CN101781785A - Method for plating high corrosion resistant aluminum-manganese alloy on surface of magnesium alloy - Google Patents
Method for plating high corrosion resistant aluminum-manganese alloy on surface of magnesium alloy Download PDFInfo
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- CN101781785A CN101781785A CN200910300182A CN200910300182A CN101781785A CN 101781785 A CN101781785 A CN 101781785A CN 200910300182 A CN200910300182 A CN 200910300182A CN 200910300182 A CN200910300182 A CN 200910300182A CN 101781785 A CN101781785 A CN 101781785A
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000005260 corrosion Methods 0.000 title claims abstract description 28
- 238000007747 plating Methods 0.000 title claims abstract description 26
- 229910000914 Mn alloy Inorganic materials 0.000 title claims abstract description 22
- -1 aluminum-manganese Chemical compound 0.000 title claims abstract description 21
- 230000007797 corrosion Effects 0.000 title abstract description 26
- 238000000576 coating method Methods 0.000 claims abstract description 66
- 239000011248 coating agent Substances 0.000 claims abstract description 65
- 150000003839 salts Chemical class 0.000 claims abstract description 30
- 238000009713 electroplating Methods 0.000 claims description 25
- 229910052725 zinc Inorganic materials 0.000 claims description 22
- 239000011701 zinc Substances 0.000 claims description 22
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 12
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 4
- 229940055858 aluminum chloride anhydrous Drugs 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 2
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims 2
- 238000004070 electrodeposition Methods 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 14
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 238000005516 engineering process Methods 0.000 abstract description 7
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 238000004381 surface treatment Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000011253 protective coating Substances 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 34
- 239000008399 tap water Substances 0.000 description 34
- 235000020679 tap water Nutrition 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 239000011734 sodium Substances 0.000 description 16
- 239000011780 sodium chloride Substances 0.000 description 16
- VZWGHDYJGOMEKT-UHFFFAOYSA-J sodium pyrophosphate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O VZWGHDYJGOMEKT-UHFFFAOYSA-J 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 238000005498 polishing Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000004913 activation Effects 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- 229910045601 alloy Inorganic materials 0.000 description 8
- 239000000956 alloy Substances 0.000 description 8
- 238000005034 decoration Methods 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 8
- 238000005246 galvanizing Methods 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 229910018131 Al-Mn Inorganic materials 0.000 description 7
- 229910018461 Al—Mn Inorganic materials 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 7
- 239000004141 Sodium laurylsulphate Substances 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 7
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 7
- 238000004506 ultrasonic cleaning Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000007772 electroless plating Methods 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000013325 dietary fiber Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
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- Electroplating Methods And Accessories (AREA)
Abstract
The invention relates to a method for preparing high corrosion resistant aluminum-manganese alloy on the surface of a magnesium alloy, namely preparing a coating on the surface of the magnesium alloy so as to improve the corrosion resistance and rigidity of the magnesium alloy, and belongs to the technical field of metal surface treatment. The method for preparing the high corrosion resistant aluminum-manganese alloy on the surface of the manganese alloy is characterized in that: an aluminum-manganese alloy is plated on the surface of the magnesium alloy by adopting a method of low-temperature molten salt plating; the magnesium alloy is subjected to pre-galvanization in aqueous solution before the aluminum-manganese alloy is plated so as to prevent the corrosion of the magnesium alloy in the molten salt and improve the binding force between the coating and a matrix. The coating is more uniform and dense by controlling various parameters during plating in the molten salt, so the corrosion resistance of the surface is improved. Due to the method, the obtained aluminum-manganese alloy coating is uniform and bright, has firm binding with the matrix, has strong rigidity and corrosion resistance, and is an ideal protective coating for the magnesium alloy. The whole technology has the advantages of simple flow, cheap device, environmental friendliness, and the like.
Description
Technical field:
The present invention relates to a kind ofly prepare the method for high alufer, belong to field of metal surface treatment technology at Mg alloy surface.
Background technology:
Magnesium alloy has advantages such as density is little, specific tenacity is high, capability of electromagnetic shielding is good, and is described as 21 century green engineering material, is with a wide range of applications in automotive industry, aerospace industry and electronic industry.Yet shortcomings such as solidity to corrosion is poor, wear no resistance, hardness is low become the bottleneck problem of restriction magnesium alloy practical application, have limited its large-area use.Therefore, can use in the middle of the rugged environment more in order to make magnesium alloy, it is very necessary to develop corresponding magnesium alloy surface treatment.
Magnesium alloy anticorrosion aspect, a kind of means of effective raising corrosion stability of magnesium alloy are electroplated other solidity to corrosion preferred metal coating at Mg alloy surface exactly.Yet,, make and directly electroplate or electroless plating is very difficult at Mg alloy surface because magnesium alloy electrochemical properties very active and the different matrix phase is widely different.Zinc and nickel are only two kinds of metals that can directly plate on magnesium alloy.Based on these two kinds of metal plating, the electroplated coating that grows up at Mg alloy surface has Zn, Cu, Ni, Ni-Cr-Cu etc., and chemical plating coating mainly is Ni, Zn-P alloy coat etc.Method (as thermospray, surface heat diffusion, magnetron sputtering, ion plating, vapour deposition etc.) by other physics or chemistry also can prepare metallic coatings such as Al, TiN at Mg alloy surface, but the corresponding technology imperfection that exists, therefore the difficulty and the defective of aspects such as the erosion resistance of coating, thickness, homogeneity and bonding force are to the research of these processing methodes and use far away from electroplating or electroless plating many.At present, the typical process in Mg alloy surface plating and electroless plating has the zinc of soaking copper facing and chemical nickel plating:
1) soaks zinc copper facing
Through after the oil removing, alkali cleaning, acidleach, surface active, magnesium alloy directly is dipped in the chemical tank of nonelectrolyte can obtain one deck zinc settled layer as thin as a wafer.Its technical process is: oil removing → alkali cleaning → acidleach → activate → soak zinc → soak other metal of copper → plating.The zinc layer soaks the copper layer and protected owing to as thin as a wafer, need add on the zinc layer again.This processing method is not only complicated, and it is difficult to obtain uniformity in conjunction with good coating.
2) chemical nickel plating
With respect to soaking zinc copper facing bottoming, much easy in the technology of Mg alloy surface direct chemical nickel plating.Its technical process is: oil removing → alkaline etching → activation (generally using hydrofluoric acid) → chemical nickel plating.Nickel layer can directly use as protective layer, also can be used as bottom, carries out electronickelling or other metal again.Nickel layer improves the surface hardness of magnesium alloy greatly, strengthened wear resistance, but the bonding force of coating and matrix is limited, generally need to improve the bonding force of coating and matrix by subsequent heat treatment, and its corrosion resistance nature is unsatisfactory, exist at coating under the situation of pin hole or tiny crack, the matrix magnesium alloy has the danger of accelerated corrosion.
In recent years, the plating of carrying out aluminium and aluminium alloy in fused salt or ionic liquid has obtained common attention.Electroplate aluminum or aluminum alloy based on muriatic electrodeless fused salt, its service temperature is between 120-250 ℃, and this has great importance for preparing metal plating at low-melting Mg alloy surface.Electroplate the Al-Mn alloy layer obtain by molten chloride, have excellent solidity to corrosion, ornamental, oxidation-resistance, processibility, and the conventional aqueous solution coating electroplating out incomparable dense non-porous, no hydrogen embrittlement, and characteristic such as substrate caking power is strong.The Al-Mn alloy layer with amorphous microstructure structure that particularly contains manganese 15%～35%, because its excellent solidity to corrosion, the red rust time of origin in neutral salt spray test reached more than 4 years, was containing Cl
-Pitting potential in the solution has very high using value and application prospects than the high nearly 400mV of fine aluminium.
Summary of the invention:
The objective of the invention is to overcome the difficulty of prior art, a kind of method of plating high corrosion resistant aluminum-manganese alloy on surface of magnesium alloy is provided, its technology is simple, in high anti-corrosion, the high rigidity of Mg alloy surface preparation, in conjunction with good Al-Mn alloy coat.
At above-mentioned purpose, technical scheme of the present invention is:
The present invention prepares the method for Al-Mn alloy at Mg alloy surface, and is at first zinc-plated in advance to magnesium alloy in the aqueous solution, and then electroplates the Al-Mn alloy in molten fused salt, and this technology is specific as follows:
1. technical process
Mechanical polishing → degreasing → washing → alkaline etch → washing → activation → washing → electro-galvanizing → washing → bright dipping → washing → Electroplating Aluminum → washing → drying;
2. technological specification
2.1 mechanical polishing
The purpose of polishing is dietary fibres and an adhesive in order to remove magnesium alloy work-piece surface, and the refinement workpiece surface improves the smooth finish of workpiece surface, reaches the purpose of chamfering, and wedge angle and burr must polish off, in case next procedure is exerted an influence.
2.2 degreasing
The purpose of degreasing is to remove the greasy dirt of Mg alloy surface, makes the workpiece surface cleaning, with the disadvantageous effect of avoiding surperficial grease that coating is formed.The method of degreasing can adopt the alkali electroless oil removing, the oil removing under ultrasonic wave of also available acetone and other organic solvent.
2.3 alkaline etch
The purpose of alkalescence etch is to remove Mg alloy surface oxide skin, necessary constantly turning workpieces during etch, and the etch time is wanted strict control, and the process of washing is constantly observed workpiece surface, gets final product when surface corrosion evenly is silver gray.Its processing condition are as follows:
Na
4P
2O
7.10H
2O 40g/L；
Na
2CO
3 3.7g/L；
NaNO
3 5g/L；
NaH
2PO
4.2H
2O 5g/L；
All the other are water.
T (temperature) 50-75 (℃);
T (time) 0.5-5 (min).
Perhaps, following processing condition are adopted in alkaline etch:
H
3PO
4 2～5ml/L；
All the other are water.
40～70 ℃ of temperature;
Handled 0.5～5 minute.
2.4 activation
Adjust Mg alloy surface, perform preparation for pre-zinc-plated.Its prescription is as follows:
HF 30ml/L；
ZnO 20-30g/L；
All the other are water.
T (temperature) 10-35 (℃);
T (time) 0.5-5 (min).
2.5 it is zinc-plated in advance
Pre-zinc coating can prevent that magnesium alloy from corroding in fused salt, improve the bonding force of Al-Mn alloy layer and matrix.Its solution formula is as follows:
ZnSO
4.7H
2O 35.6g/L；
Na
4P
2O
7.10H
2O 134g/L；
C
6H
5Na
3O
7.2H
2O 10g/L；
KF.2H
2O 10g/L；
C
12H
25SO
4Na 0.1g/L；
All the other are water.
Current density 0.1-1A/dm
2
T (temperature) 40-70 (℃);
T (time) 30-90 (min).
As bottom, pre-zinc coating comprises and soaks zinc coating or electro-galvanized layer that thickness is 1-20um at the pre-zinc coating of Mg alloy surface.
If because problem coating in above-mentioned electroplate liquid such as material has the appearance of pin hole, it is zinc-plated to carry out secondary after above-mentioned plating bath is electroplated 5-20 minute, and the galvanized prescription of secondary is as follows:
ZnO 10g/L；
NaOH 120g/L；
Ekem-221A additive 10ml/L;
Ekem-221B additive 4ml/L;
All the other are water.
Current density 0.5-2.5A/dm
2
T (temperature) 10-35 (℃);
T (time) 5-30 (min).
2.6 bright dipping
Zinc coating is bright more smooth after the bright dipping, and remained on surface alkali lye also is removed, and provides good bottom for electroplating the Al-Mn alloy, and light-emitting solution adopts following prescription:
HNO
3 3ml/100ml；
HCl 1ml/100ml；
All the other are water.
T (temperature) 10-35 (℃);
T (time) 5-30 (s).
2.7 Electroplating Aluminum manganese alloy
Electroplating Aluminum adopts AlCl
3+ NaCl+KCl+MnCl
2The inorganic fused salt system, AlCl
3Purify by the distillation condensation method before use, before NaCl, KCl use 400 ℃ dry 4 hours down, MnCl
2By MnCl
2.4H
2O obtains after the dehydration in 2 hours of 250 ℃ of dryings.By weight percentage, the composition of inorganic fused salt system is: Aluminum chloride anhydrous 65～90%; Sodium-chlor, Repone K or the mixture of the two 5～30%; Manganese chloride anhydrous accounts for 0.5～5%.After fused salt melts, can in melting salt, feed exsiccant HCl gas and remove moisture and adopt low current density that methods such as fused salt preelectrolysis are purified fused salt.
In the Electroplating Aluminum process, service temperature is 120～250 ℃, and electroplating time is 5～180 minutes, current density 0.5～10A/dm
2, the alumal thickness of coating of acquisition is 5-60um.
Can directly in atmosphere, carry out in the electroplating process, also can adopt rare gas element to protect to prevent the plating bath volatilization.In the electroplating process, can adopt fused salt to stir to improve rate of deposition and to improve quality of coating.
Plating tank can adopt glass, quartz, poly-tetrafluoro and lead etc. that fused salt is chemically inert material and make.
Compared with prior art, the present invention has following significant advantage:
1. coating is evenly bright, has excellent decoration;
2. binding force of cladding material is good, with substrate combinating strength up to more than the 50MPa;
3. the corrosion resisting property of coating is superior, and solidity to corrosion is than all high in the common metal coating of Mg alloy surface preparation;
4. alloy layer presents high rigidity, has improved the wear resistance of magnesium alloy greatly;
5. have in the whole process of preparation that equipment is cheap, raw material is easy to get, industrial practicability characteristics such as flow process is simple, simple operation and environmental friendliness.
Embodiment:
Below in conjunction with embodiment the present invention is described further.
Embodiment 1
1. material is prepared: after the AZ31B magnesium alloy cutting polishing, use the ultrasonic cleaning oil removing in acetone soln.
2. etch: Na
4P
2O
7.10H
2O 40g/L, Na
2CO
33.7g/L, NaNO
35g/L, NaH
2PO
4.2H
2O 5g/L, all the other are water.50～70 ℃ of temperature were handled 0.5～5 minute, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute.
3. activation: HF 30ml/L, ZnO 20g/L, all the other are water.10～35 ℃ of temperature were handled 0.5～5 minute, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute.
4. electro-galvanizing: ZnSO
4.7H
2O 35.6g/L, Na
4P
2O
7.10H
2O 134g/L, C
6H
5Na
3O
7.2H
2O 10g/L, KF.2H
2O 10g/L, sodium lauryl sulphate 0.1g/L, all the other are water.PH=8.5～10.0,40～70 ℃ of temperature, cathode current density 0.2～0.5A/dm
2, the time is 50 minutes, cleans 1～2 minute with tap water immediately after the taking-up, uses washed with de-ionized water again 1～2 minute, the present embodiment zinc coating thickness is about 6～8um.
5. Electroplating Aluminum manganese alloy: by weight percentage, AlCl
377%, NaCl 11%, and KCl 11%, MnCl
21% fully is melted into liquid fused salt, cathode current density 4A/dm in 170 ℃
2, 30 minutes time, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute, dry up at last.
The alumal coating that present embodiment obtains is silvery white in color, and evenly light has excellent decoration.Thickness of coating is about 30um, and manganese content is about 22wt%; Coating and substrate combinating strength are greater than 50MPa, and Vickers' hardness is 424～484HV; In the 3.5wt% sodium chloride solution from corrosion electric current density than matrix magnesium alloy 3～4 orders of magnitude that descend, soak that coating does not have breakage after 60 days.
Embodiment 2
1. material is prepared: after the AZ31B magnesium alloy cutting polishing, use the ultrasonic cleaning oil removing in acetone soln.
2. etch: Na
4P
2O
7.10H
2O 40g/L, Na
2CO
33.7g/L, NaNO
35g/L, NaH
2PO
4.2H
2O 5g/L, all the other are water.50～70 ℃ of temperature were handled 0.5～5 minute, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute.
3. activation: HF 30ml/L, ZnO 20g/L, all the other are water.10～35 ℃ of temperature were handled 0.5～5 minute, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute.
4. electro-galvanizing: ZnSO
4.7H
2O 35.6g/L, Na
4P
2O
7.10H
2O 134g/L, C
6H
5Na
3O
7.2H
2O 10g/L, KF.2H
2O 10g/L, sodium lauryl sulphate 0.1g/L, all the other are water.PH=8.5～10.0,40～70 ℃ of temperature, cathode current density 0.2～0.5A/dm
2, the time is 50 minutes, cleans 1～2 minute with tap water immediately after the taking-up, uses washed with de-ionized water again 1～2 minute, the present embodiment zinc coating thickness is about 6～8um.
5. Electroplating Aluminum manganese alloy: by weight percentage, AlCl
376%, NaCl 11%, and KCl 11%, MnCl
22% fully is melted into liquid fused salt, cathode current density 4A/dm in 170 ℃
2, 30 minutes time, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute, dry up at last.
The alumal coating that present embodiment obtains is silvery white in color, and evenly light has excellent decoration.Thickness of coating is about 30um, and manganese content is about 30wt%; Coating and substrate combinating strength are greater than 50MPa, and Vickers' hardness is 424～484HV; In the 3.5wt% sodium chloride solution from corrosion electric current density than matrix magnesium alloy 3～4 orders of magnitude that descend, soak that coating does not have breakage after 60 days.
Embodiment 3
1. material is prepared: after the AZ31B magnesium alloy cutting polishing, use the ultrasonic cleaning oil removing in acetone soln.
2. etch: Na
4P
2O
7.10H
2O 40g/L, Na
2CO
33.7g/L, NaNO
35g/L, NaH
2PO
4.2H
2O 5g/L, all the other are water.50～70 ℃ of temperature were handled 0.5～5 minute, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute.
3. activation: HF 30ml/L, ZnO 20g/L, all the other are water.10～35 ℃ of temperature were handled 0.5～5 minute, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute.
4. electro-galvanizing: ZnSO
4.7H
2O 35.6g/L, Na
4P
2O
7.10H
2O 134g/L, C
6H
5Na
3O
7.2H
2O 10g/L, KF.2H
2O 10g/L, sodium lauryl sulphate 0.1g/L, all the other are water.PH=8.5～10.0,40～70 ℃ of temperature, cathode current density 0.2～0.5A/dm
2, the time is 50 minutes, cleans 1～2 minute with tap water immediately after the taking-up, uses washed with de-ionized water again 1～2 minute, the present embodiment zinc coating thickness is about 6～8um.
5. bright dipping: HNO
330ml/L, HCl 10ml/L, all the other are water.16～35 ℃ of temperature were handled 5～30 seconds, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute.
6. Electroplating Aluminum manganese alloy: by weight percentage, AlCl
376%, NaCl 11%, and KCl 11%, MnCl
22% fully is melted into liquid fused salt, cathode current density 4A/dm in 210 ℃
2, 30 minutes time, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute, dry up at last.
The alumal coating that present embodiment obtains is silvery white in color, and evenly light has excellent decoration.Thickness of coating is about 30um, and manganese content is about 33wt%; Coating and substrate combinating strength are greater than 50MPa, and Vickers' hardness is 424～484HV; In the 3.5wt% sodium chloride solution from corrosion electric current density than matrix magnesium alloy 3～4 orders of magnitude that descend, soak that coating does not have breakage after 60 days.
Embodiment 4
1. material is prepared: after the AZ91D magnesium alloy cutting polishing, use the ultrasonic cleaning oil removing in acetone soln.
2. etch: H
3PO
42～5ml/L, all the other are water.40～70 ℃ of temperature were handled 0.5～5 minute, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute.
3. electro-galvanizing: ZnSO
4.7H
2O 36g/L, Na
4P
2O
7.10H
2O 134g/L, C
6H
5Na
3O
7.2H
2O 10g/L, KF.2H
2O 10g/L, sodium lauryl sulphate 0.1g/L, all the other are water.PH=9.0～10.0,40～70 ℃ of temperature, cathode current density 0.1～0.5A/dm
2, 60 minutes time, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute, the present embodiment zinc coating thickness is about 6～8um.
4. bright dipping: HNO
330ml/L, HCl 10ml/L, all the other are water.16～35 ℃ of temperature were handled 5～30 seconds, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute.
5. Electroplating Aluminum manganese alloy: by weight percentage, AlCl
376.5%, NaCl 11%, and KCl 11%, MnCl
21.5% fully is melted into liquid fused salt, cathode current density 4A/dm in 170 ℃
2, 30 minutes time, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute, dry up at last.
The alumal coating that present embodiment obtains is silvery white in color, and evenly light has excellent decoration.Thickness of coating is about 30um, and manganese content is about 28wt%; Coating and substrate combinating strength are greater than 50MPa, and Vickers' hardness is 424～484HV; In the 3.5wt% sodium chloride solution from corrosion electric current density than matrix magnesium alloy 3～4 orders of magnitude that descend, soak that coating does not have breakage after 60 days.
Embodiment 5
1. material is prepared: after the AZ91D magnesium alloy cutting polishing, use the ultrasonic cleaning oil removing in acetone soln.
2. etch: Na
4P
2O
7.10H
2O 40g/L, Na
2CO
33.7g/L, NaNO
35g/L, NaH
2PO
4.2H
2O 5g/L, all the other are water.50～70 ℃ of temperature were handled 0.5～5 minute, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute.
3. activation: HF 30ml/L, ZnO 20g/L, all the other are water.10～35 ℃ of temperature were handled 0.5～5 minute, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute.
4. electro-galvanizing: ZnSO
4.7H
2O 35.6g/L, Na
4P
2O
7.10H
2O 134g/L, C
6H
5Na
3O
7.2H
2O 10g/L, KF.2H
2O 10g/L, sodium lauryl sulphate 0.1g/L, all the other are water.PH=8.5～10.0,40～70 ℃ of temperature, cathode current density 0.2～0.5A/dm
2, the time is 50 minutes, cleans 1～2 minute with tap water immediately after the taking-up, uses washed with de-ionized water again 1～2 minute, the present embodiment zinc coating thickness is about 6～8um.
5. bright dipping: HNO
330ml/L, HCl 10ml/L, all the other are water.16～35 ℃ of temperature were handled 5～30 seconds, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute.
6. Electroplating Aluminum manganese alloy: by weight percentage, AlCl
376.5%, NaCl 11%, and KCl 11%, MnCl
21.5% fully is melted into liquid fused salt, cathode current density 4A/dm in 170 ℃
2, 30 minutes time, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute, dry up at last.
The alumal coating that present embodiment obtains is silvery white in color, and evenly light has excellent decoration.Thickness of coating is about 30um, and manganese content is about 28wt%; Coating and substrate combinating strength are greater than 50MPa, and Vickers' hardness is 424～484HV; In the 3.5wt% sodium chloride solution from corrosion electric current density than matrix magnesium alloy 3～4 orders of magnitude that descend, soak that coating does not have breakage after 60 days.
Embodiment 6
1. material is prepared: after the AZ91D magnesium alloy cutting polishing, use the ultrasonic cleaning oil removing in acetone soln.
2. etch: Na
4P
2O
7.10H
2O 40g/L, Na
2CO
33.7g/L, NaNO
35g/L, NaH
2PO
4.2H
2O 5g/L, all the other are water.50～70 ℃ of temperature were handled 0.5～5 minute, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute.
3. activation: HF 30ml/L, ZnO 20g/L, all the other are water.10～35 ℃ of temperature were handled 0.5～5 minute, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute.
4. electro-galvanizing: carry out in two steps (1) zinc-plated in advance: ZnSO
4.7H
2O 36g/L, Na
4P
2O
7.10H
2O 134g/L, C
6H
5Na
3O
7.2H
2O 10g/L, KF.2H
2O 10g/L, sodium lauryl sulphate 0.1g/L, all the other are water.PH=9.0～10.0,40～70 ℃ of temperature, cathode current density 0.1～0.5A/dm
2, the time is 5～20 minutes, cleans 1～2 minute with tap water immediately after the taking-up, uses washed with de-ionized water again 1～2 minute.(2) bright galvanization: ZnO 10g/L, NaOH 120g/L, Ekem-221A additive 10ml/L, Ekem-221B additive 4ml/L, all the other are water.10～35 ℃ of temperature, cathode current density 0.5～2.5A/dm
2, the time is 10～30 minutes, cleans 1～2 minute with tap water immediately after the taking-up, uses washed with de-ionized water again 1～2 minute.In the present embodiment, zinc coating thickness is about 5～20um.
5. bright dipping: HNO
330ml/L, HCl 10ml/L, all the other are water.16～35 ℃ of temperature were handled 5～30 seconds, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute.
6. Electroplating Aluminum manganese alloy: by weight percentage, AlCl
376.5%, NaCl 11%, and KCl 11%, MnCl
21.5% fully is melted into liquid fused salt, cathode current density 4A/dm in 170 ℃
2, 30 minutes time, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute, dry up at last.
The alumal coating that present embodiment obtains is silvery white in color, and evenly light has excellent decoration.Thickness of coating is about 30um, and manganese content is about 28wt%; Coating and substrate combinating strength are greater than 50MPa, and Vickers' hardness is 424～484HV; In the 3.5wt% sodium chloride solution from corrosion electric current density than matrix magnesium alloy 3～4 orders of magnitude that descend, soak that coating does not have breakage after 60 days.
Embodiment 7
1. material is prepared: after the AM60 magnesium alloy cutting polishing, use the ultrasonic cleaning oil removing in acetone soln.
2. etch: Na
4P
2O
7.10H
2O 40g/L, Na
2CO
33.7g/L, NaNO
35g/L, NaH
2PO
4.2H
2O 5g/L, all the other are water.50～70 ℃ of temperature were handled 0.5～5 minute, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute.
3. activation: HF 30ml/L, ZnO 20g/L, all the other are water.10～35 ℃ of temperature were handled 0.5～5 minute, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute.
4. electro-galvanizing: carry out in two steps (1) zinc-plated in advance: ZnSO
4.7H
2O 36g/L, Na
4P
2O
7.10H
2O 134g/L, C
6H
5Na
3O
7.2H
2O 10g/L, KF.2H
2O 10g/L, sodium lauryl sulphate 0.1g/L, all the other are water.PH=9.0～10.0,40～70 ℃ of temperature, cathode current density 0.1～0.5A/dm
2, the time is 5～20 minutes, cleans 1～2 minute with tap water immediately after the taking-up, uses washed with de-ionized water again 1～2 minute.(2) bright galvanization: ZnO 10g/L, NaOH 120g/L, Ekem-221A additive 10ml/L, Ekem-221B additive 4ml/L, all the other are water.10～35 ℃ of temperature, cathode current density 0.5～2.5A/dm
2, the time is 10～30 minutes, cleans 1～2 minute with tap water immediately after the taking-up, uses washed with de-ionized water again 1～2 minute.In the present embodiment, zinc coating thickness is about 5～20um.
5. bright dipping: HNO
330ml/L, HCl 10ml/L, all the other are water.16～35 ℃ of temperature were handled 5～30 seconds, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute.
6. Electroplating Aluminum manganese alloy: by weight percentage, AlCl
376.5%, NaCl 11%, and KCl 11%, MnCl
21.5% fully is melted into liquid fused salt, cathode current density 4A/dm in 170 ℃
2, 30 minutes time, cleaned 1～2 minute with tap water immediately after the taking-up, used washed with de-ionized water again 1～2 minute, dry up at last.
The alumal coating that present embodiment obtains is silvery white in color, and evenly light has excellent decoration.Thickness of coating is about 30um, and manganese content is about 28wt%; Coating and substrate combinating strength are greater than 50MPa, and Vickers' hardness is 424～484HV; In the 3.5wt% sodium chloride solution from corrosion electric current density than matrix magnesium alloy 3～4 orders of magnitude that descend, soak that coating does not have breakage after 60 days.
Claims (7)
1. the anti-corrosion method of a Mg alloy surface is characterized in that: through magnesium alloy workpiece Electroplating Aluminum manganese alloy in inorganic fused salt of pre-treatment.
2. magnesium alloy fused salt Electroplating Aluminum manganese alloy according to claim 1 pre-treatment is characterized in that: as bottom, pre-zinc coating comprises and soaks zinc coating or electro-galvanized layer that thickness is 1-20um at the pre-zinc coating of Mg alloy surface.
3. the method for magnesium alloy plating alumal according to claim 1 is characterized in that: the Electroplating Aluminum manganese alloy adopts inorganic molten molten salt system, and by weight percentage, the composition of inorganic fused salt system is: Aluminum chloride anhydrous 65～90%; Sodium-chlor, Repone K or the mixture of the two 5～30%; Manganese chloride anhydrous 0.5～5%.
4. the method for magnesium alloy plating alumal according to claim 3, it is characterized in that: in the Electroplating Aluminum manganese alloy process, service temperature is 120～250 ℃, plating mode comprises direct current electrode position or pulse plating, electroplating time is 5～180 minutes, current density 0.5～10A/dm2, the alumal thickness of coating of acquisition is 5-60um.
5. the method for Mg alloy surface Electroplating Aluminum manganese alloy according to claim 3 is characterized in that: Aluminum chloride anhydrous is purified by the method for distillation condensation, feeds dry HCl gas and remove moisture in fused salt electrolysis liquid.
6. the method for magnesium alloy plating alumal according to claim 3 is characterized in that: in the electroplating process, directly carry out in atmosphere; Perhaps, adopt rare gas element to protect to prevent the plating bath volatilization; In the electroplating process, adopt fused salt to stir to improve rate of deposition and to improve quality of coating.
7. the method for magnesium alloy plating alumal according to claim 3 is characterized in that: plating tank adopts glass, quartz, poly-tetrafluoro or lead etc. that fused salt is chemically inert material and makes.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101914791A (en) * | 2010-09-15 | 2010-12-15 | 武汉钢铁(集团)公司 | Method for electroplating corrosion resistant aluminum-manganese alloy layer |
| CN102477537A (en) * | 2010-11-26 | 2012-05-30 | 鸿富锦精密工业（深圳）有限公司 | Casing and preparation method thereof |
| CN103147101A (en) * | 2013-02-19 | 2013-06-12 | 上海交通大学 | Magnesium alloy surface diffusion coating preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914791A (en) * | 2010-09-15 | 2010-12-15 | 武汉钢铁(集团)公司 | Method for electroplating corrosion resistant aluminum-manganese alloy layer |
| CN102477537A (en) * | 2010-11-26 | 2012-05-30 | 鸿富锦精密工业（深圳）有限公司 | Casing and preparation method thereof |
| CN102477537B (en) * | 2010-11-26 | 2014-08-20 | 鸿富锦精密工业（深圳）有限公司 | Casing and preparation method thereof |
| CN103147101A (en) * | 2013-02-19 | 2013-06-12 | 上海交通大学 | Magnesium alloy surface diffusion coating preparation method |
| CN103147101B (en) * | 2013-02-19 | 2015-04-22 | 上海交通大学 | Magnesium alloy surface diffusion coating preparation method |
| EP2971262A4 (en) * | 2013-03-14 | 2016-12-21 | Xtalic Corp | Electrodeposition in ionic liquid electrolytes |
| US10190227B2 (en) | 2013-03-14 | 2019-01-29 | Xtalic Corporation | Articles comprising an electrodeposited aluminum alloys |
| WO2014150508A1 (en) | 2013-03-15 | 2014-09-25 | United Technologies Corporation | Sacrificial coating and procedure for electroplating aluminum on aluminum alloys |
| EP2971269A4 (en) * | 2013-03-15 | 2016-11-09 | United Technologies Corp | Sacrificial coating and procedure for electroplating aluminum on aluminum alloys |
| US11401619B2 (en) | 2013-03-15 | 2022-08-02 | United Technologies Corporation | Sacrificial coating and procedure for electroplating aluminum on aluminum alloys |
| CN103266291B (en) * | 2013-05-15 | 2016-04-13 | 新疆大学 | A kind of hot dip aluminum plating Mn series alloy layer method |
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