CN103255410A - Preparation method of magnesium alloy corrosion resistant prevention coating - Google Patents
Preparation method of magnesium alloy corrosion resistant prevention coating Download PDFInfo
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Abstract
The invention relates to a preparation method of a magnesium alloy corrosion resistant coating. The method is characterized in that spherical aluminum powder or spherical aluminum powder and SiC or Al2O3 powder are adopted, compressed air is used as an air source, and then a coating is prepared by a low-temperature pneumatic spraying method. The adopted powder comprises 100% of aluminum powder or 70-98wt% of aluminum powder and 30-2wt% of hard particles. After-treatment is performed by ceramic shot blasting or a 518 sealant produced by the Beijing Institute of Aeronautical Materials. Compared with the prior art, an aluminum coating prepared by the low-temperature pneumatic spraying method is dense with low porosity and high hardness, has good bonding strength with a base body, and has good corrosion resistance and wear resistance, thereby being a good protection coating for corrosion resistance 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 height, electromagnetic wave shielding is good and be easy to advantages such as recovery, in fields such as aviation, automobile, electronics wide application prospect is arranged.Therefore magnesium alloy is lighter by 35% than aluminium alloy, and has special toughness and damping capacity, utilizes its high intensity-weight characteristic to make the combiner of aircraft, as the wheel box of the transmission of vertiplane and wheel box, fixed wing aircraft etc.But the electrochemical activity of magnesium alloy is higher, with other metallographic phase relatively be the positive polarity metallic substance, therefore in the component system with multiple metallic substance combination, when preventing that corrosive medium from existing since the preferential and accelerated corrosion of the magnesium alloy that the galvanic corrosion effect causes must protect magnesium alloy.Magnesium alloy surface protective method commonly used at present mainly contains anodic oxidation treatment, differential arc oxidation processing, plating and electroless plating, chemical conversion film processing etc.Wherein differential arc oxidization technique has been broken through the restriction of conventional anodization technology to operating voltage, and its technology is simple, efficient is high, pollution-free, but it exists in technology poor reproducibility, price height, the rete and contains deficiencies such as micropore, crackle.Plating and electroless plating are traditional process for treating surface, and its technology can be brought environmental pollution etc. usually.Contain sexavalent chrome in the chemical conversion membrane treatment process, have toxicity, contaminate environment, treatment cost of waste liquor are also high.
The metallic aluminium coating not only has the effect of isolating corrosive medium as a kind of erosion shield, and still is a kind of positive polarity material for body materials such as iron and steel, therefore is widely used as the anticorrosion of steel and iron member.Aluminium and alloy coat thereof also are widely used in a kind of corrosion protection coating of magnesium alloy.Result of study to the Mg alloy surface thermal spraying aluminum shows that sprayed-on Al layer is dense, and is good with matrix bond, and the corrosion resistance nature of magnesium alloy also increases.
The pneumatic spraying of low temperature is the emerging surface engineering technology that development in recent years is got up, and utilizes the pneumatic spraying technology of low temperature successfully to realize the preparation of pure metal, alloy and compound coating, and is showing advantage aspect the preparation nano-structured coating.The coating of cold-starting spraying technology preparation has characteristics such as oxide content is low, the coating thermal stresses is little, hardness is high, bonding strength is good, has been subjected in recent years paying close attention to widely; And the pneumatic spraying technology of low temperature has that cost is low, efficient is high, environmental protection, can realize characteristics such as compound coating and thick coating preparation, becomes the up-and-coming youngster of spraying industry.
Utilize the pneumatic spraying technology of low temperature to prepare aluminum coating at Mg alloy surface, not only can access coating densification, corrosion-resistant coating that bonding strength is high, and can adjust and control the composition of coating according to the coating performance demand, improve the abrasion resistance properties of protective coating.Utilize the pneumatic spraying technology of low temperature to prepare the technology that aluminum coating is a kind of less energy-consumption, environmental type at Mg alloy surface.
Summary of the invention
The present invention designs the preparation method that the anticorrosive protective coating of a kind of magnesium alloy is provided at above-mentioned prior art situation just, its objective is under the prerequisite of the density that guarantees coating and bonding strength, aluminium powder and hard particles component proportions in the control coating, improve coating hardness, realize anticorrosive, anti abrasive premium properties.
The objective of the invention is to be achieved through the following technical solutions:
The preparation method of the anticorrosive protective coating of this kind magnesium alloy, comprise pre-treatment to magnesium alloy matrix surface, coating preparation and to the postprocessing working procedures of coating, it is characterized in that: coating preparation adopts the low temperature Gad dynamic coating apparatus to finish, the working parameter of this device is: be powder feeding gas and cleaning gas with the high pressure air, pressure is not less than 2.5MPa, the powder feeding gaseous tension is 1.5～2.5MPa, 30～600 ℃ of temperature, the 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 the weight percent of spherical aluminium powder and hard particles is in the mixture: 70～98%, 30～2%, and hard particles is Al
2O
3Or SiC powder;
It is one of following two kinds that the using method of coated material adopts:
(1) spherical aluminium powder is directly formed coating at the spraying magnesium alloy substrate.
(2) earlier spherical aluminium powder and hard-particle powder are mixed, in grinding in ball grinder after 48～72 hours, direct spray-on coating on magnesium alloy substrate.
Magnesium alloy matrix surface is carried out pretreated process is: at first adopting mean particle size is the diamantane sand of 700 μ m or the quartz sand of 150～250 μ m, depressing of 0.4～0.6MPa magnesium alloy matrix surface is carried out sandblast, clean with acetone then, clean in back one hour and carry out coating preparation.
After coating preparation is finished, adopt the mode of aftertreatment with density and the corrosion resistance of raising coating,
Postprocessing working procedures is one of following method:
(1) coating is carried out shot peening, adopting particle diameter is the ceramic pellet of 0.15mm, and pressure is 0.06～0.08MPa;
(2) coating is carried out sealing treatment, the 518 hole sealing agent applying coating surfaces of adopting the Beijing Research Inst. of Aeronautic Material to produce, dry back film forming.
Coat-thickness is 50～300 μ m.
Technical solution of the present invention has the following advantages:
1, the powder Heating temperature is lower, and the basic non-oxidation phenomenon of coating can keep the rerum natura of initial particle preferably;
2, spraying temperature is low, does not have too much heat to be delivered to processed workpiece surface in the spraying process; Coating is very little to the heat affecting of matrix, can not cause the high temperature deformation of matrix workpiece;
3, the coating inter-laminar stress is lower, and mainly is stress, is conducive to deposit thicker coating;
4, compare with other technologies of preparing of coating, have the coating densification, voidage is low, hardness is high, advantage such as coated component, thickness are easy to control.
Embodiment
Be further described below with reference to the technical solution of the present invention of embodiment:
The spherical aluminium powder of used coating material, hard, wear-resistant particle Al
2O
3Or SiC is the commercially available prod.The pneumatic paint finishing of low temperature is provided by Russian Academy Of Sciences siberian branch.
Embodiment 1
Matrix adopting ZM6 magnesium alloy, workpiece size is 100mm * 50mm * 5mm, spraying face is of a size of 100mm * 50mm.The pneumatic spraying coated material of low temperature is the spherical aluminium powder of granularity in 22～52 mu m ranges, before the spraying body material is carried out sandblast and clean, adopt the pneumatic paint finishing of low temperature to prepare the coating preparation aluminum coating in 1 hour, high pressure air is powder feeding gas and cleaning gas, powder feeding pressure 2.4Mpa, nebulizer gas pressure 2.2MPa; Gas temperature is 300 ℃; Spray distance is 20mm; Powder feeding rate is 1.16g/s; The spraying spacing distance is 2mm; Nozzle is 30mm/s with respect to the substrate translational speed.Obtain the coating that thickness is 150～300 μ m, adopting particle diameter is the ceramic pellet of 0.15mm, is under 0.06～0.08MPa coating to be carried out the shot-peening aftertreatment at pressure.
With scanning electron microscope the combination of surface, cross section pattern, coating and the body material of coating is analyzed; Adopt EDS to analyze the composition in coatingsurface, cross section; Adopt the metallographicobservation method to measure the porosity of coating; The result shows: the coating densification, and surface and cross section do not have tangible hole and tiny crack; Coating does not have other elements to exist except aluminium element; The coating voidage is 0.8%; The combination of coating and matrix is good, and bonding surface does not have tangible hole and occurs.
Coating hardness adopts Buehler type microhardness tester to measure remaining impression size and calculates, and selecting load for use is 245mN, and the loading time is 15s, and every sample is chosen 5 test point calculating mean values, and the result is 60.
With the electrochemical method of electrokinetic potential polarization scan and the corrosion resistance of neutral salt spray test evaluation and examination coating.Test polarization curve under the room temperature in 3.5%NaCl solution, 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 the Q-FOG salt-spray cabinet according to the requirement of GB10125.The result shows: the corrosion potential of aluminum coating is-850mV that corrosion electric current density is 3.17 μ A/cm
2Salt air corrosion 200h does not have corrosion, and salt-fog test 1000h is etched the matrix not.
Embodiment 2
Matrix adopting ZM6 magnesium alloy, specimen size is 100mm * 50mm * 5mm, spraying face is of a size of 100mm * 50mm.The pneumatic spraying coated material of low temperature is spherical aluminium powder and granularity the hard, wear-resistant particle Al the scope of 50～100 μ ms in of granularity in 22～52 mu m ranges
2O
3Mixed powder, spherical aluminium powder and hard, wear-resistant particle Al
2O
3Weight percent be 75%, 25%.With mixed powder grinding in ball grinder 48～72 hours; Before the spraying body material is carried out sandblast and clean, adopt the pneumatic paint finishing of low temperature to prepare the coating preparation 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 ℃; Spray distance is 15mm; Powder feeding rate is 1.16g/s; The spraying spacing distance is 2mm; Nozzle is 50mm/s with respect to the substrate translational speed.Obtain the coating that thickness is 150～300 μ m, obtain the coating that thickness is 120～200 μ m, adopting particle diameter is the ceramic pellet of 0.15mm, is under 0.06～0.08MPa coating to be carried out the shot-peening aftertreatment at pressure.
With scanning electron microscope the combination of surface, cross section pattern, coating and the body material of coating is analyzed; Adopt EDS to analyze the composition in coatingsurface, cross section; Adopt the metallographicobservation method to measure the porosity of coating; The result shows: the coating densification, and surface and cross section do not have tangible hole and tiny crack; Coating does not have other elements to exist except aluminium element; The coating voidage is 0.5%; The combination of coating and matrix is good, and bonding surface does not have tangible hole and occurs.
Coating hardness adopts Buehler type microhardness tester to measure remaining impression size and calculates, and selecting load for use is 245mN, and the loading time is 15s, and every sample is chosen 5 test point calculating mean values, and the result is 62.
Embodiment 3
Matrix adopting ZM6 magnesium alloy, specimen size is 100mm * 50mm * 5mm, spraying face is of a size of 100mm * 50mm.The pneumatic spraying coated material of low temperature is the spherical aluminium powder of granularity in 22～52 mu m ranges and the mixed powder of the hard, wear-resistant particle SiC of granularity in the scope of 22～52 μ m, spherical aluminium powder and hard, wear-resistant particle Al
2O
3Weight percent be 90%, 10%.With mixed powder grinding in ball grinder 48～72 hours; Before the spraying body material is carried out sandblast and clean, adopt the pneumatic paint finishing of low temperature to prepare the coating preparation 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 ℃; Spray distance is 15mm; Powder feeding rate is 1.16g/s; The spraying spacing distance is 2mm; Nozzle is 50mm/s with respect to the substrate translational speed.Obtain the coating that thickness is 50～150 μ m; Sealing treatment is carried out to coating in the 518 hole sealing agent applying coating surfaces of adopting the Beijing Research Inst. of Aeronautic Material to produce.
With scanning electron microscope the combination of surface, cross section pattern, coating and the body material of coating is analyzed; Adopt EDS to analyze the composition in coatingsurface, cross section; Adopt the metallographicobservation method to measure the porosity of coating; The result shows: the coating densification, and surface and cross section do not have tangible hole and tiny crack; Coating does not have other elements to exist except aluminium element; The coating voidage is 0.5%; The combination of coating and matrix is good, and bonding surface does not have tangible hole and occurs.
Coating hardness adopts Buehler type microhardness tester to measure remaining impression size and calculates, and selecting load for use is 245mN, and the loading time is 15s, and every sample is chosen 5 test point calculating mean values, and the result is 60.
Compared with prior art, technology is simple, efficient is high, pollution-free.Non-oxidation and phase transformation in the coating preparation process; Coating densification, microhardness are up to 60, and porosity is lower than 1%, controllable thickness; Corrosion resistance is good, and neutral salt spray test was above 1000 hours.
Claims (4)
1. the preparation method of the anticorrosive protective coating of magnesium alloy, comprise pre-treatment to magnesium alloy matrix surface, coating preparation and to the postprocessing working procedures of coating, it is characterized in that: coating preparation adopts the low temperature Gad dynamic coating apparatus to finish, the working parameter of this device is: be powder feeding gas and cleaning gas with the high pressure air, pressure is not less than 2.5MPa, the powder feeding gaseous tension is 1.5～2.5MPa, 30～600 ℃ of temperature, the 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 the weight percent of spherical aluminium powder and hard particles is in the mixture: 70～98%, 30～2%, and hard particles is Al
2O
3Or SiC powder;
It is one of following two kinds that the using method of coated material adopts:
(1) with the direct spray-on coating on magnesium alloy substrate of spherical aluminium powder;
(2) earlier spherical aluminium powder and hard-particle powder are mixed, in grinding in ball grinder after 48～72 hours, direct spray-on coating on magnesium alloy substrate.
2. the preparation method of the anticorrosive protective coating of magnesium alloy according to claim 1, it is characterized in that: magnesium alloy matrix surface is carried out pretreated process is: at first adopting mean particle size is the diamantane sand of 700 μ m or the quartz sand of 150～250 μ m, depressing of 0.4～0.6MPa magnesium alloy matrix surface is carried out sandblast, clean with acetone then, clean in back 1 hour and carry out coating preparation.
3. the preparation method of the anticorrosive protective coating of magnesium alloy according to claim 1, it is characterized in that: after coating preparation was finished, postprocessing working procedures was one of following method:
(1) coating is carried out shot peening, adopting particle diameter is the ceramic pellet of 0.15mm, and pressure is 0.06～0.08MPa;
(2) coating is carried out sealing treatment, the 518 hole sealing agent applying coating surfaces of adopting the Beijing Research Inst. of Aeronautic Material to produce, dry back film forming.
4. the preparation method of the anticorrosive protective coating of magnesium alloy according to claim 1, it is characterized in that: coat-thickness is 50～300 μ m.
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Cited By (12)
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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 |
| CN105256306A (en) * | 2015-11-05 | 2016-01-20 | 西安交通大学 | Manufacturing method for high-density cold spraying metal sedimentary body based on mixed powder |
| CN105525286A (en) * | 2016-01-06 | 2016-04-27 | 中国石油大学(华东) | Cold spraying aluminum-based self-lubrication abrasion-resistant coating and preparation method thereof |
| CN105525287A (en) * | 2016-01-06 | 2016-04-27 | 中国石油大学(华东) | Cold spraying aluminum-based self-lubrication abrasion-resistant coating and preparation method thereof |
| CN105543835A (en) * | 2016-01-06 | 2016-05-04 | 中国石油大学(华东) | Cold-spraying aluminum-base corrosion-resistant 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 |
| CN107164731A (en) * | 2017-05-26 | 2017-09-15 | 广东省新材料研究所 | A kind of preparation method of Mg alloy surface aluminium composite armor |
| CN108796493A (en) * | 2018-06-04 | 2018-11-13 | 常熟理工学院 | A kind of sealing of hole method of modifying of light metal surface cold spraying coating |
| WO2019008503A1 (en) * | 2017-07-04 | 2019-01-10 | Arcelormittal | A metallic substrate bearing a cold sprayed coating |
| 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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| 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 |
| CN105256306A (en) * | 2015-11-05 | 2016-01-20 | 西安交通大学 | Manufacturing method for high-density cold spraying metal sedimentary body based on mixed powder |
| 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 |
| 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 |
| CN105543835A (en) * | 2016-01-06 | 2016-05-04 | 中国石油大学(华东) | Cold-spraying aluminum-base corrosion-resistant coating and preparation method thereof |
| 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 |
| CN105525287A (en) * | 2016-01-06 | 2016-04-27 | 中国石油大学(华东) | Cold spraying aluminum-based self-lubrication abrasion-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 |
| CN105525286A (en) * | 2016-01-06 | 2016-04-27 | 中国石油大学(华东) | Cold spraying aluminum-based self-lubrication abrasion-resistant 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 |
| CN107164731A (en) * | 2017-05-26 | 2017-09-15 | 广东省新材料研究所 | A kind of preparation method of Mg alloy surface aluminium composite armor |
| WO2019008503A1 (en) * | 2017-07-04 | 2019-01-10 | Arcelormittal | A metallic substrate bearing a cold sprayed coating |
| CN108796493A (en) * | 2018-06-04 | 2018-11-13 | 常熟理工学院 | A kind of sealing of hole method of modifying of light metal surface cold spraying coating |
| 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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