CN101871119A - 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 membrane.
Background technology
Magnesium alloy is called as " 21 century tool development potentiality and the green engineering material of future ", has specific tenacity and specific rigidity height, 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, the magnesium alloy reclaiming is good, compliance with environmental protection requirements.In view of above advantage, magnesium alloy is widely used in fields such as automobile, electronic apparatus, aerospace, defence and military, traffic.But the magnesium alloy electropotential is low, and chemical activity is high, and stability is low, very easily corrodes in a humid environment.Though magnesium alloy can react with airborne oxygen and generate one deck natural oxide film, this oxide film 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 magnesium alloy have seriously limited its application on engineering.Therefore, the etching problem of magnesium alloy becomes " bottleneck " of the further widespread use of magnesium alloy.
The surface modification treatment technology has become one of important means of improving the magnesium alloy 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 magnesium alloy.But the general rete that obtains of chemical conversion film, anodic oxidation and vapour deposition is thin (thickness is generally in nano level or several micrometer range), and 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 magnesium alloy, but because the porousness of its structure, therefore it also is limited improving corrosion resistance nature, application techniques is divided into organic and inorganic two kinds, 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; Ion injection method cost height is difficult to realize big area processing; Coating and magnesium alloy substrate bonding force are poor, and the easy aged problem of organic coating 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 by following steps: one, magnesium alloy is carried out pre-treatment and remove surface film oxide, then pretreated magnesium alloy 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 obtain the porous ceramic coating formed by micro-arc oxidation on magnesium alloy, 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, compressed-air actuated internal pressure is 0.3 ~ 0.5MPa, 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, spray gun runs parallel, 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 magnesium alloy; Described 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 described double-component aqueous nano ceramic coating and nano-sized filler are Shenzhen auspicious magnificent quark chemical industry company limited and produce; Described 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 magnesium alloy of inorganic coating layer at 60 ~ 100 ℃ of down dry 10 ~ 20min, and then in 230 ~ 300 ℃ retort furnace sintering 20 ~ 30min, then magnesium alloy is taken out, naturally cool to room temperature, promptly prepare micro-arc oxidation/spray coating compound film at Mg alloy surface.
Magnesium alloy 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, magnesium alloy 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, distilled 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 be provided by the auspicious magnificent quark chemical industry in Shenzhen company limited, 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 company limited, but being not limited to is provided by the auspicious magnificent quark chemical industry in Shenzhen company limited, 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 big area composite membrane.Combine the advantage of differential arc oxidization technique and aerial spraying technology two class 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 magnesium alloy comprehensively.Utilize the porous characteristics of ceramic coating formed by micro-arc oxidation simultaneously, make inorganic paint good, solved the paint coatings that directly on magnesium alloy, sprays and combined poorly with magnesium alloy, easily come off, do not reach the drawback of fine protection effect with combining of ceramic coating formed by micro-arc oxidation.
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, the thickness of the transparent inorganic coating layer that obtains by aerial spraying is about 15 μ m, can block whole hole, Micro-Arc Oxidized Ceramic Coating surface, 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 magnesium alloy when having omitted directly on magnesium alloy 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/T1720-1979, test result shows that the inorganic paint adhesive force of coatings is primary standard, illustrates that inorganic coating layer and ceramic membrane bonding force are good.
The ceramic film that the present invention obtains by differential arc oxidation and the bonding force of magnesium alloy are strong, inorganic coating layer and ceramic membrane bonding force are good, then the bonding force of the composite membrane that obtains of the present invention and magnesium alloy is good, and composite membrane to corrosion resistance of magnesium alloy can raising clearly effect is arranged, than directly spraying on magnesium alloy, 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 magnesium alloy 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 magnesium alloy 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 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 orders of magnitude than the corrosion electric current density of magnesium alloy, the corrosion electric current density of the ceramic coating formed by micro-arc oxidation that obtains than step 1 has reduced by 3 orders of magnitude, and the corrosion tendency 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, differential arc oxidation of the present invention/inorganic compounding layer is at 5% NaCl(analytical pure) neutral solution and salt fog the temperature inside the box be under 35 ℃ the experiment condition behind the salt mist experiment of 72 ~ 144h, differential arc oxidation/inorganic compounding layer still is kept perfectly harmless.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 magnesium alloy.
In sum, the micro-arc oxidation/spray coating compound film that the present invention prepares and the bonding force of magnesium alloy 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 membrane; 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 magnesium alloy (do not carry out pre-treatment, there is natural oxide film on the surface) test; Fig. 5 be the Mg alloy surface inorganic coating layer sample of direct spraying inorganic paint of the contrast experiment in the embodiment 36 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 solution 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 present embodiment magnesium alloy surface micro-arc oxidation/spray coating compound film realizes by following steps: one, magnesium alloy is carried out pre-treatment and remove surface film oxide, then pretreated magnesium alloy 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 obtain the porous ceramic coating formed by micro-arc oxidation on magnesium alloy, 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, compressed-air actuated internal pressure is 0.3 ~ 0.5MPa, 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, spray gun runs parallel, 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 magnesium alloy; Described 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 described double-component aqueous nano ceramic coating and nano-sized filler are Shenzhen auspicious magnificent quark chemical industry company limited and produce; Described 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 magnesium alloy of inorganic coating layer at 60 ~ 100 ℃ of down dry 10 ~ 20min, and then in 230 ~ 300 ℃ retort furnace sintering 20 ~ 30min, then magnesium alloy 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 the present embodiment step 2 is not limited to be provided by the auspicious magnificent quark chemical industry in Shenzhen company limited, 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 company limited, but being not limited to is provided by the auspicious magnificent quark chemical industry in Shenzhen company limited, and existing commercially available nanoscale powder filler all can be used for the present invention.
Present 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 magnesium alloy are strong, then the bonding force of the composite membrane that obtains of present embodiment and magnesium alloy is good, and composite membrane to corrosion resistance of magnesium alloy can raising clearly effect is arranged, than directly spraying on magnesium alloy, and the corrosion resistance nature of simple ceramic coating formed by micro-arc oxidation is better.
Embodiment two: what present embodiment and embodiment one were different is that magnesium alloy is AZ91D magnesium alloy, AZ31B magnesium alloy, magnesium lithium alloy, MB26 or ZM5 in the step 1.Other step and parameter are identical with embodiment one.
Embodiment three: what present embodiment was different with embodiment one or two is that magnesium alloy carries out pretreated being operating as in the step 1: clean Mg alloy surface with scrubbing powder, clean with flushing with clean water then, magnesium alloy after the cleaning is used the water-proof abrasive paper sanding and polishing of 240#, 400#, 800# and 1000# successively, cleans with tap water, distilled water and acetone successively respectively then.Other step and parameter are identical with embodiment one or two.
Embodiment four: what present 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 the present embodiment, and it is big that the film surface roughness becomes.
Embodiment five: what present 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 present 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 the present 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 present 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 present 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 present 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 the present embodiment
2SiO
3Be main membrane-forming agent, NaF is little to the thicknesses of layers influence, and the effect of NaF mainly is to adjust the rete microscopic appearance, makes rete more smooth, evenly.
Embodiment ten: what present 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 present 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 present 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 the present embodiment
2SiO
3Be main membrane-forming agent, NaOH is little to the thicknesses of layers influence, and the effect of NaOH mainly is to adjust the rete microscopic appearance, makes rete more smooth, evenly.
Embodiment 13: what present 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 present 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 present 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 the present 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 to adjust the rete microscopic appearance, makes rete more smooth, evenly.
Embodiment 16: what present 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 present 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: present 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 the present embodiment, voltage constant is constant in the differential arc oxidation process, electric current is along with the carrying out of reaction constantly reduces, 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: present 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: present 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 the present embodiment, current constant is constant in the differential arc oxidation process, voltage is along with the carrying out of reaction constantly increases, 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: present 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: present 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 present 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: present 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 present 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 present 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 present 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: what present embodiment was different with one of embodiment one to 27 is that the ceramic coating formed by micro-arc oxidation surface that in the step 3 step 2 is obtained is coated with the magnesium alloy of inorganic coating layer at 80 ~ 95 ℃ of down dry 12 ~ 18min.Other step and parameter are identical with one of embodiment one to 27.
Embodiment 29: what present embodiment was different with one of embodiment one to 27 is that the ceramic coating formed by micro-arc oxidation surface that in the step 3 step 2 is obtained is coated with the magnesium alloy of inorganic coating layer at 90 ℃ of following dry 15min.Other step and parameter are identical with one of embodiment one to 27.
Embodiment 30: present 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-: present 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: present embodiment and embodiment one to one of hentriaconta-different be that inorganic paint described in the step 2 is the double-component aqueous nano ceramic coating, described 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 company limited 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 to one of hentriaconta-with embodiment one.
The micro-arc oxidation/spray coating compound film that adopts the inorganic paint of present 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 magnesium alloy bonding force.
The corrosion potential of the micro-arc oxidation/spray coating compound film that present embodiment prepares is-1.02V, corrosion potential (about 1.5V) than magnesium alloy 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 magnesium alloy, the corrosion tendency of the micro-arc oxidation/spray coating compound film of present embodiment on thermodynamics significantly diminishes; The corrosion electric current density of the micro-arc oxidation/spray coating compound film of present embodiment has reduced by 5 orders of magnitude than the corrosion electric current density of magnesium alloy, the corrosion electric current density of the ceramic coating formed by micro-arc oxidation that obtains than step 1 has reduced by 3 orders of magnitude, and the corrosion tendency of the micro-arc oxidation/spray coating compound film of present embodiment on kinetics significantly diminishes.The micro-arc oxidation/spray coating compound film that present embodiment obtains on thermodynamics and kinetics two aspects, corrosion resistance nature has all had the raising of matter.
Simultaneously, the differential arc oxidation of present embodiment/inorganic compounding layer is at 5% NaCl(analytical pure) neutral solution and salt fog the temperature inside the box be under 35 ℃ the experiment condition behind 72 salt mist experiment, differential arc oxidation/inorganic compounding layer still is kept perfectly harmless.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 magnesium alloy.
In sum, the micro-arc oxidation/spray coating compound film that present embodiment prepares and the bonding force of magnesium alloy 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 membrane; 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, 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: present embodiment and embodiment one to one of hentriaconta-different be 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, described 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 company limited produces, and nano-sized filler also is to be produced by the auspicious magnificent quark chemical industry in Shenzhen company limited.Other step and parameter are identical to hentriaconta-with embodiment one.
Silver color filler, white filler, grey filler and black filler etc. that the nano-sized filler of present embodiment provides for the auspicious magnificent quark chemical industry in Shenzhen company limited, but being not limited to is provided by the auspicious magnificent quark chemical industry in Shenzhen company limited, and existing commercially available nanoscale powder filler all can be used for present 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 the present 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 paint after, inorganic coating layer can prevent entering of extraneous corrosive medium more effectively with the micropore obstruction of ceramic coating formed by micro-arc oxidation, improves the corrosion resistance nature of magnesium alloy.Differential arc oxidation/inorganic compounding the layer that adopts the inorganic paint of present embodiment to spray to prepare is at 5% NaCl(analytical pure) neutral solution and salt fog the temperature inside the box be under 35 ℃ the experiment condition behind 144 salt mist experiment, differential arc oxidation/inorganic compounding layer still is kept perfectly harmless.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 magnesium alloy.
The corrosion potential of the differential arc oxidation of present embodiment/inorganic compounding layer is-1.02V, corrosion potential (about 1.5V) than magnesium alloy 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 magnesium alloy, the corrosion tendency of the micro-arc oxidation/spray coating compound film of present embodiment on thermodynamics significantly diminishes; The corrosion electric current density of the micro-arc oxidation/spray coating compound film of present embodiment has reduced by 5 orders of magnitude than the corrosion electric current density of magnesium alloy, the corrosion electric current density of the ceramic coating formed by micro-arc oxidation that obtains than step 1 has reduced by 3 orders of magnitude, and the corrosion tendency of the micro-arc oxidation/spray coating compound film of present embodiment on kinetics significantly diminishes.The micro-arc oxidation/spray coating compound film that present 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 present 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 magnesium alloy bonding force.
Embodiment 34: present embodiment and embodiment one to one of hentriaconta-different be 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, described 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 company limited produces, and nano-sized filler also is to be produced by the auspicious magnificent quark chemical industry in Shenzhen company limited.Other step and parameter are identical to hentriaconta-with embodiment one.
Silver color filler, white filler, grey filler and black filler etc. that the nano-sized filler of present embodiment provides for the auspicious magnificent quark chemical industry in Shenzhen company limited, but being not limited to is provided by the auspicious magnificent quark chemical industry in Shenzhen company limited, and existing commercially available nanoscale powder filler all can be used for present embodiment.
Embodiment 35: present embodiment and embodiment one to one of hentriaconta-different be 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, described 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 company limited produces, and nano-sized filler also is to be produced by the auspicious magnificent quark chemical industry in Shenzhen company limited.Other step and parameter are identical to hentriaconta-with embodiment one.
Silver color filler, white filler, grey filler and black filler etc. that the nano-sized filler of present embodiment provides for the auspicious magnificent quark chemical industry in Shenzhen company limited, but being not limited to is provided by the auspicious magnificent quark chemical industry in Shenzhen company limited, and existing commercially available nanoscale powder filler all can be used for present embodiment.
Embodiment 36: the preparation method of present embodiment magnesium alloy surface micro-arc oxidation/spray coating compound film realizes by following steps: one, the AZ31B magnesium alloy is carried out pre-treatment and remove surface film oxide, then pretreated magnesium alloy 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 obtain the porous ceramic coating formed by micro-arc oxidation on magnesium alloy, 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, compressed-air actuated internal pressure is 0.4MPa, 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, spray gun runs parallel, 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 magnesium alloy; Described inorganic paint is the easy jade for asking rain double-component aqueous nano ceramic coating that Shenzhen auspicious magnificent quark chemical industry company limited 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; Described 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 magnesium alloy dry 20min under 90 ℃ of inorganic coating layer, and then in 300 ℃ retort furnace sintering 30min, then magnesium alloy 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 the present embodiment step 1 prepares is 11.2 μ m, and roughness is 0.456 μ m, the ceramic membrane surface sem photograph as shown in Figure 1, 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 aerial spraying obtains in the micro-arc oxidation/spray coating compound film that present embodiment obtains is about 15 μ m, inorganic coating layer all covers ceramic coating formed by micro-arc oxidation, the composite membrane surface does not have micropore, shown in the sem photograph of the micro-arc oxidation/spray coating compound film that obtains as present embodiment among Fig. 2.
The cross section sem photograph of the micro-arc oxidation/spray coating compound film that present embodiment obtains as shown in Figure 3, among the figure "
" position of the micro-arc oxidation/spray coating compound film that refers to, as seen from Figure 3, the part inorganic paint embeds in the aperture of ceramic membrane deeply in the inorganic coating layer, combines well with ceramic membrane.Present embodiment has been carried out the bonding force of cut test evaluation inorganic coating layer and ceramic coating formed by micro-arc oxidation according to standard GB/T1720-1979 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, illustrates 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 retort furnace is warmed up to 500 ℃, the magnesium alloy that has micro-arc oxidation/spray coating compound film that then present embodiment is obtained is put retort furnace constant temperature 2min into, adopt manual time-keeping, taking out sample behind the constant temperature 2min immerses in the water under the previously prepd 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 to repeat 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.As seen, the micro-arc oxidation/spray coating compound film and the magnesium alloy bonding force that obtain of present embodiment is good.
Present embodiment (is not carried out pre-treatment to the micro-arc oxidation/spray coating compound film for preparing, ceramic coating formed by micro-arc oxidation and the AZ31B magnesium alloy 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, saturated calomel electrode 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.Test obtains the Tafel polarization curve as shown in Figure 4, "-▼-" is the Tafel polarization curve of present 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 magnesium alloy.As seen from Figure 4, the corrosion potential of micro-arc oxidation/spray coating compound film is-1.02V, corrosion potential (about 1.5V) than AZ31B magnesium alloy 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 of the micro-arc oxidation/spray coating compound film of present embodiment on thermodynamics significantly diminishes; The corrosion electric current density of micro-arc oxidation/spray coating compound film has reduced by 5 orders of magnitude than the corrosion electric current density of AZ31B magnesium alloy, the corrosion electric current density of the ceramic coating formed by micro-arc oxidation that obtains than step 1 has reduced by 3 orders of magnitude, and the corrosion tendency of the micro-arc oxidation/spray coating compound film of present embodiment on kinetics significantly diminishes.The micro-arc oxidation/spray coating compound film that present 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 magnesium alloy is polished with the sand paper of 240# and 1000# respectively, remove surface film oxide, then magnesium alloy 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.
Present embodiment is carried 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, 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 that experiment finishes foundation greater than 3 places.After tested, 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, as shown in Figure 5; The ceramic coating formed by micro-arc oxidation that step 1 obtains a large amount of stains occurred through salt mist experiment 24h rear surface, and some places have exposed matrix, as shown in Figure 6; The micro-arc oxidation/spray coating compound film of present 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, as shown in Figure 7.The salt mist experiment time of the micro-arc oxidation/spray coating compound film that present 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 present embodiment prepares and the bonding force of magnesium alloy 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 membrane; 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, 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 present 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, described 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 company limited produces, and the silver color filler also is to be produced by the auspicious magnificent quark chemical industry in Shenzhen company limited.Other step and parameter are identical with embodiment 36.
The thickness of the inorganic coating layer that aerial spraying obtains in the micro-arc oxidation/spray coating compound film that present embodiment obtains is about 15 μ m, and inorganic coating layer all covers ceramic coating formed by micro-arc oxidation, and the composite membrane surface does not have micropore.
Present embodiment has been carried out the bonding force of cut test evaluation inorganic coating layer and ceramic coating formed by micro-arc oxidation according to standard GB/T1720-1979 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, illustrates that inorganic coating layer and ceramic membrane bonding force are good.
Present embodiment is carried 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 present embodiment a stain only occurs through salt mist experiment 144h surface, and other place also remains intact harmless, as shown in Figure 8.Illustrate 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 magnesium alloy, corrosion resistance nature is better.
The micro-arc oxidation/spray coating compound film that present embodiment prepares and the bonding force of magnesium alloy 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 membrane; 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, 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 present embodiment and embodiment 36 were different is to adopt constant current mode differential arc oxidation 20min in the step 1, promptly obtains the porous ceramic coating formed by micro-arc oxidation on magnesium alloy, 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 are identical with embodiment 36.
The thickness of micro-arc oxidation films reaches 21 μ m in the micro-arc oxidation/spray coating compound film that present 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 membrane surface does not have micropore, as shown in Figure 9.
Present embodiment is carried 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.As seen, though micro-arc oxidation/spray coating compound film that present embodiment obtains and magnesium alloy bonding force are still fine not as the composite membrane in the embodiment 36.
The cross section sem photograph of the micro-arc oxidation/spray coating compound film that present embodiment obtains as shown in figure 10, among the figure "
" position of the micro-arc oxidation/spray coating compound film that refers to; as seen from Figure 10; the part inorganic paint embeds in the aperture of ceramic membrane deeply in the inorganic coating layer; combine with ceramic membrane well, simultaneously as can be seen, current density increases; the reaction times increases; make the thickness thickening of micro-arc oxidation films, and surface irregularity injustice, roughness become big.Present embodiment has been carried out the bonding force of cut test evaluation inorganic coating layer and ceramic coating formed by micro-arc oxidation according to standard GB/T1720-1979 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, illustrates that inorganic coating layer and ceramic membrane bonding force are good.
Present embodiment is carried 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 present embodiment a stain only occurs through salt mist experiment 80h surface, and other place also remains intact harmless.
Embodiment 39: what present embodiment and embodiment 36 were different is to adopt constant current mode differential arc oxidation 10min in the step 1, promptly obtains the porous ceramic coating formed by micro-arc oxidation on magnesium alloy, 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, described 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 company limited produces, and the silver color filler also is to be produced by the auspicious magnificent quark chemical industry in Shenzhen company limited.Other step and parameter are identical with embodiment 36.
The thickness of micro-arc oxidation films reaches 16.5 μ m in the micro-arc oxidation/spray coating compound film that the present embodiment present 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 membrane surface does not have micropore, as shown in figure 11.
The cross section sem photograph of the micro-arc oxidation/spray coating compound film that present embodiment obtains as shown in figure 12, among the figure "
" position of the micro-arc oxidation/spray coating compound film that refers to, as seen from Figure 12, the part inorganic paint embeds in the aperture of ceramic membrane deeply in the inorganic coating layer, combines well with ceramic membrane.Present embodiment has been carried out the bonding force of cut test evaluation inorganic coating layer and ceramic coating formed by micro-arc oxidation according to standard GB/T1720-1979 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, illustrates that inorganic coating layer and ceramic membrane bonding force are good.
Present embodiment is carried 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 present 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 present embodiment prepares and the bonding force of magnesium alloy 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 membrane; 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, 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 (10)
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 by following steps: one, magnesium alloy is carried out pre-treatment and remove surface film oxide, then pretreated magnesium alloy 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 obtain the porous ceramic coating formed by micro-arc oxidation on magnesium alloy, 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, compressed-air actuated internal pressure is 0.3 ~ 0.5MPa, 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, spray gun runs parallel, 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 magnesium alloy; Described 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 described double-component aqueous nano ceramic coating and nano-sized filler are Shenzhen auspicious magnificent quark chemical industry company limited and produce; Described 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 magnesium alloy of inorganic coating layer at 60 ~ 100 ℃ of down dry 10 ~ 20min, and then in 230 ~ 300 ℃ retort furnace sintering 20 ~ 30min, then magnesium alloy 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 magnesium alloy is AZ31B magnesium alloy, AZ91D magnesium alloy, MB26 magnesium alloy, ZM5 magnesium alloy 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 3 is characterized in 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.
5. according to the preparation method of claim 1,2 or 4 described a kind of magnesium alloy surface micro-arc oxidation/spray coating compound films, it is characterized in that the quantity for spray of control inorganic paint in the step 2 is 4g/s.
6. the preparation method of a kind of magnesium alloy surface micro-arc oxidation/spray coating compound film according to claim 5 is characterized in that the spray gun translational speed is 12 ~ 18cm/s in the step 2.
7. according to the preparation method of claim 1,2,4 or 6 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 the magnesium alloy of inorganic coating layer at 80 ~ 95 ℃ of down dry 12 ~ 18min.
8. the preparation method of a kind of magnesium alloy surface micro-arc oxidation/spray coating compound film according to claim 7 is characterized in that in the step 3 and then sintering 22 ~ 28min in 240 ~ 280 ℃ retort furnace.
9. according to the preparation method of claim 1,2,4,6 or 8 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, described 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 company limited 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.
10. according to the preparation method of claim 1,2,4,6 or 8 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 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, described 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 company limited produces, and nano-sized filler also is to be produced by the auspicious magnificent quark chemical industry in Shenzhen company limited.
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