CN103255410B - The preparation method of the anticorrosive protective coating of a kind of magnesium alloy - Google Patents
The preparation method of the anticorrosive protective coating of a kind of magnesium alloy Download PDFInfo
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Abstract
The present invention relates to a kind of preparation method of magnesium alloy corrosion-resistant coating, it is characterized in that: adopt spherical aluminium powder or spherical aluminium powder and SiC or Al
2o
3the powder of powder; Employing pressurized air is source of the gas, and the method for the pneumatic spraying of low temperature prepares coating.Adopt powder composition be 100% aluminium powder or 70 ~ 98% weight aluminium powders, 30 ~ 2% weight hard particles.518 hole sealing agents adopting ceramic pellet shot-peening or Beijing Research Inst. of Aeronautic Material to produce carry out aftertreatment.Compared with prior art, aluminum coating prepared by the method for the pneumatic spraying of low temperature is fine and close, porosity is low, hardness is high, good with the bonding strength of matrix, has good corrosion resistance and abrasion resistance properties, is the anticorrosive superior protection coating of a kind of magnesium alloy.
Description
Technical field
The present invention is the preparation method of the anticorrosive protective coating of a kind of magnesium alloy, belongs to the technical field of surface of metallic substance.
Background technology
Magnesium alloy has that density is low, specific tenacity and specific rigidity is high, electromagnetic wave shielding is excellent and be easy to the advantages such as recovery, has broad application prospects in fields such as aviation, automobile, electronics.Magnesium alloy is lighter than aluminium alloy by 35%, and has special toughness and damping capacity, and the strength-weight characteristic that therefore utilizes it high manufactures the combiner of aircraft, as the wheel box etc. of the transmission of vertiplane and wheel box, fixed wing aircraft.But the electrochemical activity of magnesium alloy is higher, comparing with other metallographic phase is positive polarity metallic substance, therefore, in the component system with various metals combination of materials, the preferential and accelerated corrosion of the magnesium alloy caused due to galvanic effect when existing for preventing corrosive medium must be protected magnesium alloy.Magnesium alloy surface protective method conventional at present mainly contains anodic oxidation treatment, differential arc oxidation process, plating and electroless plating, chemical conversion film process etc.Wherein differential arc oxidization technique breaches the restriction of conventional anodization technology to operating voltage, and its technique is simple, efficiency is high, pollution-free, but it exists that technique poor reproducibility, price are high, in rete containing the deficiency such as micropore, crackle.Plating and electroless plating are traditional process for treating surface, and its technique can bring environmental pollution etc. usually.Containing sexavalent chrome in chemical conversion membrane treatment process, have toxicity, contaminate environment, treatment cost of waste liquor is also high.
Metallic aluminium coating, as a kind of erosion shield, not only has the effect of isolation corrosive medium, and for the body materials such as iron and steel or a kind of positive polarity material, is therefore widely used as the anticorrosion of steel and iron member.Aluminum-aluminum alloy coating is also widely used in a kind of corrosion protection coating of magnesium alloy.Show the result of study of Mg alloy surface thermal spraying aluminum, sprayed-on Al layer is dense, is combined well with matrix, and the corrosion resistance nature of magnesium alloy also increases.
The pneumatic spraying of low temperature is the emerging surface engineering technology of development in recent years one of getting up, and utilizes the pneumatic spraying technology of low temperature successfully to realize the preparation of pure metal, alloy and compound coating, and shows advantage preparing in nano-structured coating.Coating prepared by cold-starting spraying technology has the features such as oxide content is low, coating thermal stresses is little, hardness is high, bonding strength is good, receives in recent years and pays close attention to widely; And the pneumatic spraying technology of low temperature has that cost is low, efficiency is high, environmental protection, can realize compound coating and thick coating and the feature such as to prepare, become the up-and-coming youngster of spraying industry.
The pneumatic spraying technology of low temperature is utilized to prepare aluminum coating at Mg alloy surface, not only can obtain coating densification, corrosion-resistant coating that bonding strength is high, and can according to coating performance demand, the composition of adjustment and control coating, improves the abrasion resistance properties of protective coating.The pneumatic spraying technology of low temperature is utilized to prepare at Mg alloy surface the technology that aluminum coating is a kind of less energy-consumption, environmental type.
Summary of the invention
The present invention designs for above-mentioned prior art situation the preparation method providing the anticorrosive protective coating of a kind of magnesium alloy just, its objective is under the guarantee density of coating and the prerequisite of bonding strength, control the aluminium powder in coating and hard particles component proportions, improve coating hardness, realize anticorrosive, anti abrasive premium properties.
The object of the invention is to be achieved through the following technical solutions:
The preparation method of this kind of anticorrosive protective coating of magnesium alloy, comprise the pre-treatment to magnesium alloy matrix surface, coating preparation and the postprocessing working procedures to coating, it is characterized in that: coating preparation adopts low temperature Gad dynamic coating apparatus to complete, the working parameter of this device is: take high pressure air as powder feeding gas and cleaning gas, pressure is not less than 2.5MPa, powder feeding gaseous tension is 1.5 ~ 2.5MPa, temperature 30 ~ 600 DEG C, powder feeding rate is 2 ~ 10kg/h, spray distance is 20 ~ 50mm, and translational speed is 50 ~ 100mm/s;
The composition of coated material is the mixture of spherical aluminium powder or spherical aluminium powder and hard particles, and in mixture, the weight percent of spherical aluminium powder and hard particles is: 70 ~ 98%, 30 ~ 2%, and hard particles is Al
2o
3or SiC powder;
One of following two kinds of using method employing of coated material:
(1) spherical aluminium powder is directly formed coating on spraying magnesium alloy substrate.
(2) first by spherical aluminium powder and hard-particle powder mixing, in grinding in ball grinder after 48 ~ 72 hours, directly spray-on coating on magnesium alloy substrate.
Carrying out pretreated process to magnesium alloy matrix surface is: first adopt mean particle size to be the diamantane sand of 700 μm or the quartz sand of 150 ~ 250 μm, in the pressure of 0.4 ~ 0.6MPa, sandblasting is carried out to magnesium alloy matrix surface, then with acetone cleaning, clean in latter one hour and carry out coating preparation.
After prepared by coating, adopt the mode of aftertreatment to improve density and the corrosion resistance of coating,
Postprocessing working procedures is one of following methods:
(1) carry out shot peening to coating, adopt particle diameter to be the ceramic pellet of 0.15mm, pressure is 0.06 ~ 0.08MPa;
(2) sealing treatment is carried out to coating, the 518 hole sealing agent applying coating surfaces adopting Beijing Research Inst. of Aeronautic Material to produce, film forming after dry.
Coat-thickness is 50 ~ 300 μm.
Technical solution of the present invention has the following advantages:
1, powder Heating temperature is lower, and the basic non-oxidation phenomenon of coating, can retain the physical property of initial particle preferably;
2, spraying temperature is low, does not have too much heat to be delivered to processed workpiece surface in spraying process; Coating is very little to the heat affecting of matrix, can not cause the high temperature deformation of substrate work-piece;
3, coating inter-laminar stress is lower, and mainly stress, be conducive to depositing thicker coating;
4, compared with other technologies of preparing of coating, there is the advantages such as coating densification, voidage is low, hardness is high, and coated component, thickness are easy to control.
Embodiment
Below with reference to embodiment, technical solution of the present invention is further described:
The spherical aluminium powder of used coating material, hard, wear-resistant particle Al
2o
3or SiC is commercially available prod.The pneumatic paint finishing of low temperature is provided by Russian Academy Of Sciences siberian branch.
Embodiment 1
Matrix adopts ZM6 magnesium alloy, and workpiece size is 100mm × 50mm × 5mm, and spray-coating surface is of a size of 100mm × 50mm.Low temperature pneumatic spraying coated material is the spherical aluminium powder of granularity within the scope of 22 ~ 52 μm, before spraying, sandblasting and clean are carried out to body material, adopt the pneumatic paint finishing of low temperature to prepare coating in 1 hour and prepare aluminum coating, high pressure air is powder feeding gas and cleaning gas, powder feeding pressure 2.4Mpa, nebulizer gas pressure 2.2MPa; Gas temperature is 300 DEG C; Spray distance is 20mm; Powder feeding rate is 1.16g/s; Spraying spacing distance is 2mm; Nozzle is 30mm/s relative to substrate translational speed.Obtain the coating that thickness is 150 ~ 300 μm, adopt particle diameter to be the ceramic pellet of 0.15mm, under pressure is 0.06 ~ 0.08MPa, shot-peening aftertreatment is carried out to coating.
Analyze with the combination of scanning electron microscope to the surface of coating, Cross Section Morphology, coating and body material; EDS is adopted to analyze the composition in coatingsurface, cross section; Metallographicobservation method is adopted to measure the porosity of coating; Result shows: coating is fine and close, and surface and cross section are without obvious hole and tiny crack; Coating, except aluminium element, does not have other elements; Coating voidage is 0.8%; The combination of coating and matrix is good, and bonding surface occurs without obvious hole.
Coating hardness adopts Buehler type microhardness tester to measure remaining impression Size calculation, and select load to be 245mN, the loading time is 15s, and 5 test point calculating mean values chosen by every block sample, and result is 60.
With the electrochemical method of potentiodynamic polarization scanning and the corrosion resistance of neutral salt spray test evaluation and examination coating.In 3.5%NaCl solution, test polarization curve under room temperature, supporting electrode is platinum electrode, and reference electrode is saturated calomel electrode, and scanning speed is 0.1mV/s.Neutral salt spray test carries out in Q-FOG salt-spray cabinet according to the requirement of GB10125.Result shows: the corrosion potential of aluminum coating is-850mV, and corrosion electric current density is 3.17 μ A/cm
2; Salt air corrosion 200h is corrosion-free, the non-etched the matrix of salt-fog test 1000h.
Embodiment 2
Matrix adopts ZM6 magnesium alloy, and specimen size is 100mm × 50mm × 5mm, and spray-coating surface is of a size of 100mm × 50mm.Low temperature pneumatic spraying coated material is the spherical aluminium powder of granularity within the scope of 22 ~ 52 μm and the hard, wear-resistant particle Al of granularity in the scope of 50 ~ 100 μm
2o
3mixed powder, spherical aluminium powder and hard, wear-resistant particle Al
2o
3weight percent be 75%, 25%.By mixed powder grinding in ball grinder 48 ~ 72 hours; Carry out sandblasting and clean to body material before spraying, adopt the pneumatic paint finishing of low temperature to prepare coating and prepare aluminum coating in 1 hour, high pressure air is powder feeding gas and cleaning gas, powder feeding pressure 2.4Mpa, nebulizer gas pressure 2.0MPa; Gas temperature is 300 DEG C; Spray distance is 15mm; Powder feeding rate is 1.16g/s; Spraying spacing distance is 2mm; Nozzle is 50mm/s relative to substrate translational speed.Obtain the coating that thickness is 150 ~ 300 μm, obtain the coating that thickness is 120 ~ 200 μm, adopt particle diameter to be the ceramic pellet of 0.15mm, under pressure is 0.06 ~ 0.08MPa, shot-peening aftertreatment is carried out to coating.
Analyze with the combination of scanning electron microscope to the surface of coating, Cross Section Morphology, coating and body material; EDS is adopted to analyze the composition in coatingsurface, cross section; Metallographicobservation method is adopted to measure the porosity of coating; Result shows: coating is fine and close, and surface and cross section are without obvious hole and tiny crack; Coating, except aluminium element, does not have other elements; Coating voidage is 0.5%; The combination of coating and matrix is good, and bonding surface occurs without obvious hole.
Coating hardness adopts Buehler type microhardness tester to measure remaining impression Size calculation, and select load to be 245mN, the loading time is 15s, and 5 test point calculating mean values chosen by every block sample, and result is 62.
Embodiment 3
Matrix adopts ZM6 magnesium alloy, and specimen size is 100mm × 50mm × 5mm, and spray-coating surface is of a size of 100mm × 50mm.Low temperature pneumatic spraying coated material is the spherical aluminium powder of granularity within the scope of 22 ~ 52 μm and the mixed powder of the hard, wear-resistant particle SiC of granularity in the scope of 22 ~ 52 μm, spherical aluminium powder and hard, wear-resistant particle Al
2o
3weight percent be 90%, 10%.By mixed powder grinding in ball grinder 48 ~ 72 hours; Carry out sandblasting and clean to body material before spraying, adopt the pneumatic paint finishing of low temperature to prepare coating and prepare aluminum coating in 1 hour, high pressure air is powder feeding gas and cleaning gas, powder feeding pressure 2.4Mpa, nebulizer gas pressure 2.0MPa; Gas temperature is 300 DEG C; Spray distance is 15mm; Powder feeding rate is 1.16g/s; Spraying spacing distance is 2mm; Nozzle is 50mm/s relative to substrate translational speed.Obtain the coating that thickness is 50 ~ 150 μm; The 518 hole sealing agent applying coating surfaces adopting Beijing Research Inst. of Aeronautic Material to produce, carry out sealing treatment to coating.
Analyze with the combination of scanning electron microscope to the surface of coating, Cross Section Morphology, coating and body material; EDS is adopted to analyze the composition in coatingsurface, cross section; Metallographicobservation method is adopted to measure the porosity of coating; Result shows: coating is fine and close, and surface and cross section are without obvious hole and tiny crack; Coating, except aluminium element, does not have other elements; Coating voidage is 0.5%; The combination of coating and matrix is good, and bonding surface occurs without obvious hole.
Coating hardness adopts Buehler type microhardness tester to measure remaining impression Size calculation, and select load to be 245mN, the loading time is 15s, and 5 test point calculating mean values chosen by every block sample, and result is 60.
Compared with prior art, technique is simple, efficiency is high, pollution-free.Non-oxidation and phase transformation in coating preparation process; Coating densification, microhardness are up to 60, and porosity is lower than 1%, and thickness is controlled; Corrosion resistance is excellent, and neutral salt spray test was more than 1000 hours.
Claims (1)
1. the preparation method of the anticorrosive protective coating of magnesium alloy, comprise the pre-treatment to magnesium alloy matrix surface, coating preparation and the postprocessing working procedures to coating, coating preparation adopts low temperature Gad dynamic coating apparatus to complete, it is characterized in that: matrix adopts ZM6 magnesium alloy, specimen size is 100mm × 50mm × 5mm, spray-coating surface is of a size of 100mm × 50mm, and low temperature pneumatic spraying coated material is the spherical aluminium powder of granularity within the scope of 22 ~ 52 μm and the hard, wear-resistant particle Al of granularity in the scope of 50 ~ 100 μm
2o
3mixed powder, spherical aluminium powder and hard, wear-resistant particle Al
2o
3weight percent be 75%, 25%;
By mixed powder grinding in ball grinder 48 ~ 72 hours; Carry out sandblasting and clean to body material before spraying, adopt the pneumatic paint finishing of low temperature to prepare aluminum coating in 1 hour, high pressure air is powder feeding gas and cleaning gas, powder feeding pressure 2.4Mpa, nebulizer gas pressure 2.0MPa; Gas temperature is 300 DEG C; Spray distance is 15mm; Powder feeding rate is 1.16g/s; Spraying spacing distance is 2mm; Nozzle is 50mm/s relative to substrate translational speed;
Obtaining thickness is adopt particle diameter to be the ceramic pellet of 0.15mm after the coating of 150 ~ 300 μm, under pressure is 0.06 ~ 0.08MPa, carry out shot-peening aftertreatment to coating.
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105039964A (en) * | 2015-07-10 | 2015-11-11 | 河南泛锐复合材料研究院有限公司 | Surface corrosion-resistant and abrasion-resistant composite coating for magnesium alloy and preparation method of surface corrosion-resistant and abrasion-resistant composite coating |
| CN105256306B (en) * | 2015-11-05 | 2018-06-26 | 西安交通大学 | The preparation method of high-compactness cold spraying metal deposit body based on mixed-powder |
| CN105543835B (en) * | 2016-01-06 | 2018-05-11 | 中国石油大学(华东) | A kind of cold spraying aluminium base anti-corrosion coating and preparation method thereof |
| CN105525287B (en) * | 2016-01-06 | 2018-06-12 | 中国石油大学(华东) | A kind of cold spraying aluminium base self-lubricating wear-resistant coating and preparation method thereof |
| CN105525286B (en) * | 2016-01-06 | 2018-06-12 | 中国石油大学(华东) | A kind of cold spraying aluminium base self-lubricating abrasion-resistant erosion resisting coating and preparation method thereof |
| CN106399902A (en) * | 2016-11-18 | 2017-02-15 | 无锡明盛纺织机械有限公司 | Wear-resistant and corrosion-resistant gradient coating magnesium alloy and preparation method thereof |
| CN107164731B (en) * | 2017-05-26 | 2021-08-31 | 广东省新材料研究所 | Preparation method of aluminum composite protective layer on surface of magnesium alloy |
| WO2019008404A1 (en) * | 2017-07-04 | 2019-01-10 | Arcelormittal | A metallic substrate bearing a cold sprayed coating |
| CN108796493B (en) * | 2018-06-04 | 2020-11-06 | 常熟理工学院 | Hole sealing modification method for cold spraying coating on surface of light metal |
| CN111485234A (en) * | 2020-04-29 | 2020-08-04 | 毅骋智造新材料科技(太仓)有限公司 | Method for repairing magnesium alloy surface corrosion by cold spraying |
| CN111979535A (en) * | 2020-07-22 | 2020-11-24 | 国营芜湖机械厂 | Cold spraying remanufacturing process for outer cylinder surface of undercarriage |
| CN112501605A (en) * | 2020-12-01 | 2021-03-16 | 湖北超卓航空科技股份有限公司 | Preparation method of functional composite cold spray coating |
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