CN105803457A - Preparation method of magnesium alloy surface micro-arc oxidation and chemical copper plating composite coating - Google Patents
Preparation method of magnesium alloy surface micro-arc oxidation and chemical copper plating composite coating Download PDFInfo
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- CN105803457A CN105803457A CN201410844471.0A CN201410844471A CN105803457A CN 105803457 A CN105803457 A CN 105803457A CN 201410844471 A CN201410844471 A CN 201410844471A CN 105803457 A CN105803457 A CN 105803457A
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- magnesium alloy
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Abstract
The invention provides a preparation method of a magnesium alloy surface micro-arc oxidation and chemical copper plating composite coating. The method includes: firstly conducting surface micro-arc oxidation on a magnesium alloy substrate to form a micro-arc oxidation ceramic film layer; then conducting chemical copper plating treatment on the substrate subjected to micro-arc oxidation so as to form a magnesium alloy micro-arc oxidation and chemical copper plating composite coating on the magnesium alloy surface. The micro-arc oxidation and chemical copper plating composite coating prepared by the method provided by the invention has far less defects than traditional micro-arc oxidation film layers, the corrosion resistance is improved, so that magnesium alloy can be considered as an auto-material to reduce automobile fuel consumption and save energy. The prepared coating also has conductive ability, and can expand the application of magnesium alloy in fields with conductive requirements.
Description
Technical field
The preparation method that the present invention relates to a kind of differential arc oxidation-chemical plating composite coating, the preparation method of especially a kind of magnesium alloy surface micro-arc oxidation-electroless copper composite coating.
Background technology
Magnesium alloy is to add other elementary composition alloys with magnesium for base metal.Main alloy element has aluminum, zinc, manganese, cerium, thorium and a small amount of zirconium or cadmium etc..It is mainly used in the industrial departments such as Aeronautics and Astronautics, transport, chemical industry, rocket.Being the lightest metal in practical metal, the proportion of magnesium is about the 2/3 of aluminum, is the 1/4 of ferrum.According to relevant research, what automobile was fuel used 60% is consumed in automotive dead weight, and automotive dead weight often alleviates 10%, and its fuel efficiency can improve more than 5%；Automotive dead weight often reduces 100kg, and per 100 km oil consumption can reduce about 0.7L, often saves 1L fuel and can reduce CO2 discharge 2.5g, and annual emissions reduces more than 30%.So it is very big on the impact of environment and the energy to alleviate vehicle weight, the light weight chemical conversion inexorable trend of automobile.
The feature of magnesium alloy is: density is little, is about about 1.8g/cm3, and specific strength is high, and elastic modelling quantity is big, and shock absorbing is good, it is possible to bearing the shock loading also bigger than aluminium alloy, the corrosive nature of resistance to Organic substance and alkali is good；On the other hand, magnesium alloy is poor in the corrosion resistance of sea water, even if minimal amount of corrosivity saline also can make magnesium alloy be subject to more serious corrosion, this feature limits the extensive use of magnesium alloy.Therefore, the change of Mg alloy surface performance is extremely paid close attention to by modern technologies.Differential arc oxidation, it is a kind of can deposit thick layer at the valve metals such as magnesium, aluminum, titanium and alloy surface thereof and the technology of the ultra hard ceramic film of densification, the corrosion resistance of magnesium alloy, abrasion resistance properties etc. can be significantly improved, thus have broad application prospects in fields such as Aeronautics and Astronautics, machinery, electronics, weaving, decorations.But due to micro-arc oxidation process itself, this layer of ceramic film, while growth, can leave substantial amounts of micropore on film surface, so the corrosion resistance of magnesium alloy will be caused very big impact.Simultaneously as this rete is ceramic layer, non-conductive, thus limiting Micro-Arc Oxidized Ceramic Coating not only needing good corrosion resistance but also need it to have the popularization and application in certain electric conductivity field.
In order to improve the corrosion resisting property of magnesium alloy differential arc oxidation ceramic film, and can occupy a tiny space in electric conductivity field, it is possible on magnesium alloy differential arc oxidation ceramic film, carry out chemical plating.Chemical plating is a kind of novel metal surface treatment technology, and this technology is increasingly subject to the concern of people with its simple process, energy-saving and environmental protection.Equally, in barrier propterty, this technology can improve corrosion resistance and the service life of product；In functional, the specific functions such as the wear-resistant conductive performance of workpiece, greasy property can be improved, thus one of important development direction becoming current process for treating surface.And owing to chemical plating coating contains metal material, therefore it has certain electric conductivity.
Summary of the invention
For solving above shortcomings in magnesium alloy materials differential arc oxidization technique, the preparation method that the invention provides a kind of magnesium alloy surface micro-arc oxidation-electroless copper composite coating.
For reaching goal of the invention, the technical solution adopted in the present invention is:
The preparation method of a kind of magnesium alloy surface micro-arc oxidation-electroless copper composite coating, first carries out surface by micro-arc oxidation to magnesium alloy substrate, forms Micro-Arc Oxidized Ceramic Coating；Then the matrix after differential arc oxidation is carried out electroless copper process, thus forming Microarc Oxidation-Electroless Plating of Magnesium Alloy copper composite coating at Mg alloy surface.
Magnesium alloy surface micro-arc oxidation process is:
A. magnesium alloy substrate being carried out pretreatment, basic step includes: sand papering, oil removing, and sodium hydroxide rinses with nitric acid rinsing liquid (3:1), and ultrasound wave deionized water cleans 40min, dry in vacuum environment；
B. sample is arranged on microarc oxidation equipment provided on, sample is immersed in treatment fluid as anode, and the rustless steel container with cooling system is as negative electrode, electrolyte is 15g/L sodium silicate, 4g/L potassium hydroxide, and pattern is constant current mode, electric current is 4A, and preparation time is 10min, and temperature controls at about 25 DEG C；
C. the magnesium alloy differential arc oxidation sample rinsed with deionized water that will prepare, natural drying.
Electroless copper processing procedure is:
A. sensitized treatment: the magnesium alloy substrate ambient temperatare after differential arc oxidation is entered process 30 ~ 120s in sensitizing solution；
B. activation processing: the magnesium alloy substrate ambient temperatare after sensitized treatment is entered process 10 ~ 60s in activating solution；
C. electroless copper: being put in ready chemical plating fluid by the magnesium alloy substrate after sensitization plays and activation processing, adjust its pH to 12 ~ 13, chemical plating temperature is 30 ~ 40 DEG C, and the time is 20 ~ 40min；
D. post processing: the Microarc Oxidation-Electroless Plating of Magnesium Alloy copper composite coating rinsed with deionized water that will prepare, natural drying.
Described sensitizing solution consists of: stannous chloride 10 ~ 15g/L, hydrochloric acid 5 ~ 10ml/L.
Described activating solution consists of: silver nitrate 2 ~ 10g/L, adds proper ammonia and makes solution transparent.
Described chemical plating fluid consists of: copper sulfate 10 ~ 25g/L, sodium hydroxide 8 ~ 15g/L, Nickel dichloride. 1 ~ 4g/L, EDTA20 ~ 35g/L, 2-2 bipyridyl 15 ~ 30g/L, formaldehyde 10 ~ 20ml/L.
The invention have the benefit that the defect of (1) described differential arc oxidation-electroless copper composite coating defect far fewer than tradition differential arc oxidation film layer, improve corrosion resisting property, so that magnesium alloy can be considered as automotive material, to reduce automobile fuel consumption, save the energy；(2) prepared by, coating defines conductive capability, it is possible to expand magnesium alloy in the application having the field that conduction requires；(3) cheaper starting materials, common, technique is simple, cost is low, and course of reaction is easily controlled, and is beneficial to industrialized production.
Accompanying drawing explanation
Fig. 1 is Mg alloy surface pattern: (a) (c) differential arc oxidation film layer；(b) (d) differential arc oxidation-electroless copper composite coating.
Fig. 2 is dynamic potential polarization curve figure.
Detailed description of the invention
Below in conjunction with concrete mode, the present invention is described further, it is clear that described embodiment is only a part of embodiment of the present invention, rather than whole embodiments.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under not making creative work premise, broadly fall into scope.
Embodiment 1:
Material prepares: sensitizing solution: stannous chloride 10g/L, hydrochloric acid 10ml/L；Activating solution: silver nitrate 2g/L；Chemical plating fluid: copper sulfate 10g/L, sodium hydroxide 8g/L, Nickel dichloride. 4g/L, EDTA20g/L, 2-2 bipyridyl 30g/L, formaldehyde 10ml/L；KMB8 magnesium alloy through Microarc Oxidation Surface Treatment.
Magnesium alloy substrate ambient temperatare after differential arc oxidation is entered process 120s in sensitizing solution, then ambient temperatare enters process 10s in activating solution, then by putting in chemical plating fluid through sensitization plays and activation processing magnesium alloy substrate, adjusts its pH to 12, temperature controls at about 30 DEG C, and the time is 40min.
Embodiment 2:
Material prepares: sensitizing solution: stannous chloride 12g/L, hydrochloric acid 7ml/L；Activating solution: silver nitrate 5g/L；Chemical plating fluid: copper sulfate 20g/L, sodium hydroxide 10g/L, Nickel dichloride. 3g/L, EDTA25g/L, 2-2 bipyridyl 20g/L, formaldehyde 15ml/L；KMB8 magnesium alloy through Microarc Oxidation Surface Treatment.
Magnesium alloy substrate ambient temperatare after differential arc oxidation is entered process 80s in sensitizing solution, then ambient temperatare enters process 30s in activating solution, then by putting in chemical plating fluid through sensitization plays and activation processing magnesium alloy substrate, adjusts its pH to 12, temperature controls at about 35 DEG C, and the time is 30min.
Embodiment 3:
Material prepares: sensitizing solution: stannous chloride 14g/L, hydrochloric acid 8ml/L；Activating solution: silver nitrate 8g/L；Chemical plating fluid: copper sulfate 25g/L, sodium hydroxide 13g/L, Nickel dichloride. 2g/L, EDTA30g/L, 2-2 bipyridyl 25g/L, formaldehyde 18ml/L；KMB8 magnesium alloy through Microarc Oxidation Surface Treatment.
Magnesium alloy substrate ambient temperatare after differential arc oxidation is entered process 100s in sensitizing solution, then ambient temperatare enters process 40s in activating solution, then by putting in chemical plating fluid through sensitization plays and activation processing magnesium alloy substrate, adjusts its pH to 13, temperature controls at about 32 DEG C, and the time is 30min.
Embodiment 4:
Material prepares: sensitizing solution: stannous chloride 15g/L, hydrochloric acid 5ml/L；Activating solution: silver nitrate 10g/L；Chemical plating fluid: copper sulfate 25g/L, sodium hydroxide 15g/L, Nickel dichloride. 1g/L, EDTA35g/L, 2-2 bipyridyl 15g/L, formaldehyde 20ml/L；KMB8 magnesium alloy through Microarc Oxidation Surface Treatment.
Magnesium alloy substrate ambient temperatare after differential arc oxidation is entered process 30s in sensitizing solution, then ambient temperatare enters process 60s in activating solution, then by putting in chemical plating fluid through sensitization plays and activation processing magnesium alloy substrate, adjusts its pH to 13, temperature controls at about 40 DEG C, and the time is 20min.
Adopt ISM-6510 type scanning electron microscope (SEM) to measure the surface microscopic topographic of sample, with electrochemical apparatus (Electrochemicalworkstation, CS350), sample is carried out potentiodynamic polarization test.
(1) sem analysis: all can be seen that from the high power of Fig. 1 and low power SEM picture, Mg alloy surface after differential arc oxidation has a lot of micropores, this differential arc oxidation coating is after electroless copper, surface micropore greatly reduces, illustrate that chemical plating plays a significant role for the defect minimizing of differential arc oxidation coating, and then its corrosion resistance can be improved.
(2) electro chemical analysis: from figure 2 it can be seen that the corrosion resistance relatively differential arc oxidation film layer of Microarc Oxidation-Electroless Plating of Magnesium Alloy copper composite coating is greatly improved.
Claims (5)
1. the preparation method of magnesium alloy surface micro-arc oxidation-electroless copper composite coating, it is characterised in that first magnesium alloy substrate carries out surface by micro-arc oxidation, forms Micro-Arc Oxidized Ceramic Coating；Then the matrix after differential arc oxidation is carried out electroless copper process, thus forming Microarc Oxidation-Electroless Plating of Magnesium Alloy copper composite coating at Mg alloy surface.
2. the preparation method of magnesium alloy surface micro-arc oxidation according to claim 1-electroless copper composite coating, it is characterised in that electroless copper processing procedure is:
A. sensitized treatment: under room temperature, the magnesium alloy substrate after differential arc oxidation is put into process 30 ~ 120s in sensitizing solution；
B. activation processing: under room temperature, the magnesium alloy substrate after sensitized treatment is put into process 10 ~ 60s in activating solution；
C. electroless copper: putting in chemical plating fluid by the magnesium alloy substrate after sensitization plays and activation processing, adjust its pH to 12 ~ 13, chemical plating temperature is 30 ~ 40 DEG C, and the time is 20-40min；
D. post processing: the Microarc Oxidation-Electroless Plating of Magnesium Alloy copper composite coating rinsed with deionized water that will prepare, natural drying.
3. electroless copper processing procedure according to claim 2, it is characterised in that described sensitizing solution consists of: stannous chloride 10 ~ 15g/L, hydrochloric acid 5 ~ 10ml/L.
4. electroless copper processing procedure according to claim 2, it is characterised in that described activating solution consists of: silver nitrate 2 ~ 10g/L, adds proper ammonia and makes solution transparent.
5. electroless copper processing procedure according to claim 2, it is characterised in that described chemical plating fluid consists of: copper sulfate 10 ~ 25g/L, sodium hydroxide 8 ~ 15g/L, Nickel dichloride. 1 ~ 4g/L, EDTA20 ~ 35g/L, 2-2 bipyridyl 15 ~ 30g/L, formaldehyde 10 ~ 20ml/L.
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Cited By (6)
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| CN106884195A (en) * | 2017-02-20 | 2017-06-23 | 山东省科学院新材料研究所 | A kind of plated film magnesium and its alloy and preparation method thereof |
| CN107955961A (en) * | 2017-12-05 | 2018-04-24 | 西安文理学院 | A kind of preparation method of Mg alloy surface conduction corrosion-inhibiting coating |
| CN110714219A (en) * | 2019-11-04 | 2020-01-21 | 吉林大学 | Method for electroplating nickel on magnesium alloy micro-arc oxidation surface |
| CN110791797A (en) * | 2019-10-24 | 2020-02-14 | 中国电子科技集团公司第十四研究所 | High-corrosion-resistance conductive protection method for magnesium-lithium alloy and corresponding part |
| 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 |
| CN115852367A (en) * | 2022-12-06 | 2023-03-28 | 西北有色金属研究院 | Method for preparing high-corrosion-resistance conductive composite coating on surface of magnesium alloy |
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Cited By (9)
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| CN106884195A (en) * | 2017-02-20 | 2017-06-23 | 山东省科学院新材料研究所 | A kind of plated film magnesium and its alloy and preparation method thereof |
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| CN107955961A (en) * | 2017-12-05 | 2018-04-24 | 西安文理学院 | A kind of preparation method of Mg alloy surface conduction corrosion-inhibiting coating |
| CN107955961B (en) * | 2017-12-05 | 2019-09-10 | 西安文理学院 | A kind of preparation method of Mg alloy surface conduction corrosion-inhibiting coating |
| CN110791797A (en) * | 2019-10-24 | 2020-02-14 | 中国电子科技集团公司第十四研究所 | High-corrosion-resistance conductive protection method for magnesium-lithium alloy and corresponding part |
| CN110791797B (en) * | 2019-10-24 | 2021-08-13 | 中国电子科技集团公司第十四研究所 | High-corrosion-resistance conductive protection method for magnesium-lithium alloy and corresponding part |
| CN110714219A (en) * | 2019-11-04 | 2020-01-21 | 吉林大学 | Method for electroplating nickel on magnesium alloy micro-arc oxidation surface |
| 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 |
| CN115852367A (en) * | 2022-12-06 | 2023-03-28 | 西北有色金属研究院 | Method for preparing high-corrosion-resistance conductive composite coating on surface of magnesium alloy |
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Application publication date: 20160727 |