CN101245479A - Cyanideless electro-coppering method for magnesium alloy casting parts - Google Patents
Cyanideless electro-coppering method for magnesium alloy casting parts Download PDFInfo
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- CN101245479A CN101245479A CNA2008100641221A CN200810064122A CN101245479A CN 101245479 A CN101245479 A CN 101245479A CN A2008100641221 A CNA2008100641221 A CN A2008100641221A CN 200810064122 A CN200810064122 A CN 200810064122A CN 101245479 A CN101245479 A CN 101245479A
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Abstract
A method for no cyanide copper plating of a magnesium alloy casting relates to a method for the electro-coppering of a magnesium alloy. The invention solves the defects of the existing copper plating technique of the magnesium alloy of poor combining force of a plating coat, high void ratio and unstable plating bath. The method of the invention is as follows: first, alkaline cleaning; second, organic acid washing; third, activating in a magnesium alloy surface active agent under the condition of room temperature and water washing; fourth, soaking zinc alloy; fifth, plating in electro-coppering bath under the condition that the temperature is 20-50 DEG C and the intensity of cathode current is Dk=0.5-2.5A/dm<2>. The invention is not only used for strike copper plating of the magnesium alloy but also for thickening an electro-coppering coat. The copper plating coat has bright appearance, good combining force, low void ratio and convenient maintenance. The copper plating bath has good uniform coverage ability and covering power. The method has simple technique. The magnesium alloy casting that adopts the method to plate copper has wide application range and is applicable to the fields of electronic product, car and parts thereof, vessels, aerospace, etc.
Description
Technical field
The present invention relates to a kind of method of magnesium alloy plating copper.
Background technology
Magnesium alloy has many unique advantages energy.Therefore, magnesium alloy has obtained using widely in aircraft industry, automotive industry and telecommunications industry.But the solidity to corrosion of magnesium is relatively poor, heavy corrosion easily takes place in damp atmosphere, sulfur-bearing atmosphere and marine atmosphere, thereby limited its application widely.Have only Mg alloy surface is carried out the demand that suitable processing just can make magnesium alloy adaptation corrosion-proof wear.The method of Mg alloy surface processing at present has a variety of, and the method that magnesium alloy plating is commonly used is to soak zinc earlier, the pre-copper facing of prussiate system then, and other metal of re-plating, however above-mentioned pretreatment technology will be used the prussiate of severe toxicity.People are just ceaselessly seeking other alternative technology always.Cyanide-free copper electroplating technologies such as tetra-sodium copper facing, citric acid copper facing, fluoroboric acid copper facing, thionamic acid copper facing, hydrosulphate copper facing, organic amine copper facing, carboxylate salt copper facing and HEDP copper facing successively once appearred.But all owing to binding force of cladding material poor (coming off easily), porosity height, plating bath instability shortcomings such as (poor, the easily decomposition of impurity tolerance) are not used on a large scale.
Summary of the invention
The objective of the invention is to have in order to solve existing magnesium alloy cyanide-free copper electroplating technology that binding force of cladding material is poor, porosity height, its large-scale problem of using of the unsettled drawbacks limit of plating bath; And provide a kind of method of Mg alloy castings non-cyanide copper electroplating.The invention relates to a kind of cyanideless electro-plating copper technology that is used for Mg alloy castings, both can be used for the pre-copper facing of Mg alloy castings, also can be used for the copper electroplating layer thickening.
The method of Mg alloy castings non-cyanide copper electroplating is realized by following step among the present invention: one, alkali cleaning: under 40～60 ℃ condition, Mg alloy castings is soaked 8～10min in alkaline wash, wash then three to five times; Two, organic pickling: under the condition of room temperature, the Mg alloy castings after step 1 is handled is soaked 5～30s in the organic acid washing lotion, wash then three to five times; Three, activation: under the condition of room temperature Mg alloy castings is being activated 5～15min in the magnesium alloy surface activation agent, washing then three to five times; Four, soak zinc alloy: a, under 60～90 ℃ of conditions, soak 5～15min with Mg alloy castings in the zinc alloy immersion liquid; B, under the condition of room temperature, the Mg alloy castings that will soak behind the zinc alloy activates 2～10s in concentration is the salpeter solution of 20%～50% (weight), the process operation of a is once set by step again; Five, electro-coppering: at 20～50 ℃ temperature, cathode current density D
k=0.5～2.5A/dm
2Condition under, Mg alloy castings plating in copper electroplating solution that will be after step 4 is handled.
The mean thickness δ of gained copper coating can calculate by following formula:
Every liter of alkaline wash is made up of the water of 20～70g sodium hydroxide, 10～30g sodium phosphate and surplus in the step 1.
The concentration of organic acid washing lotion is 60～800g/L in the step 2, and organic acid is one or more the combination in oxalic acid, citric acid, tartrate, phosphoric acid, organic see acid, the organic hydrochlorate of seeing; Wherein organic acid of seeing is hydroxy ethylene two acid (HEDP) or the ethylenediamine tetraacetic methene acid (EDTMP) of seeing of seeing, and organic hydrochlorate of seeing is the ethylenediamine tetraacetic methene sour sodium (EDTMPS) of seeing.
Every liter of magnesium alloy surface activation agent is made up of the water of 30～150g organic acid, 50～180g fluorochemical and surplus in the step 3.Wherein said organic acid is one or more the combination in oxalic acid, citric acid, tartrate, phosphoric acid, organic see acid, the organic hydrochlorate of seeing; Described organic acid of seeing is hydroxy ethylene two acid (HEDP) or the ethylenediamine tetraacetic methene acid (EDTMP) of seeing of seeing; Described organic hydrochlorate ethylenediamine tetraacetic methene of seeing sour sodium (EDTMPS) of seeing; Described fluorochemical is Sodium Fluoride, Potassium monofluoride, Neutral ammonium fluoride or ammonium bifluoride.
Every liter of zinc alloy immersion liquid is made up of the water of 20～50g zinc sulfate, 80～150g potassium pyrophosphate, 5～15g lithium fluoride, 5～15g yellow soda ash, 0.1～10g metal sulfate, 20～60g phosphoric acid and surplus in the step 4; The pH value of zinc alloy immersion liquid is 8～11.Wherein said phosphoric acid is phosphorous acid or ortho-phosphoric acid; Described metal sulfate is one or more the combination in ferric sulfate, single nickel salt, rose vitriol, chromium sulphate, molybdenum trisulfate, Cadmium Sulphate, the cerous sulfate.
Every liter of copper electroplating solution is made up of the water of 10～25g bivalent cupric ion, 120～350g complexing agent, 10～50g salt of wormwood, 1～15mL hydrogen peroxide and surplus in the step 5; PH value=9～12 of copper electroplating solution.Wherein bivalent cupric ion is provided by in cupric chloride, copper sulfate, ventilation breather (claiming patina again), the cupric nitrate one or more.Wherein complexing agent is one or more the combination in citric acid, tartrate, organic see acid, the organic hydrochlorate of seeing; Organic acid of seeing is hydroxy ethylene two acid (HEDP), ethylenediamine tetraacetic methene acid (EDTMP) or the amino three methenes acid (ATMP) of seeing of seeing of seeing.Organic hydrochlorate of seeing is the ethylenediamine tetraacetic methene sour sodium (EDTMPS) of seeing.
The present invention both can be used for the pre-copper facing of Mg alloy castings, also can be used for the copper electroplating layer thickening.The outward appearance light of gained copper coating, bonding force is good, porosity is low, and easy to maintenance.The covering power and the covering power of electroplating solution are good.The technology of the inventive method is simple.The applied range of the Mg alloy castings after the copper facing of employing the inventive method can be used for fields such as electronic product, automobile and spare and accessory parts thereof, boats and ships and space flight and aviation.
Description of drawings
Fig. 1 is the graph of a relation between different thickness of coating and the porosity.Fig. 2 is the Photomicrograph (amplifying 3500 times) of 10 micron thickness coating.Fig. 3 is an electro-coppering coating Hull groove sample outside drawing.Fig. 4 is the Zinc alloy casting exterior view behind the scratch experiment.
Embodiment
Embodiment one: the method for Mg alloy castings non-cyanide copper electroplating is realized by following step in the present embodiment: one, alkali cleaning: under 40～60 ℃ condition, Mg alloy castings is soaked 8～10min in alkaline wash, wash then three to five times; Two, organic pickling: under the condition of room temperature, the Mg alloy castings after step 1 is handled is soaked 5～30s in the organic acid washing lotion, wash then three to five times; Three, activation: under the condition of room temperature the Mg alloy castings after step 2 is handled is being activated 5～15min in the magnesium alloy surface activation agent, washing then three to five times; Four, soak zinc alloy: a, under 60～90 ℃ of conditions, soak 5～15min with Mg alloy castings in the zinc alloy immersion liquid; B, under the condition of room temperature, the Mg alloy castings that will soak behind the zinc alloy activates 2～10s in concentration is the salpeter solution of 20%～50% (weight), the process operation of a is once set by step again; Five, electro-coppering: at 20～50 ℃ temperature, cathode current density D
k=0.5～2.5A/dm
2Condition under, Mg alloy castings plating in copper electroplating solution that will be after step 4 is handled.
The mean thickness δ of present embodiment method gained copper coating can calculate by following formula:
As seen from Figure 1, adopt the porosity of present embodiment gained copper coating low, when copper electroplating layer thickness reached more than 10 microns, the porosity of copper layer was zero, and the protective value of coating is superior, can satisfy the requirement to the porosity of coating well.The crystal grain that gained copper coating on the microcosmic can be described by Fig. 2 is more careful, and the coating outward appearance is more smooth.The glossiness of present embodiment gained copper coating is good as shown in Figure 3, the electric current wide accommodation.Adopt scratch method for test checking present embodiment to obtain the bonding force of copper coating: with draw point stroke the parallel lines at a distance of 2mm crisscross on the copper coating surface, cut reaches matrix, the results are shown in Figure 4, the zone that scratches visible is made friends with does not have the peeling and the obscission of coating, and description taken in conjunction power is good.Embodiment two: what present embodiment and embodiment one were different is: every liter of alkaline wash is made up of the water of 20～70g sodium hydroxide, 10～30g sodium phosphate and surplus in the step 1.Other is identical with embodiment one.
Embodiment three: what present embodiment and embodiment one were different is: every liter of alkaline wash is made up of the water of 30～60g sodium hydroxide, 15～25g sodium phosphate and surplus in the step 1.Other is identical with embodiment one.
Embodiment four: what present embodiment and embodiment one were different is: every liter of alkaline wash is made up of the water of 50g sodium hydroxide, 20g sodium phosphate and surplus in the step 1.Other is identical with embodiment one.
Embodiment five: what present embodiment and embodiment and embodiment one were different is: the soak time of step 2 is 10～25s.Other is identical with embodiment one.
Embodiment six: what present embodiment and embodiment and embodiment one were different is: the soak time of step 2 is 20s.Other is identical with embodiment one.
Embodiment seven: what present embodiment and embodiment one were different is: the concentration of organic acid washing lotion is 60～800g/L in the step 2, and organic acid is one or more the combination in oxalic acid, citric acid, tartrate, phosphoric acid, organic see acid, the organic hydrochlorate of seeing.Other is identical with embodiment one.
The organic acid of present embodiment, when organic hydrochlorate of seeing is composition, can be between various organic acids by any than mixing.
Present embodiment the organic acid of seeing is hydroxy ethylene two acid (HEDP) or the ethylenediamine tetraacetic methene acid (EDTMP) of seeing of seeing, and organic hydrochlorate of seeing is the ethylenediamine tetraacetic methene sour sodium (EDTMPS) of seeing.
Embodiment eight: what present embodiment and embodiment seven were different is: the concentration of organic acid washing lotion is 100～700g/L in the step 2.Other is identical with embodiment seven.
Embodiment nine: what present embodiment and embodiment seven were different is: the concentration of organic acid washing lotion is 200～500g/L in the step 2.Other is identical with embodiment seven.
Embodiment ten: what present embodiment and embodiment seven were different is: the concentration of organic acid washing lotion is 400g/L in the step 2.Other is identical with embodiment seven.
Embodiment 11: what present embodiment and embodiment one were different is: the soak time of step 2 is 8～12min.Other is identical with embodiment one.
Embodiment 12: what present embodiment and embodiment one were different is: the soak time of step 2 is 10min.Other is identical with embodiment one.
Embodiment 13: what present embodiment and embodiment one were different is: every liter of magnesium alloy surface activation agent is made up of the water of 30～150g organic acid, 50～180g fluorochemical and surplus in the step 3.Other is identical with embodiment one.
The described organic acid of present embodiment is one or more the combination in oxalic acid, citric acid, tartrate, phosphoric acid, organic see acid, the organic hydrochlorate of seeing; When organic acid is composition, can be between various organic acids by any than mixing.Described organic acid of seeing is hydroxy ethylene two acid (HEDP) or the ethylenediamine tetraacetic methene acid (EDTMP) of seeing of seeing.Described organic hydrochlorate ethylenediamine tetraacetic methene of seeing sour sodium (EDTMPS) of seeing.Described fluorochemical is Sodium Fluoride, Potassium monofluoride, Neutral ammonium fluoride or ammonium bifluoride.
Embodiment 14: what present embodiment and embodiment 13 were different is: every liter of magnesium alloy surface activation agent is made up of the water of 40～60g organic acid, 80～150g fluorochemical and surplus in the step 2.Other is identical with embodiment 13.
Embodiment 15: what present embodiment and embodiment 13 were different is: every liter of magnesium alloy surface activation agent is made up of the water of 50g organic acid, 100g fluorochemical and surplus in the step 2.Other is identical with embodiment 13.
Embodiment 16: what present embodiment and embodiment one were different is: every liter of zinc alloy immersion liquid is made up of the water of 20～50g zinc sulfate, 80～150g potassium pyrophosphate, 5～15g lithium fluoride, 5～15g yellow soda ash, 0.1～10g metal sulfate, 20～60g phosphoric acid and surplus in the step 4; The pH value of zinc alloy immersion liquid is 8～11.Other is identical with embodiment one.
The described phosphoric acid of present embodiment is phosphorous acid or ortho-phosphoric acid.Described metal sulfate is a kind of or wherein several combination in ferric sulfate, single nickel salt, rose vitriol, chromium sulphate, molybdenum trisulfate, Cadmium Sulphate, the cerous sulfate; When metal sulfate is composition, can be between various metal sulfates by any than mixing.
Embodiment 17: what present embodiment and embodiment 16 were different is: every liter of zinc alloy immersion liquid is made up of the water of 25～40g zinc sulfate, 100～130g potassium pyrophosphate, 8～12g lithium fluoride, 8～12g yellow soda ash, 2～8g metal sulfate, 30～50g phosphoric acid and surplus.Other is identical with embodiment 16.
Embodiment 18: what present embodiment and embodiment 16 were different is: every liter of zinc alloy immersion liquid is made up of the water of 30g zinc sulfate, 110g potassium pyrophosphate, 10g lithium fluoride, 10g yellow soda ash, 5g metal sulfate, 40g phosphoric acid and surplus.Other is identical with embodiment 16.
Embodiment 19: what present embodiment and embodiment one were different is: the water that every liter of copper electroplating solution contains 10～25g bivalent cupric ion, 120～350g complexing agent, 10～50g salt of wormwood, 1～15mL hydrogen peroxide and surplus in the step 5 is formed; With the pH value that 50% potassium hydroxide solution is regulated copper electroplating solution, pH value=9～12 of copper electroplating solution.Other is identical with embodiment one.
The copper electroplating solution layoutprocedure is as follows in the present embodiment: one, the weighing complexing agent injects groove, with 50% potassium hydroxide solution dissolved dilution, makes tank liquor pH value reach 5～7, adds water and stirs to 2/3 volume dilution; Two, add hydrogen peroxide behind five times of the dilute with waters, constantly adding in the groove under the stirring condition; Three, adjust pH to 8 with 50% potassium hydroxide aqueous solution, add while hot in batches and dissolved good cupric salt, make it dissolving; Four, add salt of wormwood, while stirring dissolving; Five, adjust pH between 9～12 with 50% potassium hydroxide solution; Six, filter removal impurity, add water, adopt 0.1～0.5A/dm then
2Low current density under electrolysis 6～12 hours, promptly obtain copper electroplating solution.
Embodiment 20: what present embodiment and embodiment 19 were different is: every liter of copper electroplating solution is made up of the water of 15～22g bivalent cupric ion, 150～300g complexing agent, 20～40g salt of wormwood, 5～12mL hydrogen peroxide and surplus.Other is identical with embodiment 19.
Embodiment 21: what present embodiment and embodiment 19 were different is: every liter of copper electroplating solution is made up of the water of 20g bivalent cupric ion, 200g complexing agent, 30g salt of wormwood, 10mL hydrogen peroxide and surplus.Other is identical with embodiment 19.
Embodiment 22: what present embodiment and embodiment 19 were different is: bivalent cupric ion is provided by any ratio by in cupric chloride, copper sulfate, ventilation breather (claiming patina again), the cupric nitrate one or more.Other is identical with embodiment 19.
Embodiment 23: what present embodiment and embodiment 19 were different is: complexing agent is one or more the combination in citric acid, tartrate, organic see acid, the organic hydrochlorate of seeing.Other is identical with embodiment 19.
When the complexing agent of present embodiment is composition, can be between various complexing agents by any than mixing.
Embodiment 24: what present embodiment and embodiment 23 were different is: organic acid of seeing is hydroxy ethylene two acid (HEDP), ethylenediamine tetraacetic methene acid (EDTMP) or the amino three methenes acid (ATMP) of seeing of seeing of seeing.Other is identical with embodiment 23.
Embodiment 25: what present embodiment and embodiment 23 were different is: organic hydrochlorate of seeing is the ethylenediamine tetraacetic methene sour sodium (EDTMPS) of seeing.Other is identical with embodiment 23.
Embodiment 26: the method for Mg alloy castings non-cyanide copper electroplating is realized by following step in the present embodiment: one, alkali cleaning: under 60 ℃ condition, Mg alloy castings is soaked 10min in alkaline wash, wash then three to five times; Wherein every liter of alkaline wash is by 40g sodium hydroxide and 15g sodium phosphate, and all the other are water.Two, organic pickling: under the condition of room temperature, Mg alloy castings that will be after step 1 is handled activates 20s in concentration is the phosphoric acid of 300g/L, wash then three to five times; Three, activation: under the condition of room temperature the Mg alloy castings after step 2 is handled is being activated 8min in the magnesium alloy surface activation agent, washing then three to five times; Every liter of magnesium alloy surface activation agent is by 80g citric acid and 120g hydrogen fluoride, and all the other are water.Four, soak zinc alloy: a, under 90 ℃ of conditions, soak 10min with the Mg alloy castings after step 2 is handled in the zinc alloy immersion liquid; Wherein every liter of zinc alloy immersion liquid is by 50g zinc sulfate, 120g potassium pyrophosphate, 10g lithium fluoride, 12g yellow soda ash, 1g single nickel salt and 20～60g ortho-phosphoric acid, and all the other are water; The pH value of zinc alloy immersion liquid is 9～11; B, under the condition of room temperature, the Mg alloy castings that will soak behind the zinc alloy activates 3～5s in concentration is the salpeter solution of 50% (weight), a repetitive operation is once set by step again.Five, electro-coppering: at 25 ℃ temperature, cathode current density D
k=1A/dm
2Condition under, Mg alloy castings plating in copper electroplating solution that will be after step 4 is handled; Wherein every liter of copper electroplating solution is that all the other are water, pH value=10～12 of copper electroplating solution by 45g cupric chloride, 150g hydroxy ethylene two see acid (HEDP), 80g ethylenediamine tetraacetic methene see sour sodium (EDTMPS), 30g salt of wormwood and 8mL hydrogen peroxide.
Present embodiment is used 50% potassium hydroxide solution adjusting pH value in step 5.
The Mg alloy castings trade mark is AZ91D in the present embodiment, carries out pre-copper facing bottoming and handles.
The chemical ingredients of magnesium alloy (by mass percentage): Al (aluminium) 8.5～9.5%, Cu (copper) 0.35%, Fe (iron) 0.004%, Mn (manganese) 0.17%, Ni (nickel) 0.001%, Si (silicon) 0.05%, Zn (zinc) 0.45～0.9%.
Electro-coppering coating outward appearance light, the porosity that obtains with this method low (plating is 45 minutes continuously, and porosity can reach zero), good through the bonding force of file test test coating and magnesium alloy.
Embodiment 27: what present embodiment and embodiment 26 were different is: every liter of magnesium alloy surface activation agent is that all the other are water by 150g hydroxy ethylene two see acid (HEDP) and 80g Sodium Fluoride in the step 3; The concentration of salpeter solution was 35% (weight) during the b of step 4 went on foot, and the activatory time is 5～8s in salpeter solution; Every liter of copper electroplating solution is by 55g ventilation breather, 180g hydroxy ethylene two see acid (HEDP), amino three methenes of 75g see acid (ATMP), 30g salt of wormwood and 10mL hydrogen peroxide in the step 5, all the other are water, pH value=9～11 of copper electroplating solution, electroplating copper cathode current density D
k=2.5A/dm
2Other is identical with embodiment 25.
Mg alloy castings trade mark AM60B in the present embodiment carries out pre-copper facing bottoming.
The chemical ingredients of magnesium alloy (by mass percentage): Al (aluminium) 5.5～6.5%, Cu (copper) 0.010%, Fe (iron) 0.005%, Mn (manganese) 0.25%, Ni (nickel) 0.002%, Si (silicon) 0.10%, Zn (zinc) 0.22%.
Electro-coppering coating outward appearance light, the porosity that obtains with this method low (plating is 20 minutes continuously, and porosity can reach zero), file test test bonding force is good.
Claims (10)
1, a kind of method of Mg alloy castings non-cyanide copper electroplating, the method that it is characterized in that the Mg alloy castings non-cyanide copper electroplating is realized by following step: one, alkali cleaning: under 40～60 ℃ condition, Mg alloy castings is soaked 8～10min in alkaline wash, wash then three to five times; Two, organic pickling: under the condition of room temperature, the Mg alloy castings after step 1 is handled is soaked 5～30s in the organic acid washing lotion, wash then three to five times; Three, activation: under the condition of room temperature the Mg alloy castings after step 2 is handled is being activated 5～15min in the magnesium alloy surface activation agent, washing then three to five times; Four, soak zinc alloy: a, under 60～90 ℃ of conditions, soak 5～15min with Mg alloy castings in the zinc alloy immersion liquid; B, under the condition of room temperature, the Mg alloy castings that will soak behind the zinc alloy activates 2～10s in concentration is the salpeter solution of 20%～50% (weight), the process operation of four a is once set by step again; Five, electro-coppering: at 20～50 ℃ temperature, cathode current density D
k=0.5～2.5A/dm
2Condition under, Mg alloy castings plating in copper electroplating solution that will be after step 4 is handled; Promptly finish the Mg alloy castings non-cyanide copper electroplating.
2, the method for a kind of Mg alloy castings non-cyanide copper electroplating according to claim 1 is characterized in that every liter of alkaline wash is made up of the water of 20～70g sodium hydroxide, 10～30g sodium phosphate and surplus in the step 1.
3, the method for a kind of Mg alloy castings non-cyanide copper electroplating according to claim 1, the concentration that it is characterized in that organic acid washing lotion in the step 2 is 60～800g/L, and organic acid is one or more the combination in oxalic acid, citric acid, tartrate, phosphoric acid, organic see acid, the organic hydrochlorate of seeing; Wherein organic acid of seeing is hydroxy ethylene two acid or the ethylenediamine tetraacetic methene acid of seeing of seeing; Organic hydrochlorate of seeing is the ethylenediamine tetraacetic methene sour sodium of seeing.
4, the method for a kind of Mg alloy castings non-cyanide copper electroplating according to claim 1 is characterized in that every liter of magnesium alloy surface activation agent is made up of the water of 30～150g organic acid, 50～180g fluorochemical and surplus in the step 3.
5, the method for a kind of Mg alloy castings non-cyanide copper electroplating according to claim 4 is characterized in that described organic acid is one or more the combination in oxalic acid, citric acid, tartrate, phosphoric acid, organic see acid, the organic hydrochlorate of seeing; Described organic acid of seeing is hydroxy ethylene two acid or the ethylenediamine tetraacetic methene acid of seeing of seeing; Described organic hydrochlorate of seeing is the ethylenediamine tetraacetic methene sour sodium of seeing; Described fluorochemical is Sodium Fluoride, Potassium monofluoride, Neutral ammonium fluoride or ammonium bifluoride.
6, the method for a kind of Mg alloy castings non-cyanide copper electroplating according to claim 1 is characterized in that every liter of zinc alloy immersion liquid is made up of the water of 20～50g zinc sulfate, 80～150g potassium pyrophosphate, 5～15g lithium fluoride, 5～15g yellow soda ash, 0.1～10g metal sulfate, 20～60g phosphoric acid and surplus in the step 4; The pH value of zinc alloy immersion liquid is 8～11.
7, the method for a kind of Mg alloy castings non-cyanide copper electroplating according to claim 6 is characterized in that described phosphoric acid is phosphorous acid or ortho-phosphoric acid; Described metal sulfate is a kind of or wherein several combination in ferric sulfate, single nickel salt, rose vitriol, chromium sulphate, molybdenum trisulfate, Cadmium Sulphate, the cerous sulfate.
8, the method for a kind of Mg alloy castings non-cyanide copper electroplating according to claim 1 is characterized in that every liter of copper electroplating solution is made up of the water of 10～25g bivalent cupric ion, 120～350g complexing agent, 10～50g salt of wormwood, 1～15mL hydrogen peroxide and surplus in the step 5; The pH value of copper electroplating solution is 9～12.
9, the method for a kind of Mg alloy castings non-cyanide copper electroplating according to claim 8 is characterized in that bivalent cupric ion is provided by in cupric chloride, copper sulfate, ventilation breather, the cupric nitrate one or more.
10, the method for a kind of Mg alloy castings non-cyanide copper electroplating according to claim 8 is characterized in that complexing agent is one or more the combination in citric acid, tartrate, organic see acid, the organic hydrochlorate of seeing; Wherein organic acid of seeing is hydroxy ethylene two acid, ethylenediamine tetraacetic methene acid or the amino three methenes acid of seeing of seeing of seeing; Organic hydrochlorate of seeing is the ethylenediamine tetraacetic methene sour sodium of seeing.
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