CN107955961B - A kind of preparation method of Mg alloy surface conduction corrosion-inhibiting coating - Google Patents
A kind of preparation method of Mg alloy surface conduction corrosion-inhibiting coating Download PDFInfo
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- CN107955961B CN107955961B CN201711267956.8A CN201711267956A CN107955961B CN 107955961 B CN107955961 B CN 107955961B CN 201711267956 A CN201711267956 A CN 201711267956A CN 107955961 B CN107955961 B CN 107955961B
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- magnesium alloy
- oxidation
- corrosion
- preparation
- differential arc
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/30—Anodisation of magnesium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
Abstract
The invention discloses a kind of preparation methods of Mg alloy surface conduction corrosion-inhibiting coating, belong to conductive coating field.Preparation method includes the following steps: electric conductive oxidation processing is carried out in chromatedsolution after the processing of magnesium alloy materials premenstruum (premenstrua); the non-differential arc oxidization surface of part is protected using polytetrafluoroethylene (PTFE) tooling, then each part is subjected to micro-arc oxidation treatment, disassembling fixture in sodium silicate solution.Electric conductive oxidation and differential arc oxidization technique are combined, realizes the magnesium alloy materials surface not only function of anti-corrosion but also conduction.The beneficial effects of the invention are as follows while not reducing the electric conductivity between magnesium alloy component, its antiseptic property is improved.
Description
Technical field
The invention belongs to conductive coating fields, are related to a kind of preparation method of Mg alloy surface conduction corrosion-inhibiting coating.Specifically
It is related to a kind of electric conductive oxidation and differential arc oxidation combined technology, realizes material surface not only anti-corrosion conductive function again.
Background technique
The bottleneck of limitation magnesium alloy application is that its very poor corrosion resisting property, and magnesium alloy has very high chemistry and electrification
Activity is learned, especially is highly susceptible to corrode in moist and coastal area in an atmosphere.So marine environment is all the time
Magnesium alloy uses forbidden zone.But as on-board equipment lightweight demand is more more and more urgent, have to using magnesium alloy materials,
Therefore magnesium alloy anti-corrosion becomes and must solve the problems, such as.
The common surface treatment method of magnesium alloy has chemical oxidation, anodic oxidation, the coat of metal, physical vapor heavy at present
Product, ion implanting, laser surface alloying etc..These surface treatment methods all have some disadvantages: the film that chemical oxidation generates
Layer is relatively thin, and matter is crisp porous, and wearability, corrosion resistance are bad, generally as decoration and intervening guard layer.The chemistry of magnesium alloy at present
Oxidation is main or with chromic anhydride acid or bichromate chemistry of aqueous solution processing (referred to as chromaking processing) as main component, chromate
In Cr6+With toxicity, environmental pollution is serious, and discharge is limited by environmental regulation, and treatment cost of waste liquor is high；Anodic oxygen
It is larger to change film layer hole, is unevenly distributed, is generally also only used as coating bottom；Coat of metal complex process, bath stability is poor,
Film layer is poor with basal body binding force；Physical vapour deposition (PVD) is at high cost with ion implanting；Laser surface alloying processing can generate size
Variation, need additional mechanical to process, cost is also higher, is still in infancy at home at present.
Differential arc oxidation is directly by parent metal oxidation and sinter at oxide ceramics, and film layer and substrate combinating strength are high, film layer
Thickness, which can according to need, to be controlled, and hardness and corrosion resistance are good, can be the ideal table of magnesium alloy by electrophoresis colour
Surface treatment method.But magnesium alloy differential arc oxidation oxidation film layer is made of the oxide ceramics based on MgO, this layer of ceramic layer has good
Good insulating properties, and under normal conditions, electronics are required with electromagnetic shielding performance, to keep magnesium alloy shell class part
Electromagnetic wave shielding, must be requested that between the part mutually assembled keep conduct.Therefore only with differential arc oxidization technique, only
It is able to achieve its antiseptic property, now there is an urgent need to a kind of not only anti-corrosion but also the technological approaches of conduction.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of preparation methods of Mg alloy surface conduction corrosion-inhibiting coating.
There is good corrosion resistance in order to make electronics shell not only, but also keep electromagnetic screen possessed by metal component
Function is covered, the present invention reaches above-mentioned purpose by the scheme that electric conductive oxidation is combined with differential arc oxidation, since then each
On the face being bonded to each other when component assembly, conductive oxide layer plays certain protective action, but do not influence each part base solid it
Between mutual conduction, to keep whole function solenoid, it is corrosion resistant that the other surfaces of part have differential arc oxidation layer to play the role of.Tool
Body way is first to carry out electric conductive oxidation to each part, then the face that each part and other parts are bonded to each other in assembly is carried out
Protection, then do micro-arc oxidation treatment.
To reach purpose described above, the invention provides the following technical scheme: a kind of Mg alloy surface conduction corrosion-inhibiting coating
Preparation method, comprising the following steps:
(1) electric conductive oxidation processing electric conductive oxidation: is carried out to magnesium alloy parts matrix surface；
(2) it protects: being protected the non-differential arc oxidization surface of part using polytetrafluoroethylene (PTFE) tooling；
(3) differential arc oxidation: the part after protection is subjected to micro-arc oxidation treatment, conductive oxygen when processing, other than protection face
Changing layer can be electrically shocked and wears, under the action of plasma arc conductive oxide layer substance and newly-generated magnesia experience molten sintering,
Cooled and solidified forms differential arc oxidation layer；
(4) disassembling fixture: after micro-arc oxidation treatment, magnesium alloy parts is taken out and are cleaned, and disassembling fixture.
Further, the processing of electric conductive oxidation described in step (1) carries out in chromatedsolution, and the solution formula is CrO3
3-4g/L、Na2Cr2O7 1-3g/L, NaF0.5g/L, corrosion inhibiter 0.5g/L under room temperature, handle 5-10min.
Further, before step (2) described assembly tooling, layer of silica gel is coated in non-differential arc oxidization surface, to reach sealing
Effect.
Further, micro-arc oxidation process described in step (3) specifically: microarc oxidation solution is the sodium metasilicate water of 20g/L
Solution, differential arc oxidation frequency 400Hz, duty ratio 50%, average current density 3A/dm2, 470 ± 5V of final voltage, time
47min。
Further, step (1) is described is handled before further including before carrying out electric conductive oxidation to magnesium alloy parts matrix surface
Step, the pre-treatment include carrying out alkali cleaning, washing, acid leaching process to magnesium alloy parts.
Further, the alkali washing process is by magnesium alloy parts in Na2CO3 20g/L、Na3PO4 18 g/L、Na2SiO3
In the solution of 10g/L and KOH 1g/L, Yu Wendu 50-60 DEG C, alkali cleaning 5-8min.
Further, the acid leaching process is by magnesium alloy parts in HNO3In solution, 2-3min is handled under room temperature.
The beneficial effects of the present invention are:
The electric conductive oxidation and differential arc oxidization technique that the present invention uses, can be in the same of the electric conductivity between not reducing magnesium alloy component
When, improve its antiseptic property；
After magnesium alloy materials electric conductive oxidation, material surface forms one layer of chemical composition coating, and through resistance test, this tunic is to magnesium
The electric conductivity of alloy material has little effect；
Corrosion-resistant survey is carried out using salt spray test (GJB150.11A-2009) in military hardware laboratory environment test method
Examination.After salt spray test, specimen surface is unchanged, and protecting effect is good.According to GJB150.9A-2009 military hardware laboratory ring
Damp heat test standard is tested in the test method of border, and test result meets properties of product requirement；
Currently, differential arc oxidation scheme is applied on various types of equipments again after magnesium alloy electric conductive oxidation.
Detailed description of the invention
Fig. 1 is process flow chart of the invention；
Fig. 2 is that tooling of the invention protects installation diagram；
Wherein, 1. magnesium alloy parts, 2. layer of silica gel, 3. polytetrafluoroethylene (PTFE) toolings, 4. insulated screws, 5. insulated bolts, 6.
By protection face.
Specific embodiment
Below by specific embodiment, the invention will be further described, so that those skilled in the art can be better
Understand the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
Embodiment 1
The AZ31 magnesium alloy for choosing 50 × 100 × 5mm size, it is stand-by after soaked in absolute ethyl alcohol, ultrasonic cleaning, it uses
Surface is considered and be embedded in the cold working metal that alkali cleaning, washing, acid leaching process remove the oxide of metal surface and loosely adhere to be worth doing
Dirt, soda-wash solution formula are as follows: Na2CO3(20g/L), Na3PO4(18 g/L), Na2SiO3(10g/L), KOH(1g/L), temperature
50 DEG C of degree, alkali cleaning time 6min；Acid dip solution is HNO3(70g/L) handles 2min under room temperature.
It carries out aoxidizing conductive technique, solution formula in chromatedsolution after to sample pretreating are as follows: CrO3(4g/L),
Na2Cr2O7(3g/L), NaF(0.5g/L), corrosion inhibiter (0.5g/L), take out magnesium alloy parts after handling 10min under room temperature, dry
For use.
As shown in Fig. 2, to the table for needing to be formed conductive contact surfaces on magnesium alloy parts 1 with the mutual assembly connection of other parts
Face 6 is protected, and protected mode is when being made into corresponding tooling 3, tooling and component assembly with polytetrafluoroethylene material, thereon
There is a face to be completely coincident with face to be protected is needed, before assembly tooling, coats silica gel 2 on needing face to be protected to reach
The effect of sealing.There are threaded hole or through-hole, tooling on part on the face contacted with other component assemblies under normal circumstances
It is linked and packed with magnesium alloy parts by nylon (or other insulating materials) screw 4 or bolt 5, guarantee needs protection face to cut with tooling
It closes close.
The part assembled is microarc oxidation equipment provided using bipolarity T-MAO-B200 type, is configured in sodium metasilicate and pure water
Electrolyte in (sodium silicate silicate: 20g/L) processed, micro-arc oxidation process frequency 400Hz, duty ratio 50%, average electricity
Current density 3A/dm2, 470 ± 5V of final voltage, preparation 47min.After completing micro-arc oxidation process processing, part is taken out and is cleaned,
Disassembling fixture, clears up the silica gel in protection face, and drying material carries out subsequent applications.
Retain conductive oxide layer on the face that magnesium alloy parts need mutual assembly connection by above-mentioned processing, so that different
It keeps conducting between matrix after component assembly, in addition conductive oxide layer has certain anti-corrosive properties again.The rest part of part
There is differential arc oxidation layer, the corrosion-resistant protection of the entire product after guaranteeing assembly.
2 performance test of embodiment
After the AZ31 magnesium alloy materials electric conductive oxidation of embodiment 1, material surface forms one layer of chemical composition coating, surveys through resistance
Examination, this tunic have little effect the electric conductivity of magnesium alloy materials.
Corrosion-resistant survey is carried out using salt spray test in military hardware laboratory environment test method (GJB150.11A-2009)
Examination.After salt spray test, specimen surface is unchanged, and protecting effect is good.According to damp heat test mark in GJB150.9A-2009 method
Standard is tested, and test result meets properties of product requirement.
It should be noted that the preparation method of conduction corrosion-inhibiting coating disclosed by the invention, is equally applicable to other trades mark
Magnesium alloy materials, such as AZ91 series, AM series, AS series and AE series.
Embodiment described above is only to absolutely prove preferred embodiment that is of the invention and being lifted, protection model of the invention
It encloses without being limited thereto.Those skilled in the art's made equivalent substitute or transformation on the basis of the present invention, in the present invention
Protection scope within.Protection scope of the present invention is subject to claims.
Claims (4)
1. a kind of preparation method of Mg alloy surface conduction corrosion-inhibiting coating, it is characterised in that the following steps are included:
(1) electric conductive oxidation: electric conductive oxidation processing is carried out to magnesium alloy parts matrix surface, the electric conductive oxidation is handled in chromic acid
It is carried out in salting liquid, solution formula CrO3 3-4g/L、Na2Cr2O71-3g/L, NaF0.5g/L, corrosion inhibiter 0.5g/L, often
Under temperature, 5-10min is handled；
(2) protect: the non-differential arc oxidization surface of part is protected using polytetrafluoroethylene (PTFE) tooling, the assembly tooling it
Before, layer of silica gel is coated in non-differential arc oxidization surface；
(3) part after protection differential arc oxidation: is subjected to micro-arc oxidation treatment, the micro-arc oxidation process are as follows: differential arc oxidation is molten
Liquid is the sodium silicate aqueous solution of 20g/L, differential arc oxidation frequency 400Hz, duty ratio 50%, average current density 3A/dm2, terminate
470 ± 5V of voltage, time 47min；
(4) disassembling fixture: after micro-arc oxidation treatment, magnesium alloy parts is taken out and are cleaned, and disassembling fixture.
2. the preparation method of Mg alloy surface conduction corrosion-inhibiting coating according to claim 1, it is characterised in that step (1) institute
Stating before carrying out electric conductive oxidation to magnesium alloy parts matrix surface further includes pre-treatment step, and the pre-treatment includes closing to magnesium
Metal parts carry out alkali cleaning, washing, acid leaching process.
3. the preparation method of Mg alloy surface conduction corrosion-inhibiting coating according to claim 2, it is characterised in that the alkali cleaning
Technique are as follows: magnesium alloy parts are in Na2CO3 20g/L、Na3PO4 18g/L、Na2SiO3In the solution of 10g/L and KOH1g/L, in
50-60 DEG C of temperature, alkali cleaning 5-8min.
4. the preparation method of Mg alloy surface conduction corrosion-inhibiting coating according to claim 2, it is characterised in that the acidleach
Technique are as follows: magnesium alloy parts are in HNO3In solution, 2-3min is handled under room temperature.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110983415B (en) * | 2019-12-30 | 2021-12-07 | 郑州轻研合金科技有限公司 | Magnesium-lithium alloy surface composite oxidation treatment method |
| CN112064037A (en) * | 2020-10-13 | 2020-12-11 | 贵州电网有限责任公司 | Preparation method of corrosion-resistant magnesium alloy sacrificial anode |
| CN112195457A (en) * | 2020-10-13 | 2021-01-08 | 中国电子科技集团公司第二十研究所 | Magnesium-lithium alloy surface conductive anticorrosive coating and preparation method thereof |
| CN113755927A (en) * | 2021-09-29 | 2021-12-07 | 上海交通大学 | Magnesium neodymium alloy part and composite oxidation treatment method thereof |
| CN115522245A (en) * | 2022-08-12 | 2022-12-27 | 中国航空无线电电子研究所 | Corrosion-resistant magnesium alloy airborne avionics chassis |
| CN115491666A (en) * | 2022-09-07 | 2022-12-20 | 深圳市飞航精工科技有限公司 | Conductive oxidation process for magnesium alloy high-salt-spray test |
| CN117684232A (en) * | 2024-02-02 | 2024-03-12 | 山西银光华盛镁业股份有限公司 | Local conductive oxidation treatment method based on magnesium alloy micro-arc oxidation |
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