CN103014804A - Aluminum alloy with army-green micro-arc oxidation ceramic membrane on surface and preparation method of aluminum alloy - Google Patents
Aluminum alloy with army-green micro-arc oxidation ceramic membrane on surface and preparation method of aluminum alloy Download PDFInfo
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Abstract
The invention discloses an aluminum alloy with an army-green micro-arc oxidation ceramic membrane on the surface, and a preparation method of the aluminum alloy. The aluminum alloy and the preparation method mainly solve the technical problem that most of the ceramic membranes treated by a light metal micro-arc oxidation technology existing in the prior art are off-white, white, black and the like. An electrolytic solution of the aluminum alloy comprises the following solutes: sodium phosphate, sodium silicate, sodium hexametaphosphate, sodium hydroxide, ethylene diamine tetraacetic acid, potassium dichromate, sodium carbonate, lauryl sodium sulfate and hydrogen peroxide; deionized water is adopted as a solvent; and the solutes and the solvent are blended into an alkaline electrolytic solution, stirred, placed for 1-2 hours, and then subjected to micro-arc oxidation treatment, therefore, the army-green ceramic membrane is obtained. The aluminum alloy has the benefits that the aluminum alloy is simple in preparation method, low in cost and small in environmental pollution. The prepared army-green ceramic membrane has the advantages that the army-green ceramic membrane is high in wear resistance, good in corrosion resistance, uniform in color and luster, good in stability, and compact, and does not fade easily. The army-green ceramic membrane is particularly suitable for disguise requirements of army products.
Description
Technical field
The present invention relates to the light metal surface processing technology field, specifically a kind of surface has aluminium alloy of green black colour ceramic coating formed by micro-arc oxidation and preparation method thereof.
Background technology
Aluminium alloy is known by people with lightweight, the characteristics such as specific tenacity is high, electric conductivity is high, good thermal conduction, and at machinery, electronics, space flight, aviation field widespread use, but because its hardness is low, solidity to corrosion is poor, wear resistance is low it is restricted.Therefore the surface hardness, corrosion resisting property, wear resisting property and the decorate properties that improve aluminium alloy become the key issue of present aluminium alloy development.
Differential arc oxidization technique has another name called the plasma micro-arc oxidation, and it is on the basis of common anode oxidation technology, obtains by measures such as rising impressed voltages.The voltage ratio that the common anode oxidation technology adds is lower, generally is lower than 30V, and along with the rising of impressed voltage, the anode oxide film that aluminum alloy surface has generated will be breakdown, produce hole, and final local oxide film comes off.USSR (Union of Soviet Socialist Republics) scientist finds that in late 1960s continuing boosted voltage can generate new oxide film at light metal surface, and generally this oxide film claims ceramic membrane.The surface propertys such as its wear resistance of one deck ceramic layer that obtains like this, solidity to corrosion are apparently higher than other surface strengthening treatment technology, such as anodic oxidation etc.The microhardness of measuring its coated aluminium alloy ceramic layer is 2100HV, and bonding strength is generally about 56MPa.This technical matters is simple, is a new technology of light metal material surface Hardening Treatment, has become in recent years one of study hotspot of light metal surface intensive treatment.
Along with the continuous expansion of differential arc oxidation range of application, except the aluminium alloy that requires differential arc oxidation to process has the characteristics such as high rigidity, wear-resistant, corrosion-resistant, proof voltage insulation, also require treated aluminum alloy surface to have some special color.Such as the military use product that is fit to Field Operational, except requiring above-mentioned performance, also requiring product surface is green black colour, so that camouflage.And present MAO is white or grey mostly, and color is single.At present, the preparation research of relevant green ceramic film is a lot, weak point is: contain strong corrosive material in (1) solution, solution can volatilize poisonous hydrogen fluoride in the differential arc oxidation process, easily experimenter's health is damaged (Pan Lihua, rare earth magnesium alloy micro arc oxidation green ceramic film preparation method, Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences); (2) the green ceramic film color is too shallow; Such as GEELY UNIVERSITY at Na
2SiO
3, NaoH, EDTA-Na
2, K
2Cr
2O
7Electrolytic solution in process 16min and obtain green ceramic film (Li Jiaqing, the Study on Preparation of aluminum alloy surface different colours ceramic coating formed by micro-arc oxidation, Jilin University's master thesis in 2009); The green ceramic film substrate of (3) making has blackspot and surperficial green very light, such as the NaAlO of Lanzhou University of Science ﹠ Technology
2, K
2Cr
2O
7, a small amount of NaOH and H
2O
2Prepare green ceramic film (Yan Fengyun, the preparation of magnesium alloy micro arc oxidation green ceramic film) at Mg alloy surface.
Summary of the invention
The objective of the invention is should wear-resisting, the corrosion-resistant characteristic that also will be convenient to pretend for the military use product that is fit to Field Operational, and aluminium alloy that a kind of surface has the green black colour ceramic coating formed by micro-arc oxidation and preparation method thereof is provided.
The technical scheme that realizes the object of the invention is:
A kind of surface has the preparation method of the aluminium alloy of green black colour ceramic coating formed by micro-arc oxidation, comprises the preparation of electrolytic solution, adopts AC pulse power supply to carry out the step that differential arc oxidation is processed, specifically:
(1) in the PVC plastic channel, injects the alkaline electrolyte of converting by specific components, concentration, under 10 ~ 20 ℃, stir, leave standstill after 1 ~ 2 hour and use;
Each composition weight of described alkaline electrolyte with the cumulative volume ratio is: sodium phosphate 15 ~ 45g/L, water glass 20 ~ 40g/L, Sodium hexametaphosphate 99 15 ~ 20g/L, sodium hydroxide 2 ~ 5g/L, disodium ethylene diamine tetraacetate 3 ~ 10g/L, potassium bichromate 1 ~ 4g/L, yellow soda ash 2 ~ 10g/L, sodium lauryl sulphate 1 ~ 5g/L, hydrogen peroxide 2 ~ 8g/L, and the pH value of electrolytic solution is 12～14;
(2) aluminium alloy matrix surface is polished, the polishing after in acetone and sodium hydroxide solution, carry out ultrasonic cleaning, again with washed with de-ionized water, dry up;
(3) with alloy matrix aluminum as anode, get 2 stainless steel substrates as negative electrode, with anchor clamps alloy matrix aluminum is fixed in the middle of 2 stainless steel substrates, and be immersed in fully in the alkaline electrolyte in the step (1), adopt AC pulse power supply to carry out differential arc oxidation and process, forward voltage is that 270 ~ 600V, negative voltage are that 10 ~ 100V, current density are that 10 ~ 20A/dm2, frequency are that 550～850Hz, dutycycle are 15%～45%, oxidization time is 5～60min during processing;
(4) with the alloy matrix aluminum after differential arc oxidation is processed, be to place 40 ~ 50min in 5.5～6.5,90～100 ℃ the deionized water in the pH value, take out alloy matrix aluminum, clean, dry up, can make the aluminium alloy that the surface has the green black colour ceramic coating formed by micro-arc oxidation.
Another purpose of the present invention provides the aluminium alloy that a kind of surface that makes with aforesaid method has the green black colour ceramic coating formed by micro-arc oxidation.
The thickness of described green black colour ceramic membrane is 20 μ m～35 μ m, and surface hardness is 1700～1800HV.
The invention has the beneficial effects as follows: the preparation method is simple, cost is low, environmental pollution is little, widely applicable, light metal all is suitable for, as making the green black colour ceramic membrane by differential arc oxidation at aluminium, magnesium, titanium and alloy surface thereof.The green black colour ceramic membrane of preparation has the wear resistance height, solidity to corrosion is good, color and luster is even, fine and close, good stability, the advantage such as fugitive color not, is particularly suitable for the camouflage needs of military use product.
Description of drawings
Fig. 1 is the aluminium alloy section structure synoptic diagram that surface of the present invention has the green black colour ceramic coating formed by micro-arc oxidation;
Among the figure: 1. alloy matrix aluminum 2. green black colour ceramic membranes;
Fig. 2 is embodiment 1 surface topography scanning electron microscope (SEM) photograph;
Fig. 3 is embodiment 1 Cross Section Morphology scanning electron microscope (SEM) photograph.
Embodiment
Below in conjunction with drawings and Examples content of the present invention is further elaborated, but is not limitation of the invention.
Embodiment 1
With reference to Fig. 1, a kind of surface of the present invention has the aluminium alloy of green black colour ceramic coating formed by micro-arc oxidation, is comprised of alloy matrix aluminum 1 and the green black colour ceramic membrane 2 that is laminated with on alloy matrix aluminum 1 surface.
Alloy matrix aluminum: adopt 6061 type aluminium alloys, size: 30mm * 20mm * 3mm.
Preparation method of the present invention is:
(1) in the PVC plastic channel, injects the alkaline electrolyte of converting by specific components, concentration, under 10 ~ 20 ℃, stir, leave standstill after 1 ~ 2 hour and use;
Each composition weight of described alkaline electrolyte with electrolytic solution cumulative volume ratio is: sodium phosphate 25g/L, Sodium hexametaphosphate 99 15g/L, sodium hydroxide 4g/L, disodium ethylene diamine tetraacetate 3g/L, potassium bichromate 3g/L, yellow soda ash 4g/L, sodium lauryl sulphate 2g/L, hydrogen peroxide 2g/L, and the pH value is 12～14;
(2) polish smooth to the surface scratch direction aluminium alloy matrix surface consistent with the water-proof abrasive paper of 400#, 600#, 800#, 1000# successively, in acetone and sodium hydroxide solution, carry out ultrasonic cleaning 15min after the polishing, again with washed with de-ionized water, dry up, remove the oxide compound on surface;
(3) with alloy matrix aluminum as anode, get 2 stainless steel substrates as negative electrode, with anchor clamps alloy matrix aluminum is fixed in the middle of 2 stainless steel substrates, and be immersed in fully in the alkaline electrolyte of step (1), adopt AC pulse power supply to carry out differential arc oxidation and process, forward voltage is that 358 ~ 400V, negative voltage are that 25V, current density are 20A/dm during processing
2, pulse-repetition is that 550Hz, dutycycle are 15%, the positive pulse number is 15, the negative pulse number is 3, oxidization time is 60min;
(4) with the alloy matrix aluminum after differential arc oxidation is processed, be 5.5～6.5 in the pH value, place 40 ~ 50min in 90～100 ℃ the deionized water, take out alloy matrix aluminum, use washed with de-ionized water, in distilled water, soak 10min, dry up, can make the aluminium alloy that the surface has the green black colour ceramic coating formed by micro-arc oxidation.
Utilize sem observation to green black colour ceramic membrane surface pattern scanning electron microscope Fig. 2, Cross Section Morphology scanning electron microscope Fig. 3, microhardness is 1800HV, and the thickness that detects ceramic membrane with layer thickness gauge is 33.9 μ m.
Embodiment 2
A kind of surface has the preparation of the aluminium alloy of green black colour ceramic coating formed by micro-arc oxidation, alloy matrix aluminum: adopt 6061 type aluminium alloys, size: 30mm * 20mm * 3mm.
Each composition weight of described alkaline electrolyte with electrolytic solution cumulative volume ratio is: sodium phosphate 30g/L, water glass 30g/L, Sodium hexametaphosphate 99 20g/L, sodium hydroxide 3g/L, disodium ethylene diamine tetraacetate 4g/L, potassium bichromate 3.5g/L, yellow soda ash 4g/L, sodium lauryl sulphate 3g/L, hydrogen peroxide 2g/L; The differential arc oxidation time is 20min, and current density is 10 A/dm
2, all the other preparation methods are identical with embodiment 1, and the ceramic membrane thickness that makes is 20.2 μ m, and microhardness is 1700HV.
Embodiment 3
A kind of surface has the preparation of the aluminium alloy of green black colour ceramic coating formed by micro-arc oxidation, alloy matrix aluminum: adopt 6061 type aluminium alloys, size: 20mm * 15mm * 1mm.
Each composition weight of described alkaline electrolyte with electrolytic solution cumulative volume ratio is: water glass 40g/L, Sodium hexametaphosphate 99 18g/L, sodium hydroxide 4g/L, disodium ethylene diamine tetraacetate 2g/L, potassium bichromate 4g/L, yellow soda ash 10g/L, sodium lauryl sulphate 5g/L, hydrogen peroxide 2g/L; The differential arc oxidation time is 45min, and current density is 10 A/dm
2, all the other preparation methods are identical with embodiment 1, and the ceramic membrane thickness that makes is 21.4 μ m, and microhardness is 1700HV.
Embodiment 4
A kind of surface has the preparation of the aluminium alloy of green black colour ceramic coating formed by micro-arc oxidation, alloy matrix aluminum: adopt LY type aluminium alloy, size: diameter 35mm, thickness 2mm.
Each composition weight of described alkaline electrolyte with the cumulative volume ratio is: water glass 35g/L, Sodium hexametaphosphate 99 16g/L, sodium hydroxide 2g/L, disodium ethylene diamine tetraacetate 8g/L, potassium bichromate all are 2.7g/L, yellow soda ash 10g/L, sodium lauryl sulphate 3.5g/L, hydrogen peroxide 5.5g/L; The differential arc oxidation time is 30min, and current density is 15 A/dm
2, all the other preparation methods are identical with embodiment 1, and the ceramic membrane thickness that makes is 25.7 μ m, and microhardness is 1750HV.
Claims (3)
1. a surface has the preparation method of the aluminium alloy of green black colour ceramic coating formed by micro-arc oxidation, comprises the preparation of electrolytic solution, adopts AC pulse power supply to carry out the step that differential arc oxidation is processed, and it is characterized in that:
(1) in the PVC plastic channel, injects the alkaline electrolyte of converting by specific components, concentration, under 10 ~ 20 ℃, stir, leave standstill after 1 ~ 2 hour and use;
Each composition weight of described alkaline electrolyte with electrolytic solution cumulative volume ratio is: sodium phosphate 15 ~ 45g/L, water glass 20 ~ 40g/L, Sodium hexametaphosphate 99 15 ~ 20g/L, sodium hydroxide 2 ~ 5g/L, disodium ethylene diamine tetraacetate 3 ~ 10g/L, potassium bichromate 1 ~ 4g/L, yellow soda ash 2 ~ 10g/L, sodium lauryl sulphate 1 ~ 5g/L, hydrogen peroxide 2 ~ 8g/L, and the pH value of electrolytic solution is 12～14;
(2) to after the aluminium alloy matrix surface polishing, clean, dry up;
(3) with alloy matrix aluminum as anode, stainless steel substrates is as negative electrode, be immersed in the alkaline electrolyte in the step (1), adopt AC pulse power supply to carry out differential arc oxidation and process, forward voltage is that 270 ~ 600V, negative voltage are that 10 ~ 100V, current density are that 10 ~ 20A/dm2, frequency are that 550～850Hz, dutycycle are 15%～45%, oxidization time is 5～60min during processing;
(4) with the alloy matrix aluminum after differential arc oxidation is processed, be to place 40 ~ 50min in 5.5～6.5,90～100 ℃ the deionized water in the pH value, take out alloy matrix aluminum, clean, dry up, can make the aluminium alloy that the surface has the green black colour ceramic coating formed by micro-arc oxidation.
2. the aluminium alloy that has the green black colour ceramic coating formed by micro-arc oxidation with the surface of method preparation claimed in claim 1.
3. surface according to claim 2 has the aluminium alloy of green black colour ceramic coating formed by micro-arc oxidation, it is characterized in that: the thickness of described green black colour ceramic membrane is 20～35 μ m, and surface hardness is 1700～1800HV.
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Cited By (13)
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| CN104087996A (en) * | 2014-07-28 | 2014-10-08 | 吕鹏翔 | Aluminum alloy surface easy-cleaning micro-arc oxidation ceramic membrane layer and preparation method thereof |
| CN104233427A (en) * | 2014-09-30 | 2014-12-24 | 西南交通大学 | Method for improving residual stress of aluminum alloy welding joint through micro-arc oxidation |
| CN104532320A (en) * | 2014-12-02 | 2015-04-22 | 佛山铭乾科技有限公司 | Preparation method of aluminium and titanium alloy micro arc ceramic membrane |
| CN106283152A (en) * | 2016-11-10 | 2017-01-04 | 西安工业大学 | A kind of aluminum alloy surface has pore self-sealing characteristic black ceramic layer and preparation method thereof |
| TWI571536B (en) * | 2015-09-08 | 2017-02-21 | 國立臺灣科技大學 | Method for growing a colored oxide film during micro-arc oxidation process |
| CN106435683A (en) * | 2015-08-19 | 2017-02-22 | 宁波瑞隆表面技术有限公司 | Electrolyte for preparing wear-resistant ceramic coating through micro-arc oxidation of aluminium alloy and treatment method of electrolyte |
| CN106591919A (en) * | 2016-12-09 | 2017-04-26 | 深圳市新合富力科技有限公司 | Aluminum material surface nanometer treatment process |
| CN106757267A (en) * | 2017-01-19 | 2017-05-31 | 山西平阳重工机械有限责任公司 | A kind of preparation method of cast aluminum base composite material surface green black colour micro-arc oxidation films |
| CN109402699A (en) * | 2018-11-01 | 2019-03-01 | 中国科学院兰州化学物理研究所 | A kind of aluminum alloy surface acid resistance corrosion function ceramic membrane preparation process |
| CN109576542A (en) * | 2018-12-29 | 2019-04-05 | 安徽鑫发铝业有限公司 | A kind of wear-resisting outer casing of power supply aluminum profile |
| CN109750340A (en) * | 2019-03-05 | 2019-05-14 | 东北大学 | A kind of preparation method of magnesium alloy green thermal control differential arc oxidation coating |
| CN109868386A (en) * | 2019-03-08 | 2019-06-11 | 安徽信息工程学院 | A kind of wear-resistant material and preparation method thereof |
| CN111549366A (en) * | 2020-06-08 | 2020-08-18 | 上海交通大学 | Preparation method of in-situ growth green corrosion-resistant ceramic membrane on surface of aluminum-based composite material |
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| CN104087996B (en) * | 2014-07-28 | 2016-06-01 | 大连大学 | The preparation method of aluminum alloy surface easy clean property Micro-Arc Oxidized Ceramic Coating |
| CN104087996A (en) * | 2014-07-28 | 2014-10-08 | 吕鹏翔 | Aluminum alloy surface easy-cleaning micro-arc oxidation ceramic membrane layer and preparation method thereof |
| CN104233427A (en) * | 2014-09-30 | 2014-12-24 | 西南交通大学 | Method for improving residual stress of aluminum alloy welding joint through micro-arc oxidation |
| CN104532320A (en) * | 2014-12-02 | 2015-04-22 | 佛山铭乾科技有限公司 | Preparation method of aluminium and titanium alloy micro arc ceramic membrane |
| CN106435683A (en) * | 2015-08-19 | 2017-02-22 | 宁波瑞隆表面技术有限公司 | Electrolyte for preparing wear-resistant ceramic coating through micro-arc oxidation of aluminium alloy and treatment method of electrolyte |
| TWI571536B (en) * | 2015-09-08 | 2017-02-21 | 國立臺灣科技大學 | Method for growing a colored oxide film during micro-arc oxidation process |
| CN106283152B (en) * | 2016-11-10 | 2019-06-18 | 西安工业大学 | A kind of aluminum alloy surface has self-styled pore property black ceramic layer and preparation method thereof |
| CN106283152A (en) * | 2016-11-10 | 2017-01-04 | 西安工业大学 | A kind of aluminum alloy surface has pore self-sealing characteristic black ceramic layer and preparation method thereof |
| CN106591919A (en) * | 2016-12-09 | 2017-04-26 | 深圳市新合富力科技有限公司 | Aluminum material surface nanometer treatment process |
| CN106757267A (en) * | 2017-01-19 | 2017-05-31 | 山西平阳重工机械有限责任公司 | A kind of preparation method of cast aluminum base composite material surface green black colour micro-arc oxidation films |
| CN109402699A (en) * | 2018-11-01 | 2019-03-01 | 中国科学院兰州化学物理研究所 | A kind of aluminum alloy surface acid resistance corrosion function ceramic membrane preparation process |
| CN109576542A (en) * | 2018-12-29 | 2019-04-05 | 安徽鑫发铝业有限公司 | A kind of wear-resisting outer casing of power supply aluminum profile |
| CN109750340A (en) * | 2019-03-05 | 2019-05-14 | 东北大学 | A kind of preparation method of magnesium alloy green thermal control differential arc oxidation coating |
| CN109750340B (en) * | 2019-03-05 | 2020-11-20 | 东北大学 | Preparation method of green thermal control micro-arc oxidation coating of magnesium alloy |
| CN109868386A (en) * | 2019-03-08 | 2019-06-11 | 安徽信息工程学院 | A kind of wear-resistant material and preparation method thereof |
| CN111549366A (en) * | 2020-06-08 | 2020-08-18 | 上海交通大学 | Preparation method of in-situ growth green corrosion-resistant ceramic membrane on surface of aluminum-based composite material |
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