CN101871119B - Preparation method of magnesium alloy surface micro-arc oxidation/spray coating compound film - Google Patents
Preparation method of magnesium alloy surface micro-arc oxidation/spray coating compound film Download PDFInfo
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Abstract
The invention provides a preparation method of a magnesium alloy surface micro-arc oxidation/spray coating compound film, which relates to a preparation method of a magnesium alloy surface compound film. The invention solves the problems that film layers obtained by chemical composition coating, anodic oxidation and vapor deposition in the existing magnesium alloy surface treatment method are thin and have poor corrosion resistance performance, the ion injection has high cost and is difficult to realize large-area processing, the combining force between coating layers and the magnesium alloy is poor, and organic coating layers has the defect of easy aging. The preparation method has the following steps: firstly, using micro-arc oxidation for preparing ceramic films on the surface of the magnesium alloy; then, adopting air spray coating for spraying and coating inorganic paint onto the ceramic films; and then, carrying out heat treatment to obtain the micro-arc oxidation/spray coating compound film. The method is simple, and the cost is low. The air spray coating uses porous structures of the micro-arc oxidation ceramic films, so the combination of the inorganic coating layers and the ceramic films is firm, the thickness of the compound films is between 20 and 40 mum, the self corrosion electric potential is positively moved to -1.02 V, the corrosion current density is lowered by 5 orders through being compared with that of the magnesium alloy, the magnesium alloy surface micro-arc oxidation/spray coating compound film has no damage after 72 to 144h of salt spray tests, and the corrosion resistance performance is good.
Description
Technical field
The present invention relates to a kind of preparation method of Mg alloy surface composite package.
Background technology
Magnesiumalloy is called as " 21 century tool development potentiality and the green engineering material of future ", and it is high to have specific tenacity and specific rigidity, and damping, anti-acoustic capability are good; Young's modulus is low; Plasticity ratio aluminium is low, high shield electromagnetic interference performance, advantages such as damping and amortization, perfect heat-dissipating.In addition, magnesiumalloy reclaiming property is good, compliance with environmental protection requirements.In view of above advantage, magnesiumalloy is widely used in fields such as automobile, electronic apparatus, aerospace, defence and military, traffic.But the magnesiumalloy electropotential is low, and chemical activity is high, and stability is low, very easily corrodes in a humid environment.Though magnesiumalloy can react with airborne oxygen and generate one deck natural oxide film, this sull is loose porous, not fine and close, and solidity to corrosion is poor, and metallic matrix is not had effective provide protection.These corrosive propertys of magnesiumalloy have seriously limited its application on engineering.Therefore, the etching problem of magnesiumalloy becomes " bottleneck " of the further widespread use of magnesiumalloy.
The surface modification treatment technology has become one of important means of improving the magnesiumalloy use properties at present.At present mainly comprise chemical conversion film, anodic oxidation, vapour deposition, ion implantation, differential arc oxidation and application techniques etc. about the process for treating surface of magnesiumalloy.But the general rete that obtains of chemical conversion film, anodic oxidation and vapour deposition thin (thickness is generally in nano level or several micrometer ranges) is limited to the provide protection of magnesium alloy substrate.Ion injection method can improve corrosive nature significantly, but its application cost is very high, and is difficult to realize big area processing.Differential arc oxidization technique can improve the corrosion resisting property of magnesiumalloy; But because the porousness of its structure; Therefore it also is limited improving corrosion resistance nature, and application techniques is divided into organic and inorganic two kinds, and the reload request matrix that is coated with of general Mg alloy surface has certain roughness; But its key issue is in the use easily and matrix comes off, and also there is an easy problem of aging in organic application.
Summary of the invention
The objective of the invention is to approach poor corrosion resistance in order to solve the rete that chemical conversion film, anodic oxidation, vapour deposition obtain in the existing surface treatment method of Mg alloy; The ion injection method cost is high, is difficult to realize big area processing; Coating and magnesium alloy substrate bonding force are poor, and organic coating is prone to the aged problem, the invention provides a kind of preparation method of magnesium alloy surface micro-arc oxidation/spray coating compound film.
The preparation method of magnesium alloy surface micro-arc oxidation/spray coating compound film of the present invention realizes through following steps: one, magnesiumalloy is carried out pre-treatment and remove surface film oxide; Then pretreated magnesiumalloy is placed electrolytic solution as working electrode; Stainless steel tank is as electrolyzer and counter electrode; Adopt constant voltage or constant current mode differential arc oxidation 5 ~ 20min, promptly on magnesiumalloy, obtain the porous ceramic coating formed by micro-arc oxidation, wherein electrolytic solution consists of: the Na of 6 ~ 30g/L
2SiO
3, the NaF of 0 ~ 5g/L and the NaOH of 0 ~ 5g/L, solvent is a water; During constant voltage mode, control voltage is 50 ~ 600V, and frequency is 300 ~ 2000Hz, and dutycycle is 10 ~ 45%; During constant current mode, control current density is 2 ~ 5A/dm
2, frequency is 300 ~ 2000Hz, dutycycle is 10 ~ 45%; Two, adopt the aerial spraying mode on the magnesium alloy surface micro-arc oxidation ceramic membrane that step 1 obtains, to spray inorganic coating layer; The quantity for spray of control inorganic paint is 3 ~ 5g/s, and compressed-air actuated internal pressure is 0.3 ~ 0.5MPa, and it is the spray gun of 1mm that nozzle diameter is adopted in spraying; Control spray gun and magnesium alloy surface micro-arc oxidation ceramic membrane are rectangular; The distance of spray tip and ceramic coating formed by micro-arc oxidation is 10 ~ 15cm, and spray gun runs parallel, and the spray gun translational speed is 10 ~ 20cm/s; Spray 1 ~ 2 back and forth, obtain the ceramic coating formed by micro-arc oxidation surface be coated with inorganic coating layer magnesiumalloy; Said inorganic paint is the mixture of double-component aqueous nano ceramic coating and nano-sized filler; Wherein the interpolation quality of nano-sized filler is 0% ~ 10% of an inorganic paint quality, and said double-component aqueous nano ceramic coating and nano-sized filler are Shenzhen auspicious magnificent quark chemical industry ltd and produce; Said 1 be meant back and forth spray gun in the side shifting on ceramic coating formed by micro-arc oxidation surface to opposite side, move back to origination side again; Three, the ceramic coating formed by micro-arc oxidation surface that step 2 is obtained is coated with the magnesiumalloy of inorganic coating layer at 60 ~ 100 ℃ of down dry 10 ~ 20min; And then in 230 ~ 300 ℃ retort furnace sintering 20 ~ 30min; Then magnesiumalloy is taken out; Naturally cool to room temperature, promptly prepare micro-arc oxidation/spray coating compound film at Mg alloy surface.
Magnesiumalloy carries out pretreated being operating as in the step 1 of the present invention: clean Mg alloy surface with scrubbing powder; Clean with flushing with clean water then; Magnesiumalloy after the cleaning is used the water-proof abrasive paper sanding and polishing of 240#, 360#, 800# and 1000# successively, carries out ultrasonic cleaning with tap water, zero(ppm) water and ethanol successively respectively then.
The water nano ceramic coating that adopts in the inorganic paint described in the step 2 of the present invention is not limited to provided by the auspicious magnificent quark chemical industry in Shenzhen ltd, and existing commercially available water nano ceramic coating all can be used for the present invention.The nano-sized filler of adding in the inorganic paint; Silver color filler, white filler, grey filler and the black filler etc. that provide for the auspicious magnificent quark chemical industry in Shenzhen ltd; But being not limited to is provided by the auspicious magnificent quark chemical industry in Shenzhen ltd, and existing commercially available nanoscale powder filler all can be used for the present invention.
The present invention goes on foot the preparation that realizes micro-arc oxidation/spray coating compound film by differential arc oxidation and aerial spraying two, and preparation technology is simple, and preparation process is controlled easily, and cost is low, is easy to realize the preparation of large tracts of land composite membrane.In conjunction with the advantage of two types of technology of differential arc oxidization technique and aerial spraying technology, promptly the high anti-corrosion of the high bond strength of ceramic coating formed by micro-arc oxidation and inorganic coating layer and be difficult for the aged characteristics improves the barrier propterty of magnesiumalloy comprehensively.Utilize the porous characteristics of ceramic coating formed by micro-arc oxidation simultaneously, what make inorganic paint and ceramic coating formed by micro-arc oxidation combines well, has solved the paint coatings that directly on magnesiumalloy, sprays and has combined poorly with magnesiumalloy, is prone to come off, and does not reach the drawback of fine protection effect.
The thickness of micro-arc oxidation/spray coating compound film of the present invention is at 20 ~ 40 μ m, and wherein (main crystalline phase is Mg to ceramic coating formed by micro-arc oxidation
2SiO
4And MgO) is white film; Thickness is 5 ~ 25 μ m; Thickness is far longer than the thickness of the rete that chemical conversion film, anodic oxidation, vapour deposition obtain, and the thickness of the transparent inorganic coating layer that obtains through aerial spraying can block whole hole, Micro-Arc Oxidized Ceramic Coating surface about 15 μ m; More effectively stop environmental contaminants and corrosive fluid to arrive magnesium alloy substrate; Can significantly improve the corrosion resisting property of rete, salt mist experiment greater than 72 ~ 144h after on the rete except the minority stain, can also remain intact intact.
The present invention combines differential arc oxidation and aerial spraying, and aerial spraying utilizes the vesicular structure of the ceramic film that differential arc oxidation obtains, and inorganic coating layer is combined firmly with Micro-Arc Oxidized Ceramic Coating.Micro-arc oxidation films has certain roughness; Need carry out the operation steps that shot peening obtains uneven surface to magnesiumalloy when having omitted directly on magnesiumalloy sprayed coating; The present invention can directly spray on micro-arc oxidation films; And inorganic coating layer combines with Micro-Arc Oxidized Ceramic Coating firmly; Carried out the bonding force of cut test evaluation inorganic coating layer and ceramic coating formed by micro-arc oxidation according to standard GB/T 1720-1979, test result shows that the inorganic paint adhesive force of coatings is primary standard, explains that inorganic coating layer and ceramic membrane bonding force are good.
The ceramic film that the present invention obtains through differential arc oxidation and the bonding force of magnesiumalloy are strong; Inorganic coating layer and ceramic membrane bonding force are good; Then the bonding force of the composite package that obtains of the present invention and magnesiumalloy is good; And composite package to corrosion resistance of magnesium alloy can raising effect is clearly arranged, than directly spraying on magnesiumalloy, and the corrosion resisting property of simple ceramic coating formed by micro-arc oxidation is better.
The micro-arc oxidation/spray coating compound film that the present invention prepares crackle just occurs after 500 ℃ thermal shock circulation 20 times; Then along with the increase of thermal shock number of times; Just crackle slowly increases, deepens; Until thermal shock 74 times, peeling phenomenon does not appear in micro-arc oxidation/spray coating compound film yet, and micro-arc oxidation/spray coating compound film that the present invention obtains and magnesiumalloy bonding force are good.
The corrosion potential of the micro-arc oxidation/spray coating compound film that the present invention prepares is-1.02V; Corrosion potential (about 1.5V) than magnesiumalloy has been shuffled about 500mV; And the corrosion potential of the ceramic coating formed by micro-arc oxidation that step 1 obtains (1.46V) only shuffled about 40mV, the corrosion tendency property of micro-arc oxidation/spray coating compound film of the present invention on thermodynamics significantly diminishes; The corrosion electric current density of micro-arc oxidation/spray coating compound film of the present invention has reduced by 5 one magnitude than the corrosion electric current density of magnesiumalloy; The corrosion electric current density of the ceramic coating formed by micro-arc oxidation that obtains than step 1 has reduced by 3 one magnitude, and the corrosion tendency property of micro-arc oxidation/spray coating compound film of the present invention on kinetics significantly diminishes.The micro-arc oxidation/spray coating compound film that the present invention obtains on thermodynamics and kinetics two aspects, corrosion resistance nature has all had the raising of matter.
Simultaneously, behind the salt mist experiment of 72 ~ 144h, differential arc oxidation/inorganic compounding layer still is kept perfectly harmless differential arc oxidation of the present invention/inorganic compounding layer under the experiment condition that 5% NaCl (analytical pure) neutral solution and salt fog the temperature inside the box are 35 ℃.The salt mist experiment time is 3 ~ 6 times of salt mist experiment time (24h) of the arc differential oxide ceramic layer of step 1 preparation, is 3 ~ 6 times of salt mist experiment time (24h) of the inorganic coating layer that directly spraying obtains on magnesiumalloy.
In sum, the micro-arc oxidation/spray coating compound film that the present invention prepares and the bonding force of magnesiumalloy are good, and the bonding force of the inorganic coating layer of micro-arc oxidation films and aerial spraying might as well in the composite package; Erosion resistance improves greatly, and the raising of matter has been arranged.The raising of erosion resistance is compared with independent inorganic coating layer with independent micro-arc oxidation films, micro-arc oxidation/spray coating compound film of the present invention is more effective to the raising of corrosion resistance of magnesium alloy, and is better.
Description of drawings
Fig. 1 is the sem photograph of the ceramic coating formed by micro-arc oxidation for preparing of the step 1 of embodiment 36; Fig. 2 is the sem photograph of the micro-arc oxidation/spray coating compound film that obtains of embodiment 36; Fig. 3 is the cross section sem photograph of the micro-arc oxidation/spray coating compound film that obtains of embodiment 36; Fig. 4 is the micro-arc oxidation/spray coating compound film for preparing of embodiment 36, the ceramic coating formed by micro-arc oxidation that step 1 obtains; And the Tafel graphic representation of the corrosion resistance nature of three kinds of samples of AZ31B magnesiumalloy (do not carry out pre-treatment, there is natural oxide film on the surface) test; Fig. 5 be the contrast experiment's in the embodiment 36 the Mg alloy surface inorganic coating layer sample of direct spraying inorganic paint behind salt mist experiment 24h macro morphology figure; Fig. 6 be the ceramic coating formed by micro-arc oxidation that obtains of embodiment 36 step 1 behind salt mist experiment 24h macro morphology figure; Fig. 7 is the macro morphology figure of micro-arc oxidation/spray coating compound film behind the 72h salt mist experiment that embodiment 36 obtains; Fig. 8 is the macro morphology figure of micro-arc oxidation/spray coating compound film behind the 144h salt mist experiment that embodiment 37 obtains; Fig. 9 is the sem photograph of the micro-arc oxidation/spray coating compound film that obtains of embodiment 38; Figure 10 is the sem photograph of the micro-arc oxidation/spray coating compound film that obtains of body embodiment 38; The sem photograph of the micro-arc oxidation/spray coating compound film that Figure 11 embodiment 39 obtains; Figure 12 is the cross section sem photograph of the micro-arc oxidation/spray coating compound film that obtains of embodiment 39.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of this embodiment magnesium alloy surface micro-arc oxidation/spray coating compound film realizes through following steps: one, magnesiumalloy is carried out pre-treatment and remove surface film oxide; Then pretreated magnesiumalloy is placed electrolytic solution as working electrode; Stainless steel tank is as electrolyzer and counter electrode; Adopt constant voltage or constant current mode differential arc oxidation 5 ~ 20min; Promptly on magnesiumalloy, obtain the porous ceramic coating formed by micro-arc oxidation, wherein electrolytic solution consists of: the Na of 6 ~ 30g/L
2SiO
3, the NaF of 0 ~ 5g/L and the NaOH of 0 ~ 5g/L, solvent is a water; During constant voltage mode, control voltage is 350 ~ 550V, and frequency is 300 ~ 2000Hz, and dutycycle is 10 ~ 45%; During constant current mode, control current density is 2 ~ 5A/dm
2, frequency is 300 ~ 2000Hz, dutycycle is 10 ~ 45%; Two, adopt the aerial spraying mode on the magnesium alloy surface micro-arc oxidation ceramic membrane that step 1 obtains, to spray inorganic coating layer; The quantity for spray of control inorganic paint is 3 ~ 5g/s, and compressed-air actuated internal pressure is 0.3 ~ 0.5MPa, and it is the spray gun of 1mm that nozzle diameter is adopted in spraying; Control spray gun and magnesium alloy surface micro-arc oxidation ceramic membrane are rectangular; The distance of spray tip and ceramic coating formed by micro-arc oxidation is 10 ~ 15cm, and spray gun runs parallel, and the spray gun translational speed is 10 ~ 20cm/s; Spray 1 ~ 2 back and forth, obtain the ceramic coating formed by micro-arc oxidation surface be coated with inorganic coating layer magnesiumalloy; Said inorganic paint is the mixture of double-component aqueous nano ceramic coating and nano-sized filler; Wherein the interpolation quality of nano-sized filler is 0% ~ 10% of an inorganic paint quality, and said double-component aqueous nano ceramic coating and nano-sized filler are Shenzhen auspicious magnificent quark chemical industry ltd and produce; Said 1 be meant back and forth spray gun in the side shifting on ceramic coating formed by micro-arc oxidation surface to opposite side, move back to origination side again; Three, the ceramic coating formed by micro-arc oxidation surface that step 2 is obtained is coated with the magnesiumalloy of inorganic coating layer at 60 ~ 100 ℃ of down dry 10 ~ 20min; And then in 230 ~ 300 ℃ retort furnace sintering 20 ~ 30min; Then magnesiumalloy is taken out; Naturally cool to room temperature, promptly prepare micro-arc oxidation/spray coating compound film at Mg alloy surface.
The water nano ceramic coating that adopts in the inorganic paint described in this embodiment step 2 is not limited to provided by the auspicious magnificent quark chemical industry in Shenzhen ltd, and existing commercially available water nano ceramic coating all can be used for the present invention.The nano-sized filler of adding in the inorganic paint; Silver color filler, white filler, grey filler and the black filler etc. that provide for the auspicious magnificent quark chemical industry in Shenzhen ltd; But being not limited to is provided by the auspicious magnificent quark chemical industry in Shenzhen ltd, and existing commercially available nanoscale powder filler all can be used for the present invention.
This embodiment combines differential arc oxidation and aerial spraying, and aerial spraying utilizes the vesicular structure of the ceramic film that differential arc oxidation obtains, and inorganic coating layer is combined firmly with Micro-Arc Oxidized Ceramic Coating.The ceramic film that the while differential arc oxidation obtains and the bonding force of magnesiumalloy are strong; Then the bonding force of the composite package that obtains of this embodiment and magnesiumalloy is good; And composite package to corrosion resistance of magnesium alloy can raising effect is clearly arranged; Than directly spraying on magnesiumalloy, and the corrosion resistance nature of simple ceramic coating formed by micro-arc oxidation is better.
Embodiment two: what this embodiment and embodiment one were different is that magnesiumalloy is AZ91D magnesiumalloy, AZ31B magnesiumalloy, magnesium lithium alloy, MB26 or ZM5 in the step 1.Other step and parameter are identical with embodiment one.
Embodiment three: what this embodiment was different with embodiment one or two is that magnesiumalloy carries out pretreated being operating as in the step 1: clean Mg alloy surface with scrubbing powder; Clean with flushing with clean water then; Magnesiumalloy after the cleaning is used the water-proof abrasive paper sanding and polishing of 240#, 400#, 800# and 1000# successively, uses tap water, zero(ppm) water and acetone then respectively successively.Other step and parameter are identical with embodiment one or two.
Embodiment four: what this embodiment and embodiment one, two or three were different is to adopt constant voltage or constant current mode differential arc oxidation 10 ~ 18min in the step 1.Other step and parameter are identical with embodiment one, two or three.
Along with the increase of differential arc oxidation time, the rate of rise of rete diminishes in this embodiment, and it is big that the film surface roughness becomes.
Embodiment five: what this embodiment and embodiment one, two or three were different is to adopt constant voltage or constant current mode differential arc oxidation 15min in the step 1.Other step and parameter are identical with embodiment one, two or three.
Embodiment six: what this embodiment was different with one of embodiment one to five is that electrolytic solution consists of in the step 1: the Na of 6 ~ 30g/L
2SiO
3, solvent is a water.Other step and parameter are identical with one of embodiment one to five.
Na in this embodiment
2SiO
3Be membrane-forming agent, under other processing condition fixed situation, Na
2SiO
3Concentration big more, thicknesses of layers is big more.
Embodiment seven: what this embodiment was different with one of embodiment one to five is that electrolytic solution consists of in the step 1: the Na of 10 ~ 20g/L
2SiO
3, solvent is a water.Other step and parameter are identical with one of embodiment one to five.
Embodiment eight: what this embodiment was different with one of embodiment one to five is that electrolytic solution consists of in the step 1: the Na of 15g/L
2SiO
3, solvent is a water.Other step and parameter are identical with one of embodiment one to five.
Embodiment nine: what this embodiment was different with one of embodiment one to five is that electrolytic solution consists of in the step 1: the Na of 6 ~ 30g/L
2SiO
3With the NaF of 0.1 ~ 5g/L, solvent is a water.Other step and parameter are identical with one of embodiment one to five.
Na in this embodiment
2SiO
3Be main membrane-forming agent, NaF is little to the thicknesses of layers influence, and the effect of NaF mainly is an adjustment rete microscopic appearance, makes rete more smooth, evenly.
Embodiment ten: what this embodiment was different with one of embodiment one to five is that electrolytic solution consists of in the step 1: the Na of 10 ~ 20g/L
2SiO
3With the NaF of 0.5 ~ 2g/L, solvent is a water.Other step and parameter are identical with one of embodiment one to five.
Embodiment 11: what this embodiment was different with one of embodiment one to five is that electrolytic solution consists of in the step 1: the Na of 15g/L
2SiO
3With the NaF of 1g/L, solvent is a water.Other step and parameter are identical with one of embodiment one to five.
Embodiment 12: what this embodiment was different with one of embodiment one to five is that electrolytic solution consists of in the step 1: the Na of 6 ~ 30g/L
2SiO
3With the NaOH of 0.1 ~ 5g/L, solvent is a water.Other step and parameter are identical with one of embodiment one to five.
Na in this embodiment
2SiO
3Be main membrane-forming agent, NaOH is little to the thicknesses of layers influence, and the effect of NaOH mainly is an adjustment rete microscopic appearance, makes rete more smooth, evenly.
Embodiment 13: what this embodiment was different with one of embodiment one to five is that electrolytic solution consists of in the step 1: the Na of 10 ~ 20g/L
2SiO
3With the NaOH of 1 ~ 2g/L, solvent is a water.Other step and parameter are identical with one of embodiment one to five.
Embodiment 14: what this embodiment was different with one of embodiment one to five is that electrolytic solution consists of in the step 1: the Na of 15g/L
2SiO
3With the NaOH of 1.5g/L, solvent is a water.Other step and parameter are identical with one of embodiment one to five.
Embodiment 15: what this embodiment was different with one of embodiment one to five is that electrolytic solution consists of in the step 1: the Na of 6 ~ 20g/L
2SiO
3, the NaF of 1 ~ 3g/L and the NaOH of 1 ~ 3g/L, solvent is a water.Other step and parameter are identical with one of embodiment one to five.
Na in this embodiment
2SiO
3Be main membrane-forming agent, NaF and NaOH are little to the thicknesses of layers influence, and the effect of NaF and NaOH mainly is an adjustment rete microscopic appearance, makes rete more smooth, evenly.
Embodiment 16: what this embodiment was different with one of embodiment one to five is that electrolytic solution consists of in the step 1: the Na of 6 ~ 10g/L
2SiO
3, the NaF of 1.5 ~ 2.5g/L and the NaOH of 1.5 ~ 2.5g/L, solvent is a water.Other step and parameter are identical with one of embodiment one to five.
Embodiment 17: what this embodiment was different with one of embodiment one to five is that electrolytic solution consists of in the step 1: the Na of 6g/L
2SiO
3, the NaF of 2g/L and the NaOH of 2g/L, solvent is a water.Other step and parameter are identical with one of embodiment one to five.
Embodiment 18: this embodiment is different with one of embodiment one to 17 is in the step 1 during constant voltage mode, and control voltage is 400 ~ 500V, and frequency is 500 ~ 1500Hz, and dutycycle is 20 ~ 40%.Other step and parameter are identical with one of embodiment one to 17.
Adopt constant voltage mode to carry out differential arc oxidation in this embodiment; Voltage constant is constant in the differential arc oxidation process, and electric current is along with the carrying out of reaction constantly reduces, and reason is the carrying out along with the differential arc oxidation reaction; The thickness of ceramic membrane constantly increases; Resistance constantly increases, and is applying under the constant situation of voltage, and electric current reduces gradually.
Embodiment 19: this embodiment is different with one of embodiment one to 17 is in the step 1 during constant voltage mode, and control voltage is 450V, and frequency is 1000Hz, and dutycycle is 30%.Other step and parameter are identical with one of embodiment one to 17.
Embodiment 20: this embodiment is different with one of embodiment one to 17 is in the step 1 during constant current mode, and control current density is 2 ~ 5A/dm
2, frequency is 500 ~ 1500Hz, dutycycle is 20 ~ 40%.Other step and parameter are identical with one of embodiment one to 17.
Adopt constant current mode to carry out differential arc oxidation in this embodiment; Current constant is constant in the differential arc oxidation process, and voltage is along with the carrying out of reaction constantly increases, and reason is the carrying out along with the differential arc oxidation reaction; The thickness of ceramic membrane constantly increases; Resistance constantly increases, and is applying under the constant situation of electric current, and voltage increases gradually.
Embodiment 21: this embodiment is different with one of embodiment one to 17 is in the step 1 during constant current mode, and control current density is 3A/dm
2, frequency is 1000Hz, dutycycle is 30%.Other step and parameter are identical with one of embodiment one to 17.
Embodiment 22: this embodiment is different with one of embodiment one to 21 is that the quantity for spray of control inorganic paint in the step 2 is 4g/s.Other step and parameter are identical with embodiment one to 21.
Embodiment 23: what this embodiment was different with one of embodiment one to 22 is that compressed-air actuated internal pressure is 0.4MPa in the step 2.Other step and parameter are identical with one of embodiment one to 22.
Embodiment 24: this embodiment is different with one of embodiment one to 23 is that the distance of spray tip and ceramic coating formed by micro-arc oxidation is 12cm in the step 2.Other step and parameter are identical with one of embodiment one to 23.
Embodiment 25: what this embodiment was different with one of embodiment one to 24 is that the spray gun translational speed is 12 ~ 18cm/s in the step 2.Other step and parameter are identical with one of embodiment one to 24.
Embodiment 26: what this embodiment was different with one of embodiment one to 24 is that the spray gun translational speed is 15cm/s in the step 2.Other step and parameter are identical with one of embodiment one to 24.
Embodiment 27: what this embodiment was different with one of embodiment one to 26 is to spray 1 back and forth.Other step and parameter are identical with one of embodiment one to 26.
Embodiment 28: this embodiment is different with one of embodiment one to 27 be the ceramic coating formed by micro-arc oxidation surface that in the step 3 step 2 obtained be coated with inorganic coating layer magnesiumalloy at 80 ~ 95 ℃ of down dry 12 ~ 18min.Other step and parameter are identical with one of embodiment one to 27.
Embodiment 29: this embodiment is different with one of embodiment one to 27 is the ceramic coating formed by micro-arc oxidation surface that in the step 3 step 2 the obtained magnesiumalloy that is coated with inorganic coating layer at 90 ℃ of dry 15min down.Other step and parameter are identical with one of embodiment one to 27.
Embodiment 30: this embodiment is different with one of embodiment one to 29 is sintering 22 ~ 28min in the step 3 and then in 240 ~ 280 ℃ retort furnace.Other step and parameter are identical with one of embodiment one to 29.
The embodiment hentriaconta-: this embodiment is different with one of embodiment one to 29 is sintering 25min in the step 3 and then in 260 ℃ retort furnace.Other step and parameter are identical with one of embodiment one to 29.
Embodiment 32: what this embodiment was different with embodiment one to one of hentriaconta-is that inorganic paint described in the step 2 is the double-component aqueous nano ceramic coating; Said double-component aqueous nano ceramic coating is the easy jade for asking rain double-component aqueous nano ceramic coating that Shenzhen auspicious magnificent quark chemical industry ltd produces; The double-component aqueous nano ceramic coating is that the ratio of 1.5:1 joins B component among the component A in the mass ratio of component A and B component, and dispersed with stirring was used after 3 hours.Other step and parameter are identical with embodiment one to one of hentriaconta-.
The micro-arc oxidation/spray coating compound film that adopts the inorganic paint of this embodiment to spray to obtain crackle just occurs after 500 ℃ thermal shock circulation 20 times; Then along with the increase of thermal shock number of times; Just crackle slowly increases, deepens; Until thermal shock 74 times, peeling phenomenon does not appear in micro-arc oxidation/spray coating compound film yet, and is good with the magnesiumalloy bonding force.
The corrosion potential of the micro-arc oxidation/spray coating compound film that this embodiment prepares is-1.02V; Corrosion potential (about 1.5V) than magnesiumalloy has been shuffled about 500mV; And the corrosion potential of the ceramic coating formed by micro-arc oxidation that step 1 obtains (1.46V); Only shuffled about 40mV than the corrosion potential (about 1.5V) of magnesiumalloy, the corrosion tendency property of the micro-arc oxidation/spray coating compound film of this embodiment on thermodynamics significantly diminishes; The corrosion electric current density of the micro-arc oxidation/spray coating compound film of this embodiment has reduced by 5 one magnitude than the corrosion electric current density of magnesiumalloy; The corrosion electric current density of the ceramic coating formed by micro-arc oxidation that obtains than step 1 has reduced by 3 one magnitude, and the corrosion tendency property of the micro-arc oxidation/spray coating compound film of this embodiment on kinetics significantly diminishes.The micro-arc oxidation/spray coating compound film that this embodiment obtains on thermodynamics and kinetics two aspects, corrosion resistance nature has all had the raising of matter.
Simultaneously, behind 72 salt mist experiment, differential arc oxidation/inorganic compounding layer still is kept perfectly harmless the differential arc oxidation of this embodiment/inorganic compounding layer under the experiment condition that 5% NaCl (analytical pure) neutral solution and salt fog the temperature inside the box are 35 ℃.The salt mist experiment time is 3 times of salt mist experiment time (24h) of the arc differential oxide ceramic layer of step 1 preparation, is 3 times of salt mist experiment time (24h) of the inorganic coating layer that directly spraying obtains on magnesiumalloy.
In sum, the micro-arc oxidation/spray coating compound film that this embodiment prepares and the bonding force of magnesiumalloy are good, and the bonding force of the inorganic coating layer of micro-arc oxidation films and aerial spraying might as well in the composite package; Erosion resistance improves greatly, and the raising of matter has been arranged.The raising of corrosion resistance is compared with independent inorganic coating layer with independent micro-arc oxidation films, the micro-arc oxidation/spray coating compound film of present embodiment is more effective to the raising of corrosion resistance of magnesium alloy, and is better.
Embodiment 33: what this embodiment was different with embodiment one to one of hentriaconta-is that inorganic paint described in the step 2 is the mixture of double-component aqueous nano ceramic coating and nano-sized filler; Wherein the interpolation quality of nano-sized filler is 1% ~ 10% of an inorganic paint quality; Said double-component aqueous nano ceramic coating is the easy jade for asking rain double-component aqueous nano ceramic coating that Shenzhen auspicious magnificent quark chemical industry ltd produces, and nano-sized filler also is to be produced by the auspicious magnificent quark chemical industry in Shenzhen ltd.Other step and parameter are identical with embodiment one to hentriaconta-.
The nano-sized filler of this embodiment is silver color filler, white filler, grey filler and the black filler etc. that Shenzhen auspicious magnificent quark chemical industry ltd provides; But being not limited to is provided by the auspicious magnificent quark chemical industry in Shenzhen ltd, and existing commercially available nanoscale powder filler all can be used for this embodiment.
Be that the ratio of 1.5:1 joins B component among the component A with the double-component aqueous nano ceramic coating in the mass ratio of component A and B component in this embodiment, and dispersed with stirring added nano-sized filler again and continues to stir after 1 ~ 3 hour and can use after 3 hours.
Present embodiment is added nano-sized filler in inorganic coating after, inorganic coating layer can prevent the entering of extraneous corrosive medium more effectively with the micropore obstruction of ceramic coating formed by micro-arc oxidation, improves the decay resistance of magnesium alloy.Behind 144 salt mist experiment, differential arc oxidation/inorganic compounding layer still is kept perfectly harmless differential arc oxidation/inorganic compounding the layer that adopts the inorganic paint of this embodiment to spray to prepare under the experiment condition that 5% NaCl (analytical pure) neutral solution and salt fog the temperature inside the box are 35 ℃.The salt mist experiment time is 6 times of salt mist experiment time (24h) of the arc differential oxide ceramic layer of step 1 preparation, is 6 times of salt mist experiment time (24h) of the inorganic coating layer that directly spraying obtains on magnesiumalloy.
The corrosion potential of the differential arc oxidation of this embodiment/inorganic compounding layer is-1.02V; Corrosion potential (about 1.5V) than magnesiumalloy has been shuffled about 500mV; And the corrosion potential of the ceramic coating formed by micro-arc oxidation that step 1 obtains (1.46V); Only shuffled about 40mV than the corrosion potential (about 1.5V) of magnesiumalloy, the corrosion tendency property of the micro-arc oxidation/spray coating compound film of this embodiment on thermodynamics significantly diminishes; The corrosion electric current density of the micro-arc oxidation/spray coating compound film of this embodiment has reduced by 5 one magnitude than the corrosion electric current density of magnesiumalloy; The corrosion electric current density of the ceramic coating formed by micro-arc oxidation that obtains than step 1 has reduced by 3 one magnitude, and the corrosion tendency property of the micro-arc oxidation/spray coating compound film of this embodiment on kinetics significantly diminishes.The micro-arc oxidation/spray coating compound film that this embodiment obtains on thermodynamics and kinetics two aspects, corrosion resistance nature has all had the raising of matter.
The micro-arc oxidation/spray coating compound film that adopts the inorganic paint of this embodiment to spray to obtain crackle just occurs after 500 ℃ thermal shock circulation 20 times; Then along with the increase of thermal shock number of times; Just crackle slowly increases, deepens; Until thermal shock 74 times, peeling phenomenon does not appear in micro-arc oxidation/spray coating compound film yet, and is good with the magnesiumalloy bonding force.
Embodiment 34: what this embodiment was different with embodiment one to one of hentriaconta-is that inorganic paint described in the step 2 is the mixture of double-component aqueous nano ceramic coating and nano-sized filler; Wherein the interpolation quality of nano-sized filler is 2% ~ 8% of an inorganic paint quality; Said double-component aqueous nano ceramic coating is the easy jade for asking rain double-component aqueous nano ceramic coating that Shenzhen auspicious magnificent quark chemical industry ltd produces, and nano-sized filler also is to be produced by the auspicious magnificent quark chemical industry in Shenzhen ltd.Other step and parameter are identical with embodiment one to hentriaconta-.
The nano-sized filler of this embodiment is silver color filler, white filler, grey filler and the black filler etc. that Shenzhen auspicious magnificent quark chemical industry ltd provides; But being not limited to is provided by the auspicious magnificent quark chemical industry in Shenzhen ltd, and existing commercially available nanoscale powder filler all can be used for this embodiment.
Embodiment 35: what this embodiment was different with embodiment one to one of hentriaconta-is that inorganic paint described in the step 2 is the mixture of double-component aqueous nano ceramic coating and nano-sized filler; Wherein the interpolation quality of nano-sized filler is 5% of an inorganic paint quality; Said double-component aqueous nano ceramic coating is the easy jade for asking rain double-component aqueous nano ceramic coating that Shenzhen auspicious magnificent quark chemical industry ltd produces, and nano-sized filler also is to be produced by the auspicious magnificent quark chemical industry in Shenzhen ltd.Other step and parameter are identical with embodiment one to hentriaconta-.
The nano-sized filler of this embodiment is silver color filler, white filler, grey filler and the black filler etc. that Shenzhen auspicious magnificent quark chemical industry ltd provides; But being not limited to is provided by the auspicious magnificent quark chemical industry in Shenzhen ltd, and existing commercially available nanoscale powder filler all can be used for this embodiment.
Embodiment 36: the preparation method of this embodiment magnesium alloy surface micro-arc oxidation/spray coating compound film realizes through following steps: one, the AZ31B magnesiumalloy is carried out pre-treatment and remove surface film oxide; Then pretreated magnesiumalloy is placed electrolytic solution as working electrode; Stainless steel tank is as electrolyzer and counter electrode; Adopt constant current mode differential arc oxidation 5min, promptly on magnesiumalloy, obtain the porous ceramic coating formed by micro-arc oxidation, wherein electrolytic solution consists of: the Na of 6g/L
2SiO
3, the NaF of 2g/L and the NaOH of 2g/L, solvent is a water; Control current density is 2A/dm
2, frequency is 300Hz, dutycycle is 45%; Two, adopt the aerial spraying mode on the magnesium alloy surface micro-arc oxidation ceramic membrane that step 1 obtains, to spray inorganic coating layer; The quantity for spray of control inorganic paint is 3 ~ 5g/s, and compressed-air actuated internal pressure is 0.4MPa, and it is the spray gun of 1mm that nozzle diameter is adopted in spraying; Control spray gun and magnesium alloy surface micro-arc oxidation ceramic membrane are rectangular; The distance of spray tip and ceramic coating formed by micro-arc oxidation is 12cm, and spray gun runs parallel, and the spray gun translational speed is 15cm/s; Spraying 2 back and forth, obtain the ceramic coating formed by micro-arc oxidation surface be coated with inorganic coating layer magnesiumalloy; Said inorganic paint is the easy jade for asking rain double-component aqueous nano ceramic coating that Shenzhen auspicious magnificent quark chemical industry ltd produces, and be that the ratio of 1.5:1 joins B component among the component A in the mass ratio of component A and B component, and dispersed with stirring is used after 3 hours; Said 1 be meant back and forth spray gun in the side shifting on ceramic coating formed by micro-arc oxidation surface to opposite side, move back to origination side again; Three, the ceramic coating formed by micro-arc oxidation surface that step 2 is obtained is coated with magnesiumalloy dry 20min under 90 ℃ of inorganic coating layer; And then in 300 ℃ retort furnace sintering 30min; Then magnesiumalloy is taken out; Naturally cool to room temperature, promptly prepare micro-arc oxidation/spray coating compound film at Mg alloy surface.
The thickness of the ceramic coating formed by micro-arc oxidation that this embodiment step 1 prepares is 11.2 μ m, and roughness is 0.456 μ m, and the ceramic membrane surface sem photograph is as shown in Figure 1, and visible ceramic membrane surface is evenly smooth, has been covered with the micropore of even micro-aperture.
The thickness of the inorganic coating layer that the micro-arc oxidation/spray coating compound film air spraying that this embodiment obtains obtains is about 15 μ m; Inorganic coating layer all covers ceramic coating formed by micro-arc oxidation; The composite package surface does not have micropore, shown in the sem photograph of the micro-arc oxidation/spray coating compound film that obtains like this embodiment among Fig. 2.
The cross section sem photograph of the micro-arc oxidation/spray coating compound film that this embodiment obtains is as shown in Figure 3; The position of "
" micro-arc oxidation/spray coating compound film that refers among the figure; Visible by Fig. 3; The part inorganic paint embeds in the aperture of ceramic membrane deeply in the inorganic coating layer, combines well with ceramic membrane.This embodiment has carried out the bonding force of cut test evaluation inorganic coating layer and ceramic coating formed by micro-arc oxidation according to standard GB/T 1720-1979 to the micro-arc oxidation/spray coating compound film that obtains simultaneously; Test result shows that the inorganic paint adhesive force of coatings is primary standard, explains that inorganic coating layer and ceramic membrane bonding force are good.
Present embodiment is carried out the thermal shock experiment to the micro-arc oxidation/spray coating compound film that obtains; Concrete operations are: constant temperature after Muffle furnace is warmed up to 500 ℃, and the magnesium alloy that has micro-arc oxidation/spray coating compound film that then present embodiment is obtained is put Muffle furnace constant temperature 2min into, adopts manual time-keeping; Taking out sample behind the constant temperature 2min immerses in the water under the preprepared room temperature immediately; Treat to cool off fully the back taking-up and dry up, and examine the variation of film surface, this is a circulation; Continue the repetition aforesaid operations, observe film surface and change.Experimental result shows, micro-arc oxidation/spray coating compound film crackle just occurs after thermal shock 20 times, and along with the increase of thermal shock number of times, just crackle slowly increases, deepens then, and until thermal shock 74 times, peeling phenomenon does not appear in micro-arc oxidation/spray coating compound film yet.It is thus clear that micro-arc oxidation/spray coating compound film that this embodiment obtains and magnesiumalloy bonding force are good.
This embodiment (does not carry out pre-treatment to the micro-arc oxidation/spray coating compound film for preparing, ceramic coating formed by micro-arc oxidation and the AZ31B magnesiumalloy that step 1 obtains; There is natural oxide film on the surface) three kinds of samples carry out the corrosion resistance nature test; Adopt the CHI660a electrochemical workstation; In three-electrode system, sample is a working electrode, and bare area is 1cm
2, SCE is a reference electrode, platinized platinum is a supporting electrode.Corrosive medium is the 3.5%NaCl aqueous solution, and pH=7, probe temperature are 25 ℃.Ta Feier (Tafel) polarization curve test scan speed is 1mV/s, and sweep interval is open circuit potential-0.2～0V.It is as shown in Figure 4 that test obtains the Tafel polarization curve; "-▼-" is the Tafel polarization curve of this embodiment to the micro-arc oxidation/spray coating compound film for preparing among the figure; "-●-" the Tafel polarization curve of the ceramic coating formed by micro-arc oxidation that obtains for step 1, "-■-" is the Tafel polarization curve of AZ31B magnesiumalloy.Visible by Fig. 4; The corrosion potential of micro-arc oxidation/spray coating compound film is-1.02V; Corrosion potential (about 1.5V) than AZ31B magnesiumalloy has been shuffled about 500mV; And the corrosion potential of the ceramic coating formed by micro-arc oxidation that step 1 obtains (1.46V) only shuffled about 40mV, the corrosion tendency property of the micro-arc oxidation/spray coating compound film of this embodiment on thermodynamics significantly diminishes; The corrosion electric current density of micro-arc oxidation/spray coating compound film has reduced by 5 one magnitude than the corrosion electric current density of AZ31B magnesiumalloy; The corrosion electric current density of the ceramic coating formed by micro-arc oxidation that obtains than step 1 has reduced by 3 one magnitude, and the corrosion tendency property of the micro-arc oxidation/spray coating compound film of this embodiment on kinetics significantly diminishes.The micro-arc oxidation/spray coating compound film that this embodiment obtains on thermodynamics and kinetics two aspects, corrosion resistance nature has all had the raising of matter.
As a comparison; Carry out following simultaneous test: the AZ31B magnesiumalloy is polished with the sand paper of 240# and 1000# respectively; Remove surface film oxide; Then magnesiumalloy is carried out sandblasting, magnesium alloy surface spraying inorganic paint (being inorganic paint described in this implementation step two), must obtain inorganic coating layer again at Mg alloy surface.
This embodiment carries out salt mist experiment to three kinds of samples of the Mg alloy surface inorganic coating layer of the micro-arc oxidation/spray coating compound film for preparing, ceramic coating formed by micro-arc oxidation that step 1 obtains and above-mentioned simultaneous test; SaltSprayTest adopts is 5% NaCl (analytical pure) neutral solution, and salt fog the temperature inside the box is 35 ℃; In the experimentation, every 24h checks that once salt-fog test criterion is: with the most serious one side of the two-sided middle corrosion of sample is judgment basis, and the stain or the hot spot that occur with specimen surface serve as experiment end foundation greater than 3 places.Through test, directly spray the Mg alloy surface inorganic coating layer sample salt mist experiment 24h of inorganic paint, large-area corrosion pit just appears in specimen surface, and dope layer is corroded and peels off, and is as shown in Figure 5; A large amount of stains has appearred in the surface behind the ceramic coating formed by micro-arc oxidation process salt mist experiment 24h that step 1 obtains, and some places have exposed matrix, and are as shown in Figure 6; The micro-arc oxidation/spray coating compound film of this embodiment more stain just occurs through salt mist experiment 72h surface, and other place also remains intact harmless, and whole rete does not have obscission, and is as shown in Figure 7.The salt mist experiment time of the micro-arc oxidation/spray coating compound film that this embodiment prepares is 3 times of salt mist experiment time of independent micro-arc oxidation films or independent inorganic coating layer.
In sum, the micro-arc oxidation/spray coating compound film that this embodiment prepares and the bonding force of magnesiumalloy are good, and the bonding force of the inorganic coating layer of micro-arc oxidation films and aerial spraying might as well in the composite package; Erosion resistance improves greatly, and the raising of matter has been arranged.The raising of corrosion resistance is compared with independent inorganic coating layer with independent micro-arc oxidation films, the micro-arc oxidation/spray coating compound film of present embodiment is more effective to the raising of corrosion resistance of magnesium alloy, and is better.
Embodiment 37: what this embodiment and embodiment 36 were different is that inorganic paint described in the step 2 is the mixture of double-component aqueous nano ceramic coating and silver color filler; Wherein the interpolation quality of silver color filler is 5% of an inorganic paint quality; Said double-component aqueous nano ceramic coating is the easy jade for asking rain double-component aqueous nano ceramic coating that Shenzhen auspicious magnificent quark chemical industry ltd produces, and the silver color filler also is to be produced by the auspicious magnificent quark chemical industry in Shenzhen ltd.Other step and parameter and embodiment 30 six phases are together.
The thickness of the inorganic coating layer that the micro-arc oxidation/spray coating compound film air spraying that this embodiment obtains obtains is about 15 μ m, and inorganic coating layer all covers ceramic coating formed by micro-arc oxidation, and the composite package surface does not have micropore.
This embodiment has carried out the bonding force of cut test evaluation inorganic coating layer and ceramic coating formed by micro-arc oxidation according to standard GB/T 1720-1979 to the micro-arc oxidation/spray coating compound film that obtains; Test result shows that the inorganic paint adhesive force of coatings is a primary standard, explains that inorganic coating layer and ceramic membrane bonding force are good.
This embodiment carries out salt mist experiment to the micro-arc oxidation/spray coating compound film for preparing, and the salt mist experiment parameter is the same with salt mist experiment described in criterion and the embodiment 36.Salt mist experiment is the result show, the micro-arc oxidation/spray coating compound film of this embodiment a stain only occurs through salt mist experiment 144h surface, and other place also remains intact harmless, and is as shown in Figure 8.Explain that the micro-arc oxidation/spray coating compound film that the inorganic paint of the mixture that adopts double-component aqueous nano ceramic coating and silver color filler obtains is better to the barrier propterty of magnesiumalloy, corrosion resistance nature is better.
The micro-arc oxidation/spray coating compound film that this embodiment prepares and the bonding force of magnesiumalloy are good, and the bonding force of the inorganic coating layer of micro-arc oxidation films and aerial spraying might as well in the composite package; Erosion resistance improves greatly, and the raising of matter has been arranged.The raising of corrosion resistance is compared with independent inorganic coating layer with independent micro-arc oxidation films, the micro-arc oxidation/spray coating compound film of present embodiment is more effective to the raising of corrosion resistance of magnesium alloy, and is better.
Embodiment 38: what this embodiment and embodiment 36 were different is to adopt constant current mode differential arc oxidation 20min in the step 1, promptly on magnesiumalloy, obtains the porous ceramic coating formed by micro-arc oxidation, and wherein electrolytic solution consists of: the Na of 6g/L
2SiO
3, the NaF of 2g/L and the NaOH of 2g/L, solvent is a water; Control current density is 5A/dm
2, frequency is 2000Hz, dutycycle is 45%.Other step and parameter and embodiment 30 six phases are together.
The thickness of micro-arc oxidation films reaches 21 μ m in the micro-arc oxidation/spray coating compound film that this embodiment obtains; The thickness of the inorganic coating layer that aerial spraying obtains is about 15 μ m; Inorganic coating layer all covers ceramic coating formed by micro-arc oxidation, and the composite package surface does not have micropore, and is as shown in Figure 9.
This embodiment carries out the thermal shock experiment to the micro-arc oxidation/spray coating compound film that obtains, described in concrete operations such as the embodiment 36.Experimental result shows, micro-arc oxidation/spray coating compound film crackle occurs after thermal shock 12 times, and along with the increase of thermal shock number of times, crackle slowly increases, deepens then, and until thermal shock 70 times, peeling phenomenon appears in micro-arc oxidation/spray coating compound film.Thus it is clear that, though micro-arc oxidation/spray coating compound film that this embodiment obtains and magnesiumalloy bonding force are still fine not as the composite package in the embodiment 36.
The cross section sem photograph of the micro-arc oxidation/spray coating compound film that this embodiment obtains is shown in figure 10; The position of "
" micro-arc oxidation/spray coating compound film that refers among the figure; Visible by Figure 10, the part inorganic paint embeds in the aperture of ceramic membrane deeply in the inorganic coating layer, combines with ceramic membrane well; Can find out simultaneously; Current density increases, and the reaction times increases, and makes the thickness thickening of micro-arc oxidation films; Surface irregularity is uneven, and it is big that roughness becomes.This embodiment has carried out the bonding force of cut test evaluation inorganic coating layer and ceramic coating formed by micro-arc oxidation according to standard GB/T 1720-1979 to the micro-arc oxidation/spray coating compound film that obtains; Test result shows that the inorganic paint adhesive force of coatings is a primary standard, explains that inorganic coating layer and ceramic membrane bonding force are good.
This embodiment carries out salt mist experiment to the micro-arc oxidation/spray coating compound film for preparing, and the salt mist experiment parameter is the same with salt mist experiment described in the embodiment 36 with criterion.Salt mist experiment is the result show, the micro-arc oxidation/spray coating compound film of this embodiment a stain only occurs through salt mist experiment 80h surface, and other place also remains intact harmless.
Embodiment 39: what this embodiment and embodiment 36 were different is to adopt constant current mode differential arc oxidation 10min in the step 1, promptly on magnesiumalloy, obtains the porous ceramic coating formed by micro-arc oxidation, and wherein electrolytic solution consists of: the Na of 6g/L
2SiO
3, the NaF of 2g/L and the NaOH of 2g/L, solvent is a water; Control current density is 3A/dm
2, frequency is 300Hz, dutycycle is 45%; Inorganic paint described in the step 2 is the mixture of double-component aqueous nano ceramic coating and silver color filler; Wherein the interpolation quality of silver color filler is 5% of an inorganic paint quality; Said double-component aqueous nano ceramic coating is the easy jade for asking rain double-component aqueous nano ceramic coating that Shenzhen auspicious magnificent quark chemical industry ltd produces, and the silver color filler also is to be produced by the auspicious magnificent quark chemical industry in Shenzhen ltd.Other step and parameter and embodiment 30 six phases are together.
The thickness of micro-arc oxidation films reaches 16.5 μ m in the micro-arc oxidation/spray coating compound film that this embodiment of this embodiment obtains; The thickness of the inorganic coating layer that aerial spraying obtains is about 15 μ m; Inorganic coating layer all covers ceramic coating formed by micro-arc oxidation; The composite package surface does not have micropore, and is shown in figure 11.
The cross section sem photograph of the micro-arc oxidation/spray coating compound film that this embodiment obtains is shown in figure 12; The position of "
" micro-arc oxidation/spray coating compound film that refers among the figure; Visible by Figure 12; The part inorganic paint embeds in the aperture of ceramic membrane deeply in the inorganic coating layer, combines well with ceramic membrane.This embodiment has carried out the bonding force of cut test evaluation inorganic coating layer and ceramic coating formed by micro-arc oxidation according to standard GB/T 1720-1979 to the micro-arc oxidation/spray coating compound film that obtains; Test result shows that the inorganic paint adhesive force of coatings is a primary standard, explains that inorganic coating layer and ceramic membrane bonding force are good.
This embodiment carries out salt mist experiment to the micro-arc oxidation/spray coating compound film for preparing, and the salt mist experiment parameter is the same with salt mist experiment described in criterion and the embodiment 36.Salt mist experiment is the result show, the micro-arc oxidation/spray coating compound film of this embodiment a stain only occurs through salt mist experiment 144h surface, and other place also remains intact harmless.
The micro-arc oxidation/spray coating compound film that this embodiment prepares and the bonding force of magnesiumalloy are good, and the bonding force of the inorganic coating layer of micro-arc oxidation films and aerial spraying might as well in the composite package; Erosion resistance improves greatly, and the raising of matter has been arranged.The raising of corrosion resistance is compared with independent inorganic coating layer with independent micro-arc oxidation films, the micro-arc oxidation/spray coating compound film of present embodiment is more effective to the raising of corrosion resistance of magnesium alloy, and is better.
Claims (8)
1. the preparation method of a magnesium alloy surface micro-arc oxidation/spray coating compound film; The preparation method who it is characterized in that micro-arc oxidation/spray coating compound film on the Mg alloy surface realizes through following steps: one, magnesiumalloy is carried out pre-treatment and remove surface film oxide; Then pretreated magnesiumalloy is placed electrolytic solution as working electrode; Stainless steel tank is as electrolyzer and counter electrode; Adopt constant voltage or constant current mode differential arc oxidation 5～20min, promptly on magnesiumalloy, obtain the porous ceramic coating formed by micro-arc oxidation, wherein electrolytic solution consists of: the Na of 6～30g/L
2SiO
3, the NaF of 0～5g/L and the NaOH of 0～5g/L, solvent is a water; During constant voltage mode, control voltage is 50～600V, and frequency is 300～2000Hz, and dutycycle is 10～45%; During constant current mode, control current density is 2～5A/dm
2, frequency is 300～2000Hz, dutycycle is 10～45%; Two, adopt the aerial spraying mode on the magnesium alloy surface micro-arc oxidation ceramic membrane that step 1 obtains, to spray inorganic coating layer; The spraying rate of control inorganic paint is 3～5g/s, and compressed-air actuated internal pressure is 0.3～0.5MPa, and it is the spray gun of 1mm that nozzle diameter is adopted in spraying; Control spray gun and magnesium alloy surface micro-arc oxidation ceramic membrane are rectangular; The distance of spray tip and ceramic coating formed by micro-arc oxidation is 10～15cm, and spray gun runs parallel, and the spray gun translational speed is 10～20cm/s; Spray 1～2 back and forth, obtain the ceramic coating formed by micro-arc oxidation surface be coated with inorganic coating layer magnesiumalloy; Said inorganic paint is the double-component aqueous nano ceramic coating, and said double-component aqueous nano ceramic coating is that Shenzhen auspicious magnificent quark chemical industry ltd produces; Said 1 be meant back and forth spray gun in the side shifting on ceramic coating formed by micro-arc oxidation surface to opposite side, move back to origination side again; Three, the ceramic coating formed by micro-arc oxidation surface that step 2 is obtained is coated with the magnesiumalloy of inorganic coating layer at 60～100 ℃ of down dry 10～20min; And then in 230～300 ℃ retort furnace sintering 20～30min; Then magnesiumalloy is taken out; Naturally cool to room temperature, promptly prepare micro-arc oxidation/spray coating compound film at Mg alloy surface.
2. the preparation method of a kind of magnesium alloy surface micro-arc oxidation/spray coating compound film according to claim 1 is characterized in that magnesiumalloy is AZ31B magnesiumalloy, AZ91D magnesiumalloy, MB26 magnesiumalloy, ZM5 magnesiumalloy or magnesium lithium alloy in the step 1.
3. the preparation method of a kind of magnesium alloy surface micro-arc oxidation/spray coating compound film according to claim 1 and 2 is characterized in that electrolytic solution consists of in the step 1: the Na of 6～30g/L
2SiO
3, solvent is a water.
4. the preparation method of a kind of magnesium alloy surface micro-arc oxidation/spray coating compound film according to claim 1 and 2 is characterized in that the spraying rate of control inorganic paint in the step 2 is 4g/s.
5. the preparation method of a kind of magnesium alloy surface micro-arc oxidation/spray coating compound film according to claim 4 is characterized in that the spray gun translational speed is 12～18cm/s in the step 2.
6. according to the preparation method of claim 1,2 or 5 described a kind of magnesium alloy surface micro-arc oxidation/spray coating compound films, it is characterized in that the ceramic coating formed by micro-arc oxidation surface that in the step 3 step 2 is obtained is coated with magnesiumalloy dry 12～18min under 80～95 ℃ of inorganic coating layer.
7. the preparation method of a kind of magnesium alloy surface micro-arc oxidation/spray coating compound film according to claim 6 is characterized in that in the step 3 and then sintering 22～28min in 240～280 ℃ retort furnace.
8. according to the preparation method of claim 1,2,5 or 7 described a kind of magnesium alloy surface micro-arc oxidation/spray coating compound films; It is characterized in that inorganic paint described in the step 2 is the double-component aqueous nano ceramic coating; Said double-component aqueous nano ceramic coating is the easy jade for asking rain double-component aqueous nano ceramic coating that Shenzhen auspicious magnificent quark chemical industry ltd produces; The double-component aqueous nano ceramic coating is that 1.5: 1 ratio joins B component among the component A in the mass ratio of component A and B component, and dispersed with stirring was used after 3 hours.
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| CN101376790A (en) * | 2007-08-30 | 2009-03-04 | 比亚迪股份有限公司 | Anti-corrosive paint for magnesium alloy and preparation thereof |
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