CN104141138A - Preparation method of micro-arc oxidation-composite chemical nickel plating coating layer on surface of magnesium alloy - Google Patents

Preparation method of micro-arc oxidation-composite chemical nickel plating coating layer on surface of magnesium alloy Download PDF

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CN104141138A
CN104141138A CN201310164631.2A CN201310164631A CN104141138A CN 104141138 A CN104141138 A CN 104141138A CN 201310164631 A CN201310164631 A CN 201310164631A CN 104141138 A CN104141138 A CN 104141138A
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magnesium alloy
composite chemical
arc oxidation
micro
nickel plating
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杜克勤
郭兴华
郭泉忠
王勇
王福会
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Institute of Metal Research of CAS
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Institute of Metal Research of CAS
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Abstract

The invention discloses a preparation method of a micro-arc oxidation-composite chemical nickel plating coating layer on the surface of a magnesium alloy, and belongs to the technical field of metal surface treatment. The preparation method comprises the following steps: firstly, the micro-arc oxidation is performed for the surface of a magnesium alloy matrix to form a porous ceramic coating layer on the surface; then, the hole sealing treatment is performed for the matrix with the porous ceramic coating layer by adopting nanometer self-assembly penetrant containing nickel salt; the nickel preplating treatment is performed for the matrix, after the hole sealing treatment, by adopting alcohol solution of sodium borohydride; and finally, the composite chemical nickel plating treatment is performed for the matrix, after the nickel preplating treatment, to form the micro-arc oxidation-composite chemical nickel plating coating layer on the surface of the magnesium alloy. The micro composite coating layer, prepared by the method, has better protective thickness, good binding force with the matrix, good corrosion resistance, high hardness, good surface brightness and full luster, effectively solves the protective requirements of high wear resistance and corrosion resistance of the magnesium alloy, and provides powerful guarantee to the further application of the magnesium alloy.

Description

A kind of preparation method of magnesium alloy surface micro-arc oxidation-composite chemical nickel plating coating
Technical field
The present invention relates to field of metal surface treatment technology, be specifically related to a kind of preparation method of magnesium alloy surface micro-arc oxidation-composite chemical nickel plating coating.
Background technology
Magnesium alloy is the metal of density minimum in structural metallic materials; compare with aluminium alloy; its Young's modulus is large; good heat dissipation; shock absorbing is good; the features such as loading capacity is large that withstand shocks, are the structural metallic materialss that meets the tool potentiality of car light, environmental protection and performance optimization development, are also 21st century to have one of metallic substance of application prospect most.In addition, magnesium alloy also has that specific tenacity is high, specific rigidity is high, damping and amortization is good, thermal conductivity is good and the high-performance such as vibration damping is good, as the substitute of iron and steel, aluminium, plastic or other material, in fields such as automotive industry, aerospace industry and electronic industries, be with a wide range of applications.Yet up to now, between its application potential and reality, still there is huge contrast, this is because magnesium is extremely active metal, Standard Electrode Potentials is-2.36V (vs.SCE), its thermodynamic stability is poor, and oxide compound (film) short texture, causes the corrosion resistance of magnesium alloy poor, this has caused magnesium alloy all very serious corrosion will occur in moist atmosphere, extra large water and soil, the obstruction that this is serious the application of magnesium alloy in various fields.In addition, the chemically reactive of magnesium alloy is higher, higher to the integrity of painting/coating, anti-physical abuse Capability Requirement, this just requires the integrity of protective layer (painting/coating), anti-physical abuse ability must reach higher level, and existing painting/coating technology is all difficult to practical requirement.Therefore the high hard anti-corrosion protective layer new technology of exploitation is the key point that promotes magnesium alloy application.It is very important in actual applications that Mg alloy surface is processed.The method of surface modification is a lot, as electrochemical process, chemical method, hot-work method etc.Some novel surface treatment methods are as Laser Surface Treatment, chromium nitride coating, Mg alloy surface deposition of aluminum etc.But up to now, a kind of protective layer that is applicable to magnesium alloy substrate of resisting severe environment also can not developed in countries in the world.
In order to improve surface anticorrosion and the wear resistance of MAGNESIUM METAL, Chinese scholars has been developed numerous surface modifications and painting/plating process, as obtained at magnesium alloy microplasma electrolytic oxide film surface recombination Amorphous Ni-P Alloy settled layer, being combined the dura mater of firm and anti-corrosion anti scuffing with matrix, is a kind of effective and feasible technical thought.On the one hand, complete nickel layer can play sealing process to multilayer ceramic film, has avoided magnesium alloy substrate to contact with the direct of corrosive medium, and the chemical stability due to metallic nickel is good on the other hand, hardness is high, has good wear-resisting and corrosion stability.But fabrication of ceramic coat of magnesium alloy has vesicular structure, directly on its surface, carry out electroless plating, because coated metal is higher than magnesium alloy current potential, after contacting with magnesium alloy, be easy to occur bimetal galvanic corrosion.Especially for complex-shaped or big area plating piece, be difficult to obtain even flawless coating.The formation of this textural defect is easy to occur local bimetallic corrosion or microcosmic galvanic corrosion phenomenon, causes the deterioration of magnesium alloy component mechanical property, can greatly accelerate corrosion process so on the contrary, causes catastrophic consequence.And in the technique of magnesium alloy matrix surface direct electroless nickel, in pretreatment liquid, need to add F-and Cr 6+, or adopt the activation of palladium salt, and both caused the pollution of environment and destruction, improved again cost, be unfavorable for the production of through engineering approaches.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art part, provide a kind of at magnesium alloy differential arc oxidation ceramic coating surface-sealing and prepare the method for composite chemical nickel plating coating, be used for improving the over-all properties that magnesium alloy substrate is anti-corrosion and wear-resisting, and improve the electroconductibility of compound coating, solved magnesium alloy anti scuffing and corrosion resistant requirement of shelter.
The present invention implements by following technical proposal:
A kind of preparation method of magnesium alloy surface micro-arc oxidation-composite chemical nickel plating coating, it is characterized in that: first the method carries out differential arc oxidation to magnesium alloy matrix surface, on its surface, form porous ceramics coating, then adopt the nanoassemble permeate agent that contains nickel salt to carry out sealing of hole processing to being shaped with the matrix of porous ceramics coating, matrix after the alcoholic solution that adopts again sodium borohydride is processed sealing of hole carries out nickel preplating processing, matrix after finally nickel preplating being processed carries out composite chemical Nickel Plating Treatment, forms magnesium alloy surface micro-arc oxidation-composite chemical nickel plating coating.
The method specifically comprises the steps:
(1) magnesium alloy matrix surface differential arc oxidation
By magnesium alloy matrix surface polish, polishing and except wet goods pre-treatment, to remove surface film oxide and impurity.Then the electrolytic solution of pretreated magnesium alloy substrate (as anode) being put into differential arc oxidation adopts high voltage pulse mode to carry out differential arc oxidation processing to matrix.The electrolytic solution of differential arc oxidation is composed as follows: water glass 2~25g/L, and sodium hydroxide 1~10g/L, sodium carbonate 5~8g/L, all the other are deionized water; Electrolyte temperature is 20~60 ℃.Pulse-repetition is 100~2000Hz, and current density is 1~5A/dm 2, the treatment time is 20~120 minutes, and oxide thickness is 5~45 μ m, and this oxide film is porous ceramic film, and porosity is 20%~50%, aperture is 2~8 μ m.
(2) sealing of hole is processed
It is that the magnesium alloy substrate that porous ceramics coating is prepared in surface adopts immersion way to put into the nanoassemble permeate agent that contains nickel salt that described sealing of hole is processed, and stirs 15-20min post-drying.
The described nanoassemble permeate agent that contains nickel salt by component A, B component and deionized water according to 1:(0.2~0.5): the part by weight of (1~2) mixes, stir 20~30min after standing pin bubble obtain; Wherein: B component is the alcoholic solution of nickelous acetate, in the alcoholic solution of described nickelous acetate, solvent is dehydrated alcohol, nickelous acetate concentration 5-25g/L.Component A is that the component by following weight part is that raw material makes by hydrolysis reaction:
40~55 parts of silane mixture liquid
0.2~1 part of hydrolyst
5~10 parts of solubility promoters
25~50 parts of deionized waters.
Described silane mixture liquid is mixed by γ-glycidyl ether oxygen propyl trimethoxy silicane (KH-560) and tetraethyl orthosilicate (TEOS), and the mol ratio of γ-glycidyl ether oxygen propyl trimethoxy silicane and tetraethyl orthosilicate is (3~5): (0.2~2).Described hydrolyst is the mixed solution of acetic acid and phytic acid, and acetic acid and phytic acid mol ratio are (3~10): (1~4); Described solubility promoter is dehydrated alcohol.
(3) nickel preplating is processed
It is that the alcoholic solution that the magnesium alloy substrate after sealing of hole is processed adopts immersion way at room temperature to put into sodium borohydride carries out nickel preplating that described nickel preplating is processed, and the treatment time is 5~10min, takes out and washes with deionized water.In the alcoholic solution of described sodium borohydride, solvent is dehydrated alcohol, and sodium borohydride concentration is 20~50g/L.
(4) composite chemical Nickel Plating Treatment
Composite chemical plating solution forms: the single nickel salt of 20~25g/L, the inferior sodium phosphate of 20~25g/L, 10~15g/L citric acid, 5~10g/L sodium acetate, alumina particle (nano level) 20~40g/L, all the other are deionized water, with ammoniacal liquor, regulate composite chemical bath pH value to 5.5~6.5; Adopt the mode of water bath with thermostatic control heating that composite chemical plating solution is heated to 65~75 ℃, then the magnesium alloy substrate after nickel preplating is put into composite chemical plating solution, solution and matrix surface are fully reacted, on the micro-arc oxidation films of matrix surface, form composite chemical nickel plating coating.Composite chemical Nickel Plating Treatment processing parameter is: service temperature is 65~75 ℃, and the electroless plating time is 30~60min, and the composite chemical nickel plating coat-thickness of acquisition is 8~10 μ m.
Described magnesium alloy is AZ91D, AZ31B, ZM5, ZM6, MB5 or magnesium-rare earth Mg-Gd-Y etc.
Advantage of the present invention and beneficial effect are as follows:
1, the nanoassemble permeate agent that contains nickel salt that the present invention is used for sealing of hole is in preparation process, its hydrolysis environment is high water concentration, can accelerate the hydrolysis reaction of silane mixture liquid, suppress the polyreaction of silane hydrolyzate intermediate, and finally form stable nanoassemble dispersion liquid.Be applicable to various magnesium alloy micro-arc oxidization ceramic coating (porous ceramic layer) surface, can form good compound action with micropore and the defect on arc differential oxide ceramic layer surface, micropore and defect are played to the effect of " sealing "; Make ceramic layer form good chemical bonding with painting interlayer, improve integral protection performance and the bonding properties of magnesium alloy differential arc oxidation compound coating, can extend to a certain extent the work-ing life of magnesium alloy differential arc oxidation compound coating in actual application, reduce maintenance cost.
2, the inventive method is the process modification to traditional chemical nickel plating, adopts without the method for palladium salt activation and carries out chemical nickel plating, does not use again F simultaneously -and Cr 6+, so raw material sources are extensive, and with low cost, material therefor low toxic and environment-friendly, preparation technology is simply efficient.Technological process is carried out at ambient temperature, has simplified the operation of composite chemical nickel plating and has reduced the pollution of technological process to environment.
3, by the inventive method, at magnesium alloy matrix surface, form multiple protective layers (thickness G reatT.GreaT.GT30 μ m), effectively isolated magnesium alloy substrate contacts with extraneous corrosive medium, there is stronger anticorrosion ability, and compound coating bonding strength is large, hardness is high, there is the performance of wear-resisting scratch-resisting wound.
4, the present invention is applicable to the magnesium alloy of AZ, ZM, MB and rare earth metal: as AZ91D, AZ31B, ZM5, ZM6, MB5 and Mg-Gd-Y etc.
Embodiment
Below in conjunction with embodiment, the present invention is further detailed explanation.
Embodiment 1
1. material is prepared: after AZ91D magnesium alloy cutting polishing, polishing, use ultrasonic cleaning oil removing in acetone soln, then in deionized water for ultrasonic, clean and remove organism and impurity.
2. differential arc oxidation: in electrolytic solution, water glass 15g/L, sodium hydroxide 2g/L, sodium carbonate 5g/L, all the other are water, temperature is 50 ℃; Adopt high voltage pulse mode to carry out differential arc oxidation, pulse-repetition is 500Hz, and current density is 2A/dm 2, oxidization time is 40 minutes, and oxide thickness is 25 μ m, and this oxide film is porous ceramic film, and porosity is 40%, aperture is 2~5 μ m.
3. sealing of hole and nickel preplating are processed
1) configuration of silane mixture liquid.Silane KH-560 and TEOS be take to ratio that mol ratio is n (KH560): n (TEOS)=3:1 and mix and stir evenly, obtain silane mixture liquid.
2) configuration of hydrolyst.Acetic acid and phytic acid be take to the ratio that mol ratio is n (acetic acid): n (phytic acid)=3:1 and mix, obtain hydrolyst.
3) configuration of solubility promoter.Solubility promoter is selected dehydrated alcohol.
4) configuration of the alcoholic solution of nickelous acetate.Nickelous acetate 10g/L, dehydrated alcohol 1L.
5) configuration of the alcoholic solution of sodium borohydride.Sodium borohydride 25g/L, dehydrated alcohol 1L.
6) configuration of the nanoassemble permeate agent that contains nickel salt.At ambient temperature, after silane mixture liquid, hydrolyst, solubility promoter and deionized water are mixed by following parts by weight, continue to stir, hydrolysis 48h, until after mixed solution clarification, obtain nanoassemble permeate agent (component A).
40 parts of silane mixture liquid
0.2 part of hydrolyst
9.8 parts of solubility promoters
50 parts of deionized waters
The alcoholic solution of nanoassemble permeate agent and nickelous acetate and deionized water are pressed after the part by weight mixing of 1:0.2:1 to the 30min that stirs, standing pin bubble.
7) sealing of hole and nickel preplating are processed
The magnesium alloy substrate that surface is prepared to ceramic coating adopts immersion way to put into the nanoassemble permeate agent that contains nickel salt, continue to stir 15min, sodium borohydride is at room temperature put in taking-up alcoholic solution after drying carries out nickel preplating, and the treatment time is 5min, takes out also and washes with deionized water.
4. composite chemical Nickel Plating Treatment
Chemical plating fluid forms: the single nickel salt of 20g/L, and the inferior sodium phosphate of 20g/L, 10g/L citric acid, 10g/L sodium acetate, alumina particle (nano level) 20g/L, all the other are deionized water, by ammoniacal liquor regulator solution pH value to 5.5.Composite chemical depositing process parameter is: service temperature is 65 ℃, and the electroless plating time is 40min, and the chemical plating thickness of acquisition is 8 μ m.
The bonding strength >35MPa of the compound coating being obtained by the present embodiment, surperficial Vickers' hardness maximum can reach 1200HV, more than resistance to neutral salt spray test reaches 1500h.
Embodiment 2
Difference from Example 1 is:
1. material is prepared: after AZ31B magnesium alloy cutting polishing, polishing, use ultrasonic cleaning oil removing in ethanol solution, then in deionized water for ultrasonic, clean and remove organism and impurity.
2. differential arc oxidation: in electrolytic solution, water glass 10g/L, sodium hydroxide 10g/L, sodium carbonate 8g/L, all the other are water, temperature is 35 ℃.Adopt high voltage pulse mode to carry out differential arc oxidation, pulse-repetition is 800Hz, and current density is 2A/dm 2, oxidization time is 60min, and oxide thickness is 15 μ m, and this oxide film is porous ceramic film, and porosity is 35%, aperture is 3~5 μ m.
3. sealing of hole and nickel preplating are processed
1) configuration of silane mixture liquid.Silane KH-560 and TEOS be take to ratio that mol ratio is n (KH560): n (TEOS)=3:2 and mix and stir evenly, obtain silane mixture liquid.
2) configuration of hydrolyst.Acetic acid and phytic acid be take to the ratio that mol ratio is n (acetic acid): n (phytic acid)=2:1 and mix, obtain hydrolyst.
3) configuration of solubility promoter.Solubility promoter is selected dehydrated alcohol.
4) configuration of the alcoholic solution of nickelous acetate.Nickelous acetate 15g/L, dehydrated alcohol 1L.
5) configuration of the alcoholic solution of sodium borohydride.Sodium borohydride 20g/L, dehydrated alcohol 1L.
6) configuration of the nanoassemble permeate agent that contains nickel salt.At ambient temperature, after silane mixture liquid, hydrolyst, solubility promoter and deionized water are mixed by following parts by weight, continue to stir, hydrolysis 48h, until after mixed solution clarification, obtain nanoassemble permeate agent (component A).
45 parts of silane mixture liquid
0.5 part of hydrolyst
9.5 parts of solubility promoters
45 parts of deionized waters
The alcoholic solution of nanoassemble permeate agent and nickelous acetate and deionized water are pressed after the part by weight mixing of 1:0.5:1 to the 30min that stirs, standing pin bubble.
7) sealing of hole and nickel preplating are processed
The magnesium alloy substrate that surface is prepared to ceramic coating adopts immersion way to put into the nanoassemble permeate agent that contains nickel salt, continue to stir 15min, sodium borohydride is at room temperature put in taking-up alcoholic solution after drying carries out nickel preplating, and the treatment time is 5min, takes out also and washes with deionized water.
4. composite chemical Nickel Plating Treatment
Chemical plating fluid forms: the single nickel salt of 20g/L, and the inferior sodium phosphate of 25g/L, 10g/L citric acid, 5g/L sodium acetate, alumina particle (nano level) 25g/L, all the other are deionized water, by ammoniacal liquor regulator solution pH value to 5.5.Composite chemical depositing process parameter is: service temperature is 65 ℃, and the electroless plating time is 40min, and the chemical plating thickness of acquisition is 8 μ m.
The bonding strength >33MPa of the compound coating being obtained by the present embodiment, surperficial Vickers' hardness maximum can reach 1300HV, more than resistance to neutral salt spray test reaches 1450h.
Embodiment 3
Difference from Example 1 is:
1. material is prepared: after ZM5 magnesium alloy cutting polishing, polishing, use ultrasonic cleaning oil removing in organic solvent, then in deionized water for ultrasonic, clean and remove organism and impurity.
2. differential arc oxidation: electrolytic solution mesosilicic acid sodium 20g/L, sodium hydroxide 6g/L, sodium carbonate 8g/L, all the other are water, temperature is 40 ℃; Adopt high voltage pulse mode to carry out differential arc oxidation, pulse-repetition is 1000Hz, and current density is 3A/dm 2, oxidization time is 50 minutes, and oxide thickness is 20 μ m, and this oxide film is porous ceramic film, and porosity is 50%, aperture is 6~10 μ m.
3. sealing of hole and nickel preplating are processed
1) configuration of silane mixture liquid.Silane KH-560 and TEOS be take to ratio that mol ratio is n (KH560): n (TEOS)=5:2 and mix and stir evenly, obtain silane mixture liquid.
2) configuration of hydrolyst.Acetic acid and phytic acid be take to the ratio that mol ratio is n (acetic acid): n (phytic acid)=5:2 and mix, obtain hydrolyst.
3) configuration of solubility promoter.Solubility promoter is selected dehydrated alcohol.
4) configuration of the alcoholic solution of nickelous acetate.Nickelous acetate 10g/L, dehydrated alcohol 1L.
5) configuration of the alcoholic solution of sodium borohydride.Sodium borohydride 25g/L, dehydrated alcohol 1L.
6) configuration of the nanoassemble permeate agent that contains nickel salt.At ambient temperature, after silane mixture liquid, hydrolyst, solubility promoter and deionized water are mixed by following parts by weight, continue to stir, hydrolysis 48h, until after mixed solution clarification, obtain nanoassemble permeate agent (component A).
50 parts of silane mixture liquid
0.5 part of hydrolyst
9.5 parts of solubility promoters
40 parts of deionized waters
The alcoholic solution of nanoassemble permeate agent and nickelous acetate and deionized water are pressed after the part by weight mixing of 1:0.4:1.5 to the 30min that stirs, standing pin bubble.
7) sealing of hole and nickel preplating are processed
The magnesium alloy substrate that surface is prepared to ceramic coating adopts immersion way to put into the nanoassemble permeate agent that contains nickel salt, continue to stir 15min, sodium borohydride is at room temperature put in taking-up alcoholic solution after drying carries out nickel preplating, and the treatment time is 5min, takes out also and washes with deionized water.
4. composite chemical Nickel Plating Treatment
Chemical plating fluid forms: the single nickel salt of 25g/L, and the inferior sodium phosphate of 20g/L, 15g/L citric acid, 5g/L sodium acetate, alumina particle (nano level) 30g/L, all the other are deionized water, by ammoniacal liquor regulator solution pH value to 6.0.Composite chemical depositing process parameter is: service temperature is 70 ℃, and the electroless plating time is 40min, and the chemical plating thickness of acquisition is 9 μ m.
The bonding strength >36MPa of the compound coating being obtained by the present embodiment, surperficial Vickers' hardness maximum can reach 1350HV, more than resistance to neutral salt spray test reaches 1400h.
Embodiment 4
Difference from Example 1 is:
1. material is prepared: after ZM6 magnesium alloy cutting polishing, polishing, use ultrasonic cleaning oil removing in acetone soln, then in deionized water for ultrasonic, clean and remove organism and impurity.
2. differential arc oxidation: in electrolytic solution, water glass 20g/L, sodium hydroxide 3g/L, sodium carbonate 6g/L, all the other are water, temperature is 45 ℃; Adopt high voltage pulse mode to carry out differential arc oxidation, pulse-repetition is 1500Hz, and current density is 4A/dm 2, oxidization time is 45 minutes, and oxide thickness is 20 μ m, and this oxide film is porous ceramic film, and porosity is 30%, aperture is 3~8 μ m.
3. sealing of hole and nickel preplating are processed
1) configuration of silane mixture liquid.Silane KH-560 and TEOS be take to ratio that mol ratio is n (KH560): n (TEOS)=5:1 and mix and stir evenly, obtain silane mixture liquid.
2) configuration of hydrolyst.Acetic acid and phytic acid be take to the ratio that mol ratio is n (acetic acid): n (phytic acid)=5:1 and mix, obtain hydrolyst.
3) configuration of solubility promoter.Solubility promoter is selected dehydrated alcohol.
4) configuration of the alcoholic solution of nickelous acetate.Nickelous acetate 20g/L, dehydrated alcohol 1L.
5) configuration of the alcoholic solution of sodium borohydride.Sodium borohydride 35g/L, dehydrated alcohol 1L.
6) configuration of the nanoassemble permeate agent that contains nickel salt.At ambient temperature, after silane mixture liquid, hydrolyst, solubility promoter and deionized water are mixed by following parts by weight, continue to stir, hydrolysis 48h, until after mixed solution clarification, obtain nanoassemble permeate agent (component A).
45 parts of silane mixture liquid
0.6 part of hydrolyst
9.4 parts of solubility promoters
45 parts of deionized waters
The alcoholic solution of nanoassemble permeate agent and nickelous acetate and deionized water are pressed after the part by weight mixing of 1:0.5:1.5 to the 30min that stirs, standing pin bubble.
7) sealing of hole and nickel preplating are processed
The magnesium alloy substrate that surface is prepared to ceramic coating adopts immersion way to put into the nanoassemble permeate agent that contains nickel salt, continue to stir 15min, sodium borohydride is at room temperature put in taking-up alcoholic solution after drying carries out nickel preplating, and the treatment time is 5min, takes out also and washes with deionized water.
4. composite chemical Nickel Plating Treatment
Chemical plating fluid forms: the single nickel salt of 20g/L, and the inferior sodium phosphate of 20g/L, 15g/L citric acid, 5g/L sodium acetate, alumina particle (nano level) 30g/L, all the other are deionized water, by ammoniacal liquor regulator solution pH value to 6.5.Composite chemical depositing process parameter is: service temperature is 65 ℃, and the electroless plating time is 45min, and the chemical plating thickness of acquisition is 10 μ m.
The bonding strength >35MPa of the compound coating being obtained by the present embodiment, surperficial Vickers' hardness maximum can reach 1400HV, more than resistance to neutral salt spray test reaches 1350h.
Embodiment 5
Difference from Example 1 is:
1. material is prepared: after Mg-Gd-Y magnesium alloy cutting polishing, polishing, use ultrasonic cleaning oil removing in ethanolic soln, then in deionized water for ultrasonic, clean and remove organism and impurity.
2. differential arc oxidation: in electrolytic solution, water glass 25g/L, sodium hydroxide 5g/L, sodium carbonate 7g/L, all the other are water, temperature is 40 ℃; Adopt high voltage pulse mode to carry out differential arc oxidation, pulse-repetition is 2000Hz, and current density is 5A/dm 2, oxidization time is 55 minutes, and oxide thickness is 18 μ m, and this oxide film is porous ceramic film, and porosity is 30%, aperture is 3~4 μ m.
3. sealing of hole and nickel preplating are processed
1) configuration of silane mixture liquid.Silane KH-560 and TEOS be take to ratio that mol ratio is n (KH560): n (TEOS)=4:1 and mix and stir evenly, obtain silane mixture liquid.
2) configuration of hydrolyst.Acetic acid and phytic acid be take to the ratio that mol ratio is n (acetic acid): n (phytic acid)=10:3 and mix, obtain hydrolyst.
3) configuration of solubility promoter.Solubility promoter is selected dehydrated alcohol.
4) configuration of the alcoholic solution of nickelous acetate.Nickelous acetate 15g/L, dehydrated alcohol 1L.
5) configuration of the alcoholic solution of sodium borohydride.Sodium borohydride 40g/L, dehydrated alcohol 1L.
6) configuration of the nanoassemble permeate agent that contains nickel salt.At ambient temperature, after silane mixture liquid, hydrolyst, solubility promoter and deionized water are mixed by following parts by weight, continue to stir, hydrolysis 48h, until after mixed solution clarification, obtain nanoassemble permeate agent (component A).
55 parts of silane mixture liquid
0.8 part of hydrolyst
9.2 parts of solubility promoters
35 parts of deionized waters
The alcoholic solution of nanoassemble permeate agent and nickelous acetate and deionized water are pressed after the part by weight mixing of 1:0.2:1.8 to the 30min that stirs, standing pin bubble.
7) sealing of hole and nickel preplating are processed
The magnesium alloy substrate that surface is prepared to ceramic coating adopts immersion way to put into the nanoassemble permeate agent that contains nickel salt, continue to stir 15min, sodium borohydride is at room temperature put in taking-up alcoholic solution after drying carries out nickel preplating, and the treatment time is 5min, takes out also and washes with deionized water.
4. composite chemical Nickel Plating Treatment
Chemical plating fluid forms: the single nickel salt of 24g/L, and the inferior sodium phosphate of 24g/L, 105g/L citric acid, 8g/L sodium acetate, alumina particle (nano level) 40g/L, all the other are deionized water, by ammoniacal liquor regulator solution pH value to 6.5.Composite chemical depositing process parameter is: service temperature is 65 ℃, and the electroless plating time is 50min, and the chemical plating thickness of acquisition is 10 μ m.
The bonding strength >35MPa of the compound coating being obtained by the present embodiment, surperficial Vickers' hardness maximum can reach 1450HV, more than resistance to neutral salt spray test reaches 1300h.
Above-described embodiment is the present invention at magnesium alloy matrix surface embodiment preferably; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.

Claims (12)

1. the preparation method of magnesium alloy surface micro-arc oxidation-composite chemical nickel plating coating, it is characterized in that: first the method carries out differential arc oxidation to magnesium alloy matrix surface, on its surface, form porous ceramics coating, then adopt the nanoassemble permeate agent that contains nickel salt to carry out sealing of hole processing to being shaped with the matrix of porous ceramics coating, matrix after the alcoholic solution that adopts again sodium borohydride is processed sealing of hole carries out nickel preplating processing, matrix after finally nickel preplating being processed carries out composite chemical Nickel Plating Treatment, forms magnesium alloy surface micro-arc oxidation-composite chemical nickel plating coating.
2. according to the preparation method of magnesium alloy surface micro-arc oxidation-composite chemical nickel plating coating claimed in claim 1, it is characterized in that: the electrolytic solution of differential arc oxidation consists of: water glass 2~25g/L, sodium hydroxide 1~10g/L, sodium carbonate 5~8g/L, all the other are deionized water; Electrolyte temperature is 20~60 ℃; Adopt high voltage pulse mode to carry out differential arc oxidation, pulse-repetition is 100~2000Hz, and current density is 1~5A/dm 2, oxidization time is 20~120 minutes; The oxide thickness that forms is 5~45 μ m, and this oxide film is porous ceramic film, and porosity is 20%~50%, and aperture is 2~8 μ m.
3. the preparation method of magnesium alloy surface micro-arc oxidation-composite chemical nickel plating coating according to claim 1, it is characterized in that: it is that the magnesium alloy substrate that porous ceramics coating is prepared in surface adopts immersion way to put into the nanoassemble permeate agent that contains nickel salt that described sealing of hole is processed, and stirs 15-20min post-drying.
4. according to the preparation method of magnesium alloy surface micro-arc oxidation-composite chemical nickel plating coating claimed in claim 3, it is characterized in that: described in contain nickel salt nanoassemble permeate agent by component A, B component and deionized water according to 1:(0.2~0.5): the mass ratio of (1~2) mixes, stir 20~30min after standing pin bubble obtain; Wherein: B component is the alcoholic solution of nickelous acetate, component A is that the component by following weight part is that raw material makes by hydrolysis reaction:
40~55 parts of silane mixture liquid
0.2~1 part of hydrolyst
5~10 parts of solubility promoters
25~50 parts of deionized waters.
5. according to the preparation method of magnesium alloy surface micro-arc oxidation-composite chemical nickel plating coating claimed in claim 4, it is characterized in that: in the alcoholic solution of described nickelous acetate, solvent is dehydrated alcohol, nickelous acetate concentration 5-25g/L.
6. the preparation method of magnesium alloy surface micro-arc oxidation-composite chemical nickel plating coating according to claim 4, it is characterized in that: described silane mixture liquid is mixed by γ-glycidyl ether oxygen propyl trimethoxy silicane and tetraethyl orthosilicate, the mol ratio of γ-glycidyl ether oxygen propyl trimethoxy silicane and tetraethyl orthosilicate is (3~5): (0.2~2).
7. the preparation method of magnesium alloy surface micro-arc oxidation-composite chemical nickel plating coating according to claim 4, is characterized in that: described hydrolyst is the mixed solution of acetic acid and phytic acid, and acetic acid and phytic acid mol ratio are (3~10): (1~4); Described solubility promoter is dehydrated alcohol.
8. according to the preparation method of magnesium alloy surface micro-arc oxidation-composite chemical nickel plating coating claimed in claim 1, it is characterized in that: it is that the alcoholic solution that the magnesium alloy substrate after sealing of hole is processed adopts immersion way at room temperature to put into sodium borohydride carries out nickel preplating that described nickel preplating is processed, treatment time is 5~10min, takes out and washes with deionized water.
9. according to the preparation method of the magnesium alloy surface micro-arc oxidation-composite chemical nickel plating coating described in claim 1 or 8, it is characterized in that: in the alcoholic solution of described sodium borohydride, solvent is dehydrated alcohol, and sodium borohydride concentration is 20~50g/L.
10. according to the preparation method of magnesium alloy surface micro-arc oxidation-composite chemical nickel plating coating claimed in claim 1, it is characterized in that: the process of described composite chemical Nickel Plating Treatment is: adopt the mode of water bath with thermostatic control heating that composite chemical plating solution is heated to 65~75 ℃, then the magnesium alloy substrate after nickel preplating is processed is put into composite chemical plating solution, solution and matrix surface are fully reacted, thereby form composite chemical nickel plating coating in Mg alloy surface porous ceramics coating; Composite chemical Nickel Plating Treatment processing parameter is: service temperature is 65~75 ℃, and the treatment time is 30~60min, and the composite chemical nickel plating coat-thickness of acquisition is 8~10 μ m.
11. according to the preparation method of magnesium alloy surface micro-arc oxidation-composite chemical nickel plating coating claimed in claim 10, it is characterized in that: the single nickel salt that consists of 20~25g/L of described composite chemical plating solution, the inferior sodium phosphate of 20~25g/L, 10~15g/L citric acid, 5~10g/L sodium acetate, alumina particle (nano level) 20~40g/L, all the other are deionized water; With ammoniacal liquor, regulating the pH value of composite chemical plating solution is 5.5~6.5.
12. magnesium alloy substrates according to claim 1, is characterized in that: described magnesium alloy is AZ91D, AZ31B, ZM5, ZM6, MB5 or magnesium-rare earth Mg-Gd-Y.
CN201310164631.2A 2013-05-07 2013-05-07 Preparation method of micro-arc oxidation-composite chemical nickel plating coating layer on surface of magnesium alloy Pending CN104141138A (en)

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CN105543920A (en) * 2015-12-10 2016-05-04 嘉瑞科技(惠州)有限公司 Treatment method for preparing electric conducting coating layer on surface of magnesium alloy micro-arc oxidation layer
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CN108712830A (en) * 2018-05-30 2018-10-26 广东天承科技有限公司 A kind of circuit board without palladium chemical-copper-plating process
CN110241452A (en) * 2019-07-16 2019-09-17 嘉兴学院 Magnesium alloy differential arc oxidation electrolyte and preparation method thereof and surface treatment method of Mg alloy
CN110424039A (en) * 2019-09-16 2019-11-08 东北大学 The preparation method of the anti-corrosion selfreparing differential arc oxidation coating of magnesium alloy based on hydrotalcite nano inhibition microcapsules
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CN104611751A (en) * 2015-02-21 2015-05-13 桂林理工大学 Micro-arc oxidation self-assembly composite membrane layer on surface of magnesium alloy and preparation method of micro-arc oxidation self-assembly composite membrane layer
CN105598456A (en) * 2015-09-18 2016-05-25 扬州海昌粉末冶金有限公司 Method for sealing hole of injection-molding stainless steel product in silanization way and water solution formula and application of silane coupling agent
CN105543920A (en) * 2015-12-10 2016-05-04 嘉瑞科技(惠州)有限公司 Treatment method for preparing electric conducting coating layer on surface of magnesium alloy micro-arc oxidation layer
CN108712830A (en) * 2018-05-30 2018-10-26 广东天承科技有限公司 A kind of circuit board without palladium chemical-copper-plating process
CN108712830B (en) * 2018-05-30 2021-02-26 广东天承科技股份有限公司 Palladium-free chemical copper plating process for circuit board
CN110241452A (en) * 2019-07-16 2019-09-17 嘉兴学院 Magnesium alloy differential arc oxidation electrolyte and preparation method thereof and surface treatment method of Mg alloy
CN110241452B (en) * 2019-07-16 2020-05-12 嘉兴学院 Magnesium alloy micro-arc oxidation electrolyte, preparation method thereof and magnesium alloy surface treatment method
CN110424039A (en) * 2019-09-16 2019-11-08 东北大学 The preparation method of the anti-corrosion selfreparing differential arc oxidation coating of magnesium alloy based on hydrotalcite nano inhibition microcapsules
CN110424039B (en) * 2019-09-16 2021-08-10 东北大学 Preparation method of magnesium alloy corrosion-resistant self-repairing micro-arc oxidation coating based on hydrotalcite nano corrosion-inhibiting microcapsule
CN111020672A (en) * 2019-11-30 2020-04-17 长沙新材料产业研究院有限公司 Micro-arc oxidation process for Mg-Gd-Y magnesium alloy
RU2757642C1 (en) * 2021-02-15 2021-10-19 Федеральное государственное бюджетное учреждение науки Институт физической химии и электрохимии им. А.Н. Фрумкина Российской академии наук (ИФХЭ РАН) Coating for the protection of magnesium and its alloys from corrosion and a method for its production

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Application publication date: 20141112