CN101525711B - Magnesium alloy with zinc and nickel compound plating layers and preparation method thereof - Google Patents

Magnesium alloy with zinc and nickel compound plating layers and preparation method thereof Download PDF

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CN101525711B
CN101525711B CN2009100264634A CN200910026463A CN101525711B CN 101525711 B CN101525711 B CN 101525711B CN 2009100264634 A CN2009100264634 A CN 2009100264634A CN 200910026463 A CN200910026463 A CN 200910026463A CN 101525711 B CN101525711 B CN 101525711B
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zinc
magnesium alloy
plating
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nickel
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CN101525711A (en
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薛烽
王步美
周健
白晶
孙扬善
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Southeast University
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Southeast University
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Abstract

The invention discloses a magnesium alloy with zinc and nickel compound plating layers and a preparation method thereof. A zinc plating layer of the magnesium alloy is taken as a bottom layer with the width between 20 microns and 25 microns, a nickel plating layer is taken as a surface layer, and the total width of the zinc plating layer and the nickel plating layer is less than or equal to 40 microns. The method comprises the following steps: firstly, plating preliminary treatment, i.e. zinc is activated in an acid solution and then soaked in sulphate; secondly, zinc electrodeposition, i.e. after the zinc is soaked in the sulphate in the first step, the zinc layer of the magnesium alloy is electrodeposited; thirdly, nickel bright plating, i.e. the magnesium alloy which is nicely processed in the second step is brightly plated with nickel in a nickel plating solution; fourthly, sodium silicate water solution sealing. With the method, the obtained zinc plating layer is nicely combined with a base body, has uniform width and high corrosion resistance, can be taken as a protective plating layer to be singly used and can be also taken as a transition layer to carry out plating or chemical plating or other protective or decorative platings, and the nickel plating layer obtained from the zinc plating layer by plating is nicely combined with the zinc plating layer and is uniform, exquisite, bright and beautiful.

Description

Electro-galvanizing, nickel composite deposite magnesium alloy and electro-plating method thereof
Technical field
The present invention is a kind of method at electroplating zinc on magnesium alloy, nickel composite deposite, belongs to the metal corrosion and protection technical field.
Background technology
Magnesium alloy since excellent specific properties such as little, conduction of proportion and thermal conductivity height, shockproof properties are good, good processability in electronic apparatus industry such as the vehicles such as automobile, motorcycle, computer, communication, instrument, household electrical appliances, departments such as light industry, chemical industry, metallurgy, aerospace, defence and military have obtained to use more widely.In 10 years, the market share of diecast magnesium alloy increases with the speed in every year about 18% always fast, according to estimates, will reach 850,000 tons to magnesium alloy output in 2010 in the past.
Magnesium alloy uses as structured material and has broad prospects, yet up to the present, the application of magnesium is also not general, causes the major cause of this present situation to be the etching problem of magnesium, and promptly the solidity to corrosion difference is the bottleneck that the restriction magnesium alloy is brought into play its structure properties advantage.Therefore, strengthen the corrosion prevention research of magnesium and magnesium alloy, try to explore to strengthen the approach of its erosion resistance, for giving full play to its structure properties advantage, the promotion magnesium alloy has important practical significance as the application of structured material.
Metal lining coating is one of method of magnesium alloy surface protective on magnesium alloy, compare with other surface protection technique, metal plating has weldability, good heat conductive electroconductibility, have metal-like and outward appearance, and can be according to the different service requirementss of product, the unitized construction of design coating reaches the requirement of various protected decoration effects.
What the metal lining plating layer research was maximum on the present magnesium alloy is chemical nickel plating, general basic nickel carbonate or the nickel acetate of adopting is as main salt, but magnesium alloy is because high chemically reactive, after entering chemical nickel-plating liquid, intensive corrosion and replacement(metathesis)reaction take place, simultaneously with a large amount of liberations of hydrogen, cause sedimentary nickel coating and magnesium alloy substrate bonding force poor, the local foaming or the convex surface peeling occur, these defectives can not guarantee the high anti-corrosion of coating, are difficult to the protection effect that reaches satisfied.
More feasible Mg alloy surface obtains the relative chemical plating method of metal plating by electric plating method, the life cycle of electroplate liquid is longer than chemical plating fluid, and the bonding force of coating and matrix is better than the bonding force of the nickel dam of chemical nickel plating acquisition and matrix.
Summary of the invention
Relatively poor for coating and basal body binding force that electroless plating on the present magnesium alloy obtains, and the short defective of chemical plating fluid life cycle, the present invention proposes the method for a kind of electroplating zinc on magnesium alloy, nickel composite deposite.
The technical solution used in the present invention is as follows: electroplating zinc on magnesium alloy of the present invention, nickel composite deposite comprise electro-galvanized layer and electroless nickel layer.Electro-galvanized layer is as bottom, and thickness is 20~25 μ m, and electroless nickel layer is as the top layer, the total thickness of electro-galvanized layer and electroless nickel layer≤40 μ m.
The electro-plating method of a kind of electro-galvanizing, nickel composite deposite magnesium alloy, operation as follows:
The first step, pre-electroplating treatment: the magnesium alloy sample after the degreasing is activated in 15~50 ℃ acid solution, and the time is 0.5~10 minute; Sample after the activation adopts the vitriol dip galvanizing technique to soak zinc 10 minutes;
In second step, electrodepositing zinc: the magnesium alloy that the first step is soaked behind the zinc carries out the electrodepositing zinc layer in the electrodepositing zinc layer solution with zinc acetate, complexing agent, auxiliary complex-former, inhibiter, additive compound;
Complexing agent is any one in potassium pyrophosphate, trisodium phosphate or the Seignette salt, and complexing agent concentration is 30~300g/L; Auxiliary complex-former is any one in Trisodium Citrate, Tripotassium Citrate or the lemon acid amide, and the concentration of auxiliary complex-former is 5~55g/L; Inhibiter is any one in Potassium monofluoride, Sodium Fluoride or the hydrogen fluoride amine, and density of corrosion inhibitor is 2~30g/L; Additive is several composite in OP-emulsifying agent, quadrol, dimethylamine, benzylideneacetone, myo-Inositol hexaphosphate, Vanillin, the thiocarbamide, during interpolation, the concentration in electrodepositing zinc layer solution is OP-emulsifying agent 0.01~5ml/L, quadrol 0.01~5g/L, dimethylamine 0.01~5g/L, benzylideneacetone 0.01-5g/L, myo-Inositol hexaphosphate 0.01~5g/L, Vanillin 0.01~5g/L, thiocarbamide 0.5~5g/L;
In the 3rd step, bright plating nickel: the magnesium alloy that second step was handled well carries out bright plating nickel in electronickelling solution; Electronickelling solution is by single nickel salt, nickelous chloride, buffer reagent boric acid, complexing agent Trisodium Citrate, additive o-benzoic sulfimide, propionic acid, 1, and the 4-butynediol is formed;
In the 4th step, sealing of hole: it is that the sodium silicate aqueous solution of 50~100g/L is handled 10~20min at 90~100 ℃ of following sealing of holes that the 3rd magnesium alloy handled well of step is adopted concentration, the magnesium alloy of zinc, nickel composite deposite that promptly obtained electroplating surface;
Described electroplating zinc on magnesium alloy layer is a bottom, and thickness is 20~25 μ m, and electroless nickel layer is as the top layer, the total thickness of electro-galvanized layer and electroless nickel layer≤40 μ m.
Acid solution described in the first step is a combination solution, and each concentration of component is 5~25ml/L phosphoric acid, 2~25g/L hydrogen fluoride amine, 0.005~5g/L sodium laurylsulfonate, and activation temperature is 15~50 ℃, and soak time is 0.5~10 minute.
Described vitriol dip galvanizing technique is: at each concentration of component is zinc sulfate 30g/L, yellow soda ash or salt of wormwood 5g/L, Potassium monofluoride 7g/L, potassium pyrophosphate 150g/L, soak zinc in the zinc dipping solution of pH=10.2~10.4, temperature is 70~80 ℃, and galvanizing time is 10 minutes.
The acetic acid zinc concentration is 5~55g/L in the described electrodepositing zinc layer solution.
Additive is OP-emulsifying agent 1.5ml/L, quadrol 2.5g/L, four kinds of additives of dimethylamine 2.5g/L, benzylideneacetone 2.5g/L in the described electrodepositing zinc layer solution, or adds myo-Inositol hexaphosphate 0.02g/L, three kinds of additives of Vanillin 0.01g/L, thiocarbamide 0.5g/L.
The processing parameter of electrodepositing zinc layer is: current density is 0.2~4A/dm 2, temperature is 35~65 ℃, pH=6.0~9.5.
In the electronickelling solution; the concentration of single nickel salt is 20~300g/L; the concentration of nickelous chloride is 2~50g/L; the concentration of buffer reagent boric acid is 5~30g/L; the concentration of complexing agent Trisodium Citrate is 20~30g/L, and o-benzoic sulfimide concentration is 0.01~5g/L in the additive, and propionic acid concentration is 0.01~4g/L; 1,4-butynediol concentration is 0.01~6g/L.
The electroplating temperature of electronickelling is 30~65 ℃, electroplate liquid pH=3.0~7.0, and current density is 0.2~4A/dm 2
Between each operation steps, wash sample with flowing water.
The electro-plating method of electro-galvanizing, nickel composite deposite magnesium alloy, concrete steps are as follows:
The first step, pre-electroplating treatment: the magnesium alloy sample after the degreasing is activated in 15~50 ℃ acid solution, and the time is 0.5~10 minute; Sample after the activation adopts the vitriol dip galvanizing technique to soak zinc 10 minutes; Described acid solution is a combination solution, and each concentration of component is 5~25ml/L phosphoric acid, 2~25g/L hydrogen fluoride amine, 0.005~5g/L sodium laurylsulfonate, and activation temperature is 15~50 ℃, and soak time is 0.5~10 minute.Described vitriol dip galvanizing technique is: at each concentration of component is zinc sulfate 30g/L, yellow soda ash or salt of wormwood 5g/L, Potassium monofluoride 7g/L, potassium pyrophosphate 150g/L, soak zinc in the zinc dipping solution of pH=10.2~10.4, temperature is 70~80 ℃, and galvanizing time is 10 minutes.
In second step, electrodepositing zinc: the magnesium alloy that the first step is soaked behind the zinc carries out the electrodepositing zinc layer in the electrodepositing zinc layer solution with zinc acetate, complexing agent, auxiliary complex-former, inhibiter, additive compound; Plating bath composition and the processing condition used in the electrodepositing zinc technology are as follows: zinc acetate concentration is 5~55g/L, complexing agent is a potassium pyrophosphate, in trisodium phosphate or the Seignette salt any one, complexing agent concentration is 30~300g/L, auxiliary complex-former is Trisodium Citrate or Tripotassium Citrate or lemon acid amide, concentration is 5~55g/L, inhibiter is a Potassium monofluoride, Sodium Fluoride or hydrogen fluoride amine, concentration is 2~30g/L, and each concentration of component of additive is OP-emulsifying agent 0.01~5ml/L, quadrol 0.01~5g/L, dimethylamine 0.01~5g/L, benzylideneacetone 0.01-5g/L, myo-Inositol hexaphosphate 0.01~5g/L, Vanillin 0.01~5g/L, thiocarbamide 0.5~5g/L.Current density is 0.2~4A/dm 2, temperature is 35~65 ℃, pH=6.0~9.5, and electroplating time is 30 minutes, anode adopts zine plate.
In the 3rd step, the zinc-plated back of magnesium alloy bright plating nickel: the magnesium alloy that second step was handled well carries out bright plating nickel in electronickelling solution; The concentration that plating bath and technology are respectively single nickel salt is 20~300g/L; the concentration of nickelous chloride is 2~50g/L; the concentration of buffer reagent boric acid is 5~30g/L, and the concentration of complexing agent Trisodium Citrate is 20~30g/L, and o-benzoic sulfimide concentration is 0.01~5g/L in the additive; propionic acid concentration is 0.01~4g/L; 1,4-butynediol concentration is 0.01~6g/L, and temperature is 30~65 ℃; pH=3.0~7.0, current density are 0.2~4A/dm 2, electroplating time is 30 minutes, anode adopts the pure nickel plate.
In the 4th step, the water glass hole-sealing technology: hole sealing solution adopts the sodium silicate aqueous solution of 50~100g/L, and processing parameter is 90~100 ℃ of waters bath with thermostatic control, and the sealing of hole time is 10~20min.
Beneficial effect: 1, galvanizing technique of the present invention adopts zinc acetate that zine ion is provided, the relative sulfate radical of acetate, chlorion are faint to the corrosive nature of magnesium alloy, the thickness of coating that obtains is even, the standard potential of zinc and magnesium is approaching, gained coating and matrix magnesium alloy bonding force are strong, solidity to corrosion is good, has metal appearance.Zinc coating can be protected magnesium alloy substrate more, makes it not be subjected to the corrosion of plating bath in follow-up plating bath.And zinc coating both can be used as protective coating and had used separately, also can be used as transition layer, electroplated thereon or other protectives of electroless plating or decorative coating.
2 and the present invention adopt acetate zincincation deposition zinc layer as bottom, replaced the cyanide electroplating pre-treatment step, reduced pollution to environment.
3, the electroplate liquid additive of the present invention's employing has very strong leveling effect and dissemination to coating, and adopting zinc acetate in the galvanizing flux is that the hungry zinc coating of main salt acquisition is careful smooth, the nickel coating pore convergence that electronickelling obtains on this coating does not have like this, nickel coating and bottom Zinc-binding-force are strong, nickel coating thickness is even, careful smooth, have beautiful metalluster.Behind the sealing of hole, the solidity to corrosion of top layer nickel coating just can be given full play of, and resulting composite deposite has high anti-corrosion and beautiful metal appearance.
4, electro-galvanizing of the present invention, nickel technology, solution composition is simple, is easy to control, does not contain easy decomposition composition, process stabilizing, life cycle is long.
5, raw material of the present invention is easy to get, and cost is low, is suitable for suitability for industrialized production.
Embodiment
Sample is extruding attitude AZ31 magnesium alloy,
Embodiment 1
The concrete operations step of electro-galvanizing, nickel composite deposite magnesium alloy is:
Mechanical pretreatment:, reduce surfaceness with foreign matters such as sand paper corase grind, the lubricant of the burr of removal specimen surface, oxide compound, extruding usefulness, releasing agents;
Alkali cleaning degreasing: remove the general greasy dirt, lubricant of specimen surface etc. with combination solution, wherein each concentration of component is respectively 25g/L sodium hydroxide, 20g/L sodium phosphate, 20g/L yellow soda ash, 0.05g/L sodium lauryl sulphate in the combination solution, service temperature is 70~80 ℃, and the treatment time generally is 10 minutes;
The first step, pre-electroplating treatment: activation: with the magnesium alloy sample of acid solution after to degreasing 15 ℃ of activation 1 minute, each concentration of component is 10ml/L phosphoric acid, 2g/L hydrogen fluoride amine, 0.005g/L sodium laurylsulfonate in the acid solution, the acid solution activation can be removed the oxide compound of specimen surface and the viscous deformation top layer of band stress etc., can form simultaneously the etch of suitable degree to matrix, can effectively improve the mechanical snap power of subsequent plating layer and matrix, weaken the surface electrical potential difference in addition, to reduce local galvanic cell to follow-up influence of soaking the zinc processing;
Dip galvanizing technique: with zinc dipping solution the sample after activating was handled 10 minutes down for 80 ℃, wherein each concentration of component is zinc sulfate 30g/L, potassium pyrophosphate 150g/L, Potassium monofluoride 7g/L, salt of wormwood 5g/L in the zinc dipping solution, pH=10.2~10.4.Add that before plating soaking the zinc step can form a thin zinc layer at Mg alloy surface, thus the potential difference of dwindling magnesium alloy and follow-up plated metal.
Second step, electrodepositing zinc: will be suspended on through the sample of pre-treatment in the electrodepositing zinc layer solution with zinc acetate, complexing agent, auxiliary complex-former, inhibiter, additive compound and carry out the electrodepositing zinc layer; Each concentration of component is 40g/L zinc acetate, complexing agent potassium pyrophosphate 60g/L, inhibiter Potassium monofluoride 2g/L, auxiliary complex-former lemon acid amide 5g/L, 0.5g/L thiocarbamide, 0.02g/L myo-Inositol hexaphosphate, 0.01g/L Vanillin in the electrodepositing zinc layer solution, bath temperature is controlled at 55 ℃, bath pH value is 8.0, and current density is 0.5A/dm 2, electroplated 30 minutes, the thick 23 μ m of sedimentary coating, the coating uniform and delicate has metalluster;
In the 3rd step, bright plating nickel: the magnesium alloy that second step was handled well carries out bright plating nickel in electronickelling solution; Carry out bright plating nickel in the electronickelling solution with being suspended on after the flushing of the sample flowing water after zinc-plated, bath pH value is 5.0, and bath temperature is controlled at 55 ℃, and current density is 1.0A/dm 2, electroplated 30 minutes.Each concentration of component is 30g/L single nickel salt, 12g/L nickelous chloride, 5g/L boric acid, 20g/L Trisodium Citrate, 1.0g/L o-benzoic sulfimide, 0.25g/L 1 in the electronickelling solution, nickel plating in the plating bath that 4-butynediol, propionic acid 0.01g/L form.The thick 10 μ m of coating that obtain, coating is careful smooth, has beautiful metal appearance.
More than all need flowing water flushing sample between each step, again with deionized water flowing water flushing one time.
Get the bonding strength standard according to QB/T 3821-1999 light industrial goods metal plating, adopt cross cut test and pliability test to detect the bonding force of coating.Will be through the multiple cripping test sample back and forth in 180 ° of scopes of the sample behind the zinc-plated nickel, up to the metallic matrix fracture, inspection under low power magnifying glass (for example 4 times) magnifying glass, coating should not separate or peel off; With sharp knife edges examination stripping coating, coating can not be peeled off.Cross cut test uses blade to wear into the hard steel knife of 30 ° of acute angles, draws the sub-box of 1mm * 1mm on specimen surface, should apply enough pressure during line, makes a stroke cutter once just can cut coating and just can arrive matrix metal.Is 2~3.5N/cm with finger with adhesion strength 2The glue surface plaster of scotch tape to the coating surface of having rule, place 10s, with the reinforcing of coating surface vertical direction, rapidly adhesive tape is torn, any part of coating should not peeled off from matrix metal between line.The magnesium alloy sample of zinc-plated nickel gets the bonding strength standard by QB/T 3821-1999 light industrial goods metal plating fully in the present embodiment.
According to carrying out in the GB GB/T6461-2002 employing neutral salt spray test corrosion test chamber, the 5%NaCl aqueous solution, PH=6.8,35 ± 2 ℃ of test temperatures are adopted in test, 37 ± 2 ℃ of pressurized gas preheating temperatures cleaned up the back with sample after spraying continuously 48 hours and evaluate corrosion-resistant grade.The magnesium alloy sample of zinc-plated nickel is chosen as 8 grades according to GB GB/T6461-2002 after through salt air corrosion in 48 hours in the present embodiment.
Embodiment 2
The concrete operations step of electro-galvanizing, nickel composite deposite magnesium alloy is:
Mechanical pretreatment:, reduce surfaceness with foreign matters such as sand paper corase grind, the lubricant of the burr of removal specimen surface, oxide compound, extruding usefulness, releasing agents;
Alkali cleaning degreasing: remove the general greasy dirt, lubricant of specimen surface etc. with combination solution, wherein each concentration of component is respectively 25g/L sodium hydroxide, 20g/L sodium phosphate, 20g/L yellow soda ash, 0.05g/L sodium lauryl sulphate in the combination solution, service temperature is 70~80 ℃, and the treatment time generally is 10 minutes;
The first step, pre-electroplating treatment: activation: with the magnesium alloy sample of acid solution after to degreasing 50 ℃ of activation 10 minutes, each concentration of component is 5ml/L phosphoric acid, 25g/L hydrogen fluoride amine, 5g/L sodium laurylsulfonate in the acid solution, the acid solution activation can be removed the oxide compound of specimen surface and the viscous deformation top layer of band stress etc., can form simultaneously the etch of suitable degree to matrix, can effectively improve the mechanical snap power of subsequent plating layer and matrix, weaken the surface electrical potential difference in addition, to reduce local galvanic cell to follow-up influence of soaking the zinc processing;
Dip galvanizing technique: with zinc dipping solution the sample after activating was handled 10 minutes down for 70 ℃, wherein each concentration of component is zinc sulfate 30g/L, potassium pyrophosphate 150g/L, Potassium monofluoride 7g/L, salt of wormwood 5g/L in the zinc dipping solution, pH=10.2~10.4.Add that before plating soaking the zinc step can form a thin zinc layer at Mg alloy surface, thus the potential difference of dwindling magnesium alloy and follow-up plated metal.
Second step, electrodepositing zinc: will be suspended on through the sample of pre-treatment in the electrodepositing zinc layer solution with zinc acetate, complexing agent, auxiliary complex-former, inhibiter, additive compound and carry out the electrodepositing zinc layer; Each concentration of component is 10g/L zinc acetate, complexing agent Seignette salt 260g/L, inhibiter hydrogen fluoride amine 30g/L, auxiliary complex-former Tripotassium Citrate 5g/L, 5g/L thiocarbamide, 5g/L myo-Inositol hexaphosphate, 5g/L Vanillin in the electrodepositing zinc layer solution, bath temperature is controlled at 35 ℃, bath pH value is 6.0, and current density is 4A/dm 2, electroplated 30 minutes, the thick 25 μ m of sedimentary coating, the coating uniform and delicate has metalluster;
In the 3rd step, bright plating nickel: the magnesium alloy that second step was handled well carries out bright plating nickel in electronickelling solution; Carry out bright plating nickel in the electronickelling solution with being suspended on after the flushing of the sample flowing water after zinc-plated, bath pH value is 7.0, and bath temperature is controlled at 35 ℃, and current density is 0.2A/dm 2, electroplated 30 minutes.Each concentration of component is 300g/L single nickel salt, 50g/L nickelous chloride, 25g/L boric acid, 30g/L Trisodium Citrate, 5g/L o-benzoic sulfimide, 6g/L 1 in the electronickelling solution, nickel plating in the plating bath that 4-butynediol, propionic acid 3.01g/L form.The thick 15 μ m of coating that obtain, coating is careful smooth, has beautiful metal appearance.
More than all need flowing water flushing sample between each step.
Embodiment 3
The concrete operations step of electro-galvanizing, nickel composite deposite magnesium alloy is:
Mechanical pretreatment:, reduce surfaceness with foreign matters such as sand paper corase grind, the lubricant of the burr of removal specimen surface, oxide compound, extruding usefulness, releasing agents;
Alkali cleaning degreasing: remove the general greasy dirt, lubricant of specimen surface etc. with combination solution, wherein each concentration of component is respectively 25g/L sodium hydroxide, 20g/L sodium phosphate, 20g/L yellow soda ash, 0.05g/L sodium lauryl sulphate in the combination solution, service temperature is 70~80 ℃, and the treatment time generally is 10 minutes;
The first step, pre-electroplating treatment: activation: with the magnesium alloy sample of acid solution after to degreasing 25 ℃ of activation 4 minutes, each concentration of component is 15ml/L phosphoric acid, 15g/L hydrogen fluoride amine, 1.5g/L sodium laurylsulfonate in the acid solution, the acid solution activation can be removed the oxide compound of specimen surface and the viscous deformation top layer of band stress etc., can form simultaneously the etch of suitable degree to matrix, can effectively improve the mechanical snap power of subsequent plating layer and matrix, weaken the surface electrical potential difference in addition, to reduce local galvanic cell to follow-up influence of soaking the zinc processing;
Dip galvanizing technique: with zinc dipping solution the sample after activating was handled 10 minutes down for 75 ℃, wherein each concentration of component is zinc sulfate 30g/L, potassium pyrophosphate 150g/L, Potassium monofluoride 7g/L, salt of wormwood 5g/L in the zinc dipping solution, pH=10.2~10.4.Add that before plating soaking the zinc step can form a thin zinc layer at Mg alloy surface, thus the potential difference of dwindling magnesium alloy and follow-up plated metal.
Second step, electrodepositing zinc: will be suspended on through the sample of pre-treatment in the electrodepositing zinc layer solution with zinc acetate, complexing agent, auxiliary complex-former, inhibiter, additive compound and carry out the electrodepositing zinc layer; Each concentration of component is 40g/L zinc acetate, complexing agent trisodium phosphate 60g/L, inhibiter sodium bifluoride 20g/L, auxiliary complex-former Trisodium Citrate 35g/L, OP-emulsifying agent 1.5ml/L, quadrol 2.5g/L, dimethylamine 2.5g/L, benzylideneacetone 2.5g/L in the electrodepositing zinc layer solution, bath temperature is controlled at 45 ℃, bath pH value is 8.0, and current density is 3.4A/dm 2, electroplated 30 minutes, the thick 25 μ m of sedimentary coating, the coating uniform and delicate has metalluster;
In the 3rd step, bright plating nickel: the magnesium alloy that second step was handled well carries out bright plating nickel in electronickelling solution; Carry out bright plating nickel in the electronickelling solution with being suspended on after the flushing of the sample flowing water after zinc-plated, bath pH value is 5.0, and bath temperature is controlled at 45 ℃, and current density is 2.2A/dm 2, electroplated 30 minutes.Each concentration of component is 200g/L single nickel salt, 30g/L nickelous chloride, 15g/L boric acid, 25g/L Trisodium Citrate, 2.5g/L o-benzoic sulfimide, 1.6g/L 1 in the electronickelling solution, nickel plating in the plating bath that 4-butynediol, propionic acid 2.1g/L form.The thick 10 μ m of coating that obtain, coating is careful smooth, has beautiful metal appearance.
More than all need flowing water flushing sample between each step.

Claims (9)

1. the electro-plating method of an electro-galvanizing, nickel composite deposite magnesium alloy is characterized in that, as follows operation:
The first step, pre-electroplating treatment: the magnesium alloy sample after the degreasing is activated in 15~50 ℃ acid solution, and the time is 0.5~10 minute; Sample after the activation adopts the vitriol dip galvanizing technique to soak zinc 10 minutes;
In second step, electrodepositing zinc: the magnesium alloy that the first step is soaked behind the zinc carries out the electrodepositing zinc layer in the electrodepositing zinc layer solution with zinc acetate, complexing agent, auxiliary complex-former, inhibiter, additive compound;
Complexing agent is any one in potassium pyrophosphate, trisodium phosphate or the Seignette salt, and complexing agent concentration is 30~300g/L; Auxiliary complex-former is any one in Trisodium Citrate, Tripotassium Citrate or the lemon acid amide, and the concentration of auxiliary complex-former is 5~55g/L; Inhibiter is any one in Potassium monofluoride, Sodium Fluoride or the hydrogen fluoride amine, and density of corrosion inhibitor is 2~30g/L; Additive is several composite in OP-emulsifying agent, quadrol, dimethylamine, benzylideneacetone, myo-Inositol hexaphosphate, Vanillin, the thiocarbamide, during interpolation, the concentration in electrodepositing zinc layer solution is OP-emulsifying agent 0.01~5ml/L, quadrol 0.01~5g/L, dimethylamine 0.01~5g/L, benzylideneacetone 0.01-5g/L, myo-Inositol hexaphosphate 0.01~5g/L, Vanillin 0.01~5g/L, thiocarbamide 0.5~5g/L;
In the 3rd step, bright plating nickel: the magnesium alloy that second step was handled well carries out bright plating nickel in electronickelling solution; Electronickelling solution is by single nickel salt, nickelous chloride, buffer reagent boric acid, complexing agent Trisodium Citrate, additive o-benzoic sulfimide, propionic acid, 1, and the 4-butynediol is formed;
In the 4th step, sealing of hole: it is that the sodium silicate aqueous solution of 50~100g/L is handled 10~20min at 90~100 ℃ of following sealing of holes that the 3rd magnesium alloy handled well of step is adopted concentration, the magnesium alloy of zinc, nickel composite deposite that promptly obtained electroplating surface;
Described electroplating zinc on magnesium alloy layer is a bottom, and thickness is 20~25 μ m, and electroless nickel layer is as the top layer, the total thickness of electro-galvanized layer and electroless nickel layer≤40 μ m.
2. the electro-plating method of electro-galvanizing as claimed in claim 1, nickel composite deposite magnesium alloy, it is characterized in that: the acid solution described in the first step is a combination solution, each concentration of component is 5~25ml/L phosphoric acid, 2~25g/L hydrogen fluoride amine, 0.005~5g/L sodium laurylsulfonate, activation temperature is 15~50 ℃, and soak time is 0.5~10 minute.
3. the electro-plating method of electro-galvanizing as claimed in claim 1, nickel composite deposite magnesium alloy, it is characterized in that: described vitriol dip galvanizing technique is: at each concentration of component is zinc sulfate 30g/L, yellow soda ash or salt of wormwood 5g/L, Potassium monofluoride 7g/L, potassium pyrophosphate 150g/L, soak zinc in the zinc dipping solution of pH=10.2~10.4, temperature is 70~80 ℃, and galvanizing time is 10 minutes.
4. the electro-plating method of electro-galvanizing as claimed in claim 1, nickel composite deposite magnesium alloy is characterized in that: the acetic acid zinc concentration is 5~55g/L in the described electrodepositing zinc layer solution.
5. the electro-plating method of electro-galvanizing as claimed in claim 1, nickel composite deposite magnesium alloy, it is characterized in that: additive is OP-emulsifying agent 1.5ml/L, quadrol 2.5g/L, four kinds of additives of dimethylamine 2.5g/L, benzylideneacetone 2.5g/L in the described electrodepositing zinc layer solution, or adds myo-Inositol hexaphosphate 0.02g/L, three kinds of additives of Vanillin 0.01g/L, thiocarbamide 0.5g/L.
6. the electro-plating method of electro-galvanizing as claimed in claim 1, nickel composite deposite magnesium alloy is characterized in that: the processing parameter of electrodepositing zinc layer is: current density is 0.2~4A/dm 2, temperature is 35~65 ℃, pH=6.0~9.5.
7. the electro-plating method of electro-galvanizing as claimed in claim 1, nickel composite deposite magnesium alloy; it is characterized in that: in the electronickelling solution; the concentration of single nickel salt is 20~300g/L; the concentration of nickelous chloride is 2~50g/L, and the concentration of buffer reagent boric acid is 5~30g/L, and the concentration of complexing agent Trisodium Citrate is 20~30g/L; o-benzoic sulfimide concentration is 0.01~5g/L in the additive; propionic acid concentration is 0.01~4g/L, 1, and 4-butynediol concentration is 0.01~6g/L.
8. the electro-plating method of electro-galvanizing as claimed in claim 1, nickel composite deposite magnesium alloy is characterized in that: the electroplating temperature of electronickelling is 30~65 ℃, electroplate liquid pH=3.0~7.0, and current density is 0.2~4A/dm 2
9. the electro-plating method of electro-galvanizing as claimed in claim 1, nickel composite deposite magnesium alloy is characterized in that: wash sample with flowing water between each operation steps.
CN2009100264634A 2009-04-22 2009-04-22 Magnesium alloy with zinc and nickel compound plating layers and preparation method thereof Expired - Fee Related CN101525711B (en)

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