the steps and adjustment of contents, the plating solution is stable in performance, good technical effects are obtained in each treatment, good foundation is laid for a subsequent process, a finally prepared chromium-plated layer has a strong binding force, and moreover a metal plating layer has uniform plating film thickness and high corrosion resistance. The whole plating process does not adopt cyanides, and moreover the amount of a selected fluoride is less than that of the prior art, so that the plating solution process is green and environmentally friendly.
Description
Technical field
The present invention relates to electroplating technology field, relate in particular to a kind of magnesium alloy die casting electroplating Cr onto surface combination plating solution.
Background technology
Magnesium alloy is described as the green metal structured material of 21 century, has that density is low, a specific tenacity and specific rigidity is high and damping and amortization, machinability, castability are superior, in automotive industry, space flight and aviation industry, electronic industry, has obtained increasingly extensive application.Magnesium raw material is abundant, and in natural resources, in the 8th, but as structured material, its solidity to corrosion is poor has restricted the major cause that it uses widely.
The Standard Electrode Potentials of magnesium is-2.34V, there is very high reactive behavior, in air or solution, magnesium alloy can generate one deck passive film as thin as a wafer very soon, thereby while causing plating or electroless plating, metal plating and magnesium substrate adhesion are not strong, do not reach service requirements, in addition according to known to the observation of magnesium alloy materials metal structure, magnesium alloy is compared with high magnesium, to form α phase by purity, and the β being formed by alloy ingredient forms mutually, wherein β order skewness and electromotive force are higher than α phase, therefore Mg alloy surface Potential Distributing is uneven, galvanic corrosion easily occurs in treatment solution makes Mg alloy surface plating or electroless plating become difficult, therefore wish obtains the metal plating with good combination power, before plating and electroless plating, must first to magnesium alloy materials, carry out special pre-treatment to remove surperficial passive film and segregation layer, to obtain one evenly, clean surface.
Surface pretreatment common method based on magnesium alloy plating or electroless plating has at present: Dow
[1]the zinc method of the soaking technique of company exploitation, main flow process is: oil removing → anode cleaning → acid etching → acid activation → soak zinc → cyanide electroplating.On this basis, constantly improve, as Olsen
[2]the Norsk-Hydro technique proposing: oil removing → acid etching → alkaline purification → soak zinc → cyanide electroplating, Dennis
[3]wCM technique has been proposed: oil removing → acid etching → acid activation → soak zinc → cyanide electroplating.In these pre-treating technology plating solutions, contain hypertoxic prussiate, the liquid waste disposal expense of generation is high.
Under the pressure of increasingly serious resources and environment protection; carrying out the researchs of magnesium metallic substance and anti-corrosion method thereof is one of urgent task of world's Sustainable development; although obtaining interim progress aspect magnesium alloy protection in recent years; and be applied in certain field, but still there is no to form the method that can replace traditional magnesium alloy plating completely.Therefore the electroplating technology that, hope can be developed a kind of environmental protection meets the production requirement of modern clean energy-saving.
Magnesium alloy die casting has been widely used in the fields such as automobile, traffic, aerospace, and wherein the application of some die casting needs surface that electrolytic coating is set, yet, in prior art about the report of the electroplating technology of magnesium alloy die casting seldom.
Summary of the invention
The object of the invention is to propose a kind of magnesium alloy die casting electroplating Cr onto surface plating solution, by the adjustment to bath composition, do not adopt poisonous, pollute high component, make plating technic Environmental Safety, and the corrosion-resistant height of coating of preparation, appearance looks elegant, matrix and binding force of cladding material are high.
For reaching this object, the present invention by the following technical solutions:
A kind of magnesium alloy die casting electroplating Cr onto surface combination plating solution, this combination plating solution comprises zincate solution, cyanideless electro-plating copper electrolyte, chemical nickel-plating plating solution and electrodeposited chromium plating solution four parts, wherein zincate solution consists of: zinc sulfate 20-24g/L, zinc carbonate 10-14g/L, potassium pyrophosphate 200-210g/L, sodium carbonate 8-10g/L, Potassium monofluoride 3-5g/L; Ammonium bifluoride 2-3g/L, surplus is water; Cyanideless electro-plating copper electrolyte consists of: cupric pyrophosphate 40-50g/L, and trisodium phosphate 180-200g/L, ammonium citrate 34-36g/L, Seignette salt 25-29g/L, HEDP40-50g/L, quadrol 24-28g/L, ammonium bifluoride 21-25g/L, surplus is water; The plating solution of chemical nickel plating consists of: single nickel salt 44-48g/L, inferior sodium phosphate 62-66g/L, trisodium citrate 35-39g/L, lactic acid 32-36g/L, acetic acid 36-40g/L, Sodium Fluoride 2.5-4.5g/L, NH
4hF
26.5-8.5g/L, thiocarbamide 4-6mg/L; Electrodeposited chromium plating solution consists of: chromium sulphate 135-145g/L, sodium sulfate 210-230g/L; Brometo de amonio 0.6-0.8mol/L; Boric acid 1.4-1.6mol/L; Inferior sodium phosphate 0.6-0.8mol/L; Oxalic acid 1.2-1.4mol/L; Sodium lauryl sulphate 0.03-0.05mol/L, ferrous sulfate 0.05-0.07mol/L.
Above-mentioned plating solution can be applied to following technique:
Comprise the steps: alkali cleaning → pickling → activate → soak zinc → non-cyanide copper electroplating → chemical nickel plating → electrodeposited chromium, wherein:
Dip galvanizing technique is: in above-mentioned zincate solution, soak zinc, pH value: 10.5-11.0, temperature: 63-65 ℃, time: 3-5min;
Non-cyanide copper electroplating electroplating technology is: in above-mentioned cyanideless electro-plating copper electrolyte, electroplate pH value 8.0-10, current density: 2.3-3.5A, temperature 36-40 ℃, time 35-45min;
Nickel chemical plating technology condition is: plating in above-mentioned chemical nickel-plating plating solution, pH value 4.5-5.5; Temperature 60-66 ℃, time 2.3-3.5h;
Electrodeposited chromium technique: plating in the plating solution of above-mentioned electrodeposited chromium, pH value 2.3-3.6; Technological temperature 45-55 ℃, cathode current density 17-19A/dm
2, electroplating time 15-25 minute.
The present invention has advantages of:
The present invention is by the adjustment to the selection of each step plating solution and content, make plating solution performance stable, make to process each time and all obtained good technique effect, for subsequent technique is laid a good foundation, the chromium coating bonding force of final preparation is strong, and metallic coating, coating film thickness is even, solidity to corrosion is high.Whole plating process does not adopt prussiate, and the fluorochemical amount ratio prior art of selecting is few, therefore, and this plating plating solution environmental protection.
Embodiment
Embodiment mono-
A kind of magnesium alloy die casting electroplating Cr onto surface combination plating solution, this combination plating solution comprises zincate solution, cyanideless electro-plating copper electrolyte, chemical nickel-plating plating solution and electrodeposited chromium plating solution four parts, wherein zincate solution consists of: zinc sulfate 20g/L, zinc carbonate 14g/L, potassium pyrophosphate 200g/L, sodium carbonate 10g/L, Potassium monofluoride 3g/L; Ammonium bifluoride 3g/L, surplus is water; Cyanideless electro-plating copper electrolyte consists of: cupric pyrophosphate 40g/L, and trisodium phosphate 200g/L, ammonium citrate 34g/L, Seignette salt 29g/L, HEDP40g/L, quadrol 28g/L, ammonium bifluoride 21g/L, surplus is water; The plating solution of chemical nickel plating consists of: single nickel salt 44g/L, inferior sodium phosphate 66g/L, trisodium citrate 35gL, lactic acid 36g/L, acetic acid 36g/L, Sodium Fluoride 4.5g/L, NH
4hF
26.5g/L, thiocarbamide 6mg/L; Electrodeposited chromium plating solution consists of: chromium sulphate 135g/L, sodium sulfate 230g/L; Brometo de amonio 0.6-mol/L; Boric acid 1.6mol/L; Inferior sodium phosphate 0.6mol/L; Oxalic acid 1.4mol/L; Sodium lauryl sulphate 0.03mol/L, ferrous sulfate 0.07mol/L.
Embodiment bis-
A kind of magnesium alloy die casting electroplating Cr onto surface combination plating solution, this combination plating solution comprises zincate solution, cyanideless electro-plating copper electrolyte, chemical nickel-plating plating solution and electrodeposited chromium plating solution four parts, wherein zincate solution consists of: zinc sulfate 24g/L, zinc carbonate 10g/L, potassium pyrophosphate 210g/L, sodium carbonate 8g/L, Potassium monofluoride 5g/L; Ammonium bifluoride 2g/L, surplus is water; Cyanideless electro-plating copper electrolyte consists of: cupric pyrophosphate 50g/L, and trisodium phosphate 180g/L, ammonium citrate 36g/L, Seignette salt 25g/L, HEDP50g/L, quadrol 24g/L, ammonium bifluoride 25g/L, surplus is water; The plating solution of chemical nickel plating consists of: single nickel salt 48g/L, inferior sodium phosphate 62g/L, trisodium citrate 39g/L, lactic acid 32g/L, acetic acid 40g/L, Sodium Fluoride 2.5g/L, NH
4hF
28.5g/L, thiocarbamide 4mg/L; Electrodeposited chromium plating solution consists of: chromium sulphate 145g/L, sodium sulfate 210g/L; Brometo de amonio 0.8mol/L; Boric acid 1.4mol/L; Inferior sodium phosphate 0.8mol/L; Oxalic acid 1.2mol/L; Sodium lauryl sulphate 0.05mol/L, ferrous sulfate 0.05mol/L.
Embodiment tri-
A kind of magnesium alloy die casting electroplating Cr onto surface combination plating solution, this combination plating solution comprises zincate solution, cyanideless electro-plating copper electrolyte, chemical nickel-plating plating solution and electrodeposited chromium plating solution four parts, wherein zincate solution consists of: zinc sulfate 22g/L, zinc carbonate 12g/L, potassium pyrophosphate 205g/L, sodium carbonate 9g/L, Potassium monofluoride 4g/L; Ammonium bifluoride 2.5g/L, surplus is water; Cyanideless electro-plating copper electrolyte consists of: cupric pyrophosphate 45g/L, and trisodium phosphate 190g/L, ammonium citrate 35g/L, Seignette salt 27g/L, HEDP45g/L, quadrol 26g/L, ammonium bifluoride 23g/L, surplus is water; The plating solution of chemical nickel plating consists of: single nickel salt 46g/L, inferior sodium phosphate 64g/L, trisodium citrate 37g/L, lactic acid 34g/L, acetic acid 38g/L, Sodium Fluoride 3.5g/L, NH
4hF
27.5g/L, thiocarbamide 5mg/L; Electrodeposited chromium plating solution consists of: chromium sulphate 140g/L, sodium sulfate 220g/L; Brometo de amonio 0.7mol/L; Boric acid 1.5mol/L; Inferior sodium phosphate 0.7mol/L; Oxalic acid 1.3mol/L; Sodium lauryl sulphate 0.04mol/L, ferrous sulfate 0.06mol/L.
Claims (1)
1. a magnesium alloy die casting electroplating Cr onto surface combines plating solution, it is characterized in that, this combination plating solution comprises zincate solution, cyanideless electro-plating copper electrolyte, chemical nickel-plating plating solution and electrodeposited chromium plating solution four parts, wherein zincate solution consists of: zinc sulfate 20-24g/L, zinc carbonate 10-14g/L, potassium pyrophosphate 200-210g/L, sodium carbonate 8-10g/L, Potassium monofluoride 3-5g/L; Ammonium bifluoride 2-3g/L, surplus is water; Cyanideless electro-plating copper electrolyte consists of: cupric pyrophosphate 40-50g/L, and trisodium phosphate 180-200g/L, ammonium citrate 34-36g/L, Seignette salt 25-29g/L, HEDP40-50g/L, quadrol 24-28g/L, ammonium bifluoride 21-25g/L, surplus is water; The plating solution of chemical nickel plating consists of: single nickel salt 44-48g/L, inferior sodium phosphate 62-66g/L, trisodium citrate 35-39g/L, lactic acid 32-36g/L, acetic acid 36-40g/L, Sodium Fluoride 2.5-4.5g/L, NH
4hF
26.5-8.5g/L, thiocarbamide 4-6mg/L; Electrodeposited chromium plating solution consists of: chromium sulphate 135-145g/L, sodium sulfate 210-230g/L; Brometo de amonio 0.6-0.8mol/L; Boric acid 1.4-1.6mol/L; Inferior sodium phosphate 0.6-0.8mol/L; Oxalic acid 1.2-1.4mol/L; Sodium lauryl sulphate 0.03-0.05mol/L, ferrous sulfate 0.05-0.07mol/L.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104711650A (en) * | 2015-01-28 | 2015-06-17 | 南通新源特种纤维有限公司 | Electroplating method of seamless steel pipe |
| WO2021234075A1 (en) * | 2020-05-20 | 2021-11-25 | Institut De Recherche Technologique Matériaux, Métallurgie, Procédés | Method for hard chrome plating using trivalent chromium |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104711650A (en) * | 2015-01-28 | 2015-06-17 | 南通新源特种纤维有限公司 | Electroplating method of seamless steel pipe |
| WO2021234075A1 (en) * | 2020-05-20 | 2021-11-25 | Institut De Recherche Technologique Matériaux, Métallurgie, Procédés | Method for hard chrome plating using trivalent chromium |
| FR3110606A1 (en) * | 2020-05-20 | 2021-11-26 | Institut De Recherche Technologique Matériaux, Métallurgie, Procédés | Hard chromium plating process from trivalent chromium |
| FR3110607A1 (en) * | 2020-05-20 | 2021-11-26 | Institut De Recherche Technologique Matériaux, Métallurgie, Procédés | Hard chromium plating process from trivalent chromium |
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Application publication date: 20140723 |