CN101423967B - Surface treating method of aluminum alloy material - Google Patents
Surface treating method of aluminum alloy material Download PDFInfo
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- CN101423967B CN101423967B CN2007101820883A CN200710182088A CN101423967B CN 101423967 B CN101423967 B CN 101423967B CN 2007101820883 A CN2007101820883 A CN 2007101820883A CN 200710182088 A CN200710182088 A CN 200710182088A CN 101423967 B CN101423967 B CN 101423967B
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Abstract
The invention provides a surface treatment method for an alloy material. The method comprises the step of electrophoretic painting of the alloy material, and is characterized in that the method also comprises the step of anodization of the alloy material before the electrophoretic painting. The corrosion resistance and the adhesion force of a film formed on the surface of the alloy material which is treated by the surface treatment method and coated by paint are good.
Description
Technical field
The invention relates to a kind of surface treatment method of alloy material.
Background technology
MAGNESIUM METAL and zinc standing stock in the earth are all very abundant, and because their distinctive physicals and mechanical propertys have obtained application widely at present in aerospace, automotive industry, telecommunications and people's life.But magnesium or zinc and alloy thereof belong to the very active metallic substance of chemical property, thereby being applied in to a great extent of they is restricted.
In order to address this problem, relevant technologies personnel have carried out deep research to the surface treatment method of magnesium alloy or zinc alloy, and the at present common magnesium alloy or the surface treatment method of zinc alloy have anodic oxidation, differential arc oxidation, chemical membrane, pottery covering and coating covering etc.But the sticking power and the erosion resistance of the rete that the magnesium alloy after these conventional disposal methods of process or the surface of zinc alloy form are relatively poor.CN 1908246A discloses a kind of method of Mg alloy surface being carried out carrying out after differential arc oxidation is handled again electrophoretic process, the method of described differential arc oxidation is: with water glass 5 grams per liters, potassium hydroxide 11 grams per liters and Sodium Fluoride 7 grams per liters configuration electrolytic solution, placing electrolytic solution to carry out differential arc oxidation pending magnesium alloy product handles, make anode with magnesium alloy product, stainless steel plate is made negative electrode, in 2-7 minute, the adjusting process parameter is: voltage is the 180-400 volt, frequency is the 300-450 hertz, and dutycycle is 6-12; Forming thickness at Mg alloy surface is the magnesium alloy ceramic layer of 5-20 micron.Though the sticking power and the erosion resistance of the rete that the magnesium alloy after this disposal methods of process or the surface of zinc alloy form increase, and be still relatively poor.
Summary of the invention
The sticking power and the relatively poor defective of erosion resistance that the objective of the invention is the rete that forms for the surface that overcomes the alloy material after the existing disposal methods provide the sticking power of the rete that a kind of surface that makes the alloy material after the processing forms and the erosion resistance surface treatment method of alloy material preferably.
The invention provides a kind of surface treatment method of alloy material, this method comprises carries out electrophoretic painting to alloy material, and wherein, this method is carried out anodic oxidation to alloy material earlier before also being included in electrophoretic painting.
Respectively to carrying out SaltSprayTest after magnesium alloy product after the surface treatment of embodiment and Comparative Examples and the processing of Zinc-alloy process oil paint coating, the result shows, the magnesium alloy product of embodiment occurs unusually 221-260 hour rear surface, and Zinc-alloy occurs unusual 203-227 hour rear surface; The magnesium alloy product of Comparative Examples occurs unusual 96 hours rear surfaces, Zinc-alloy occurs unusual 72 hours rear surfaces, therefore, compare with existing method, the alloy material after adopting the surface treatment method of alloy material provided by the invention to handle is better through the erosion resistance of the rete that the surface behind the oil paint coating forms.
Respectively to carrying out the sticking power test after magnesium alloy product after the surface treatment of embodiment and Comparative Examples and the processing of Zinc-alloy process oil paint coating, the result shows, the binding force of membrane mark of the magnesium alloy product of embodiment is 95-99, and the binding force of membrane mark of Zinc-alloy is 95-98; The binding force of membrane mark of the magnesium alloy product of Comparative Examples is 74, the binding force of membrane mark of Zinc-alloy is 68, therefore, compare with existing method, the alloy material after adopting the surface treatment method of alloy material provided by the invention to handle is better through the sticking power of the rete that the surface behind the oil paint coating forms.
Embodiment
The surface treatment method of alloy material provided by the invention comprises alloy material is carried out electrophoretic painting that wherein, this method is carried out anodic oxidation to alloy material earlier before also being included in electrophoretic painting.
Described anodic oxidation can be the various anodised method of routine, for example, this method can be included under the anodic oxidation condition, alloy material is put into anodic oxidation solution, with the alloy material is anode, the electro-conductive material high with chemical stability in anodic oxidation solution is negative electrode, and negative electrode is connected with negative electricity with the positive pole of power supply respectively with anode.
In the anodic oxidation of described magnesium alloy, contain the oxyhydroxide of 100-140 grams per liter, the mangaic acid aluminium potassium of 20-60 grams per liter, the Sodium Fluoride of 60-90 grams per liter and the sodium phosphate of 30-60 grams per liter in the described anodic oxidation solution; Described electro-conductive material can be in stainless steel, lead and the platinum rhodium one or more, is preferably stainless steel; Described anodised condition can comprise that current density is 2-4 ampere/square decimeter, and temperature is 10-30 ℃, and the time is 10-30 minute.
When described alloy material is zinc alloy, contain the oxyhydroxide of 10-30 grams per liter in the described anodic oxidation solution; Described electro-conductive material can be in stainless steel, lead and the platinum rhodium one or more; Described anodised condition can comprise that current density is 5-15 ampere/square decimeter, and temperature is 40-45 ℃, and the time is 5-10 minute.
Described oxyhydroxide can be sodium hydroxide and/or potassium hydroxide.
Can thoroughly clean up through the anodic oxidation solution of three roads washing after the above-mentioned anodic oxidation the alloy material surface, described washing can be soaked under the room temperature condition, at room temperature allow the alloy material anode oxide film reach surface drying then, put into baking oven then, toasted 0.5-3 hour down at 100-180 ℃, make the conversion film surface reach absolutely dry.The anode oxide film that forms with above-mentioned anode oxidation method has evenly fine and closely woven micropore, makes that follow-up electrophoretic painting layer can be tightr in conjunction with getting.
Described electrophoretic painting can be the method for the various electrophoretic paintings of routine, can be anode electro-coating or cathode electro-coating, for example, preferred cathode electro-coating, this method can be included under the electrophoretic painting condition, and alloy material is put into electrocoating paint solution, is anode with the electro-conductive material, with the alloy material is negative electrode, and negative electrode is connected with negative electricity with the positive pole of power supply respectively with anode.
Described electrocoating paint solution can be electrocoating paint solution commonly used, for example, can be the mute photoelectrophoresis lacquer of CM cathode electrodip painting, CW of Japanese clear water Co., Ltd.; The saturating color cathode electrodip painting of DP-8810 of the Shanghai gloomy coating of great power company limited, the colored two-pack cathode electrodip painting of HS-5000LB; The HDX electrocoating paint of great Jin nation border Far East Group Co.,Ltd, HSR electrocoating paint, lucky triumphant electrocoating paint, lucky grand electrocoating paint etc.The embodiment of the invention adopts is the SM electrocoating paint that Japanese clear water Co., Ltd. produces.Described electro-conductive material can be in stainless steel, lead and the platinum rhodium a kind of and several, be preferably stainless steel.
Described electrophoretic painting condition can comprise that electrophoresis temperature is 20-25 ℃, and electrophoresis time is 10-60 second, and electrophoretic voltage is the 20-70 volt, is preferably the 40-50 volt, and electrocoating paint pH is 4.2-4.8.Alloy material can be put into baking oven behind the electrophoretic painting, descends dry 30-60 minute at 120-200 ℃, treats that the dried fully back of electrocoating paint on alloy material surface is taken out.
Under the preferable case, before the surface treatment method of described alloy material also is included in and carries out anodic oxidation, there is the smeary alloy material to carry out degreasing and/or electrolytic degreasing for the surface, there is the alloy material of oxide film to carry out pickling for the surface and removes oxide film, carry out in the alkali cleaning then and the remaining acid in surface, according to this optimal way, can further improve the sticking power and the erosion resistance of the rete that the surface of alloy material forms.
Described degreasing can be adopted conventional various degreasing methods, and for example, the degreasing method of magnesium alloy can comprise that magnesium alloy is put into degreasing fluid to be soaked; Described degreasing fluid can be various magnesium alloy degreasing fluids commonly used, preferably contains the degreasing fluid of paregal O-25 of sodium lauryl sulphate, the 10-100 grams per liter of 1-10 grams per liter; The temperature of the degreasing of described magnesium alloy can be 50-60 ℃, and the time can be 10-20 minute.The degreasing method of zinc alloy can comprise Zinc-alloy is placed in the degreasing fluid, and apply ultrasonic wave in degreasing fluid; Described degreasing fluid can be various zinc alloy degreasing fluids commonly used, preferably contains the Na of 15-30 grams per liter
3PO
4, the 10-25 grams per liter Na
2CO
3With the 10-100 milliliter/liter commercially available zinc alloy remove the degreasing fluid of La Shui; The temperature of described ultrasonic degreasing can be 50-65 ℃, and the time can be 5-30 minute.After the general degreasing, fully clean alloy material with twice water again, to remove the remaining degreasing fluid in surface.
Described electrolytic degreasing can adopt the method for conventional various electrolytic degreasings, for example, this method can comprise puts into the cell body that fills degreasing fluid with alloy material as negative electrode, with electro-conductive material that anode dissolution reaction does not take place as anode, described electro-conductive material is the conventional anodic material that can be used as, for example can be stainless steel plate or carbon-point, negative electrode is connected with negative electricity with the positive pole of power supply respectively with anode, carrying out impressed current handles, described degreasing fluid can be degreasing fluid commonly used, what use in the embodiment of the invention is the good prosperous WH-68 alloy electrolytic degreasing liquid that Science and Technology Ltd. produces that grinds in Shenzhen, temperature can be 40-70 ℃, time can be 5-15 minute, described current density can be 3-10 ampere/square decimeter, can wash alloy material for water after the oil removing, be preferably and use 50-100 ℃ hot water to clean immediately, fully clean up the degreasing fluid on alloy material surface again with flowing water.
The method of described pickling can be soaked for alloy material is put into acid solution, described acid solution can contain the 5-15 milliliter/liter sulfuric acid and the 5-10 milliliter/liter hydrofluoric acid, temperature can be 10-40 ℃, the time is 1-5 second.Fully clean alloy material with twice water again after the general pickling, to remove the acid of remained on surface.
The purpose of described alkali cleaning be in and the acid that retains of alloy material pickling rear surface, described caustic washing method can be soaked for alloy material is put into alkaline solution, described alkaline solution can contain the sodium hydroxide of 5-10 grams per liter, and temperature can be 50-90 ℃, and the time is 3-10 minute.Fully clean alloy material with twice water again after the general alkali cleaning, to remove the alkali of remained on surface.
The surface treatment method of alloy material of the present invention is the surface treatment method of the alloy material after the pre-treatment to the application of alloy material surface oil lacquer improves, according to method of the present invention alloy material is carried out again alloy material being carried out oil paint coating after the surface treatment, can further improve the sticking power and the erosion resistance of the rete that the surface of alloy material forms, but also the paint of application different colours as required.
Described oil paint coating is handled the method that can adopt spraying, and used paint can be various paint commonly used, for example alkyd varnish, epoxy resin-based paint or polyurethane paint, and what embodiments of the invention were used is the Resins, epoxy paint that BASF AG produces.After oil paint coating is handled, can be 150-300 ℃ of oven dry 30-180 minute down, until with paint drying.
Among the present invention, described alloy material is preferably magnesium alloy and/or zinc alloy material.The thickness tester of the Pocket-Surfix FN2.2 model that the thickness of all retes can be produced with German PHYNIX company among the present invention records.
Below will be for a more detailed description to the present invention by embodiment.Among each embodiment, unless specified otherwise, the solvent of used solution is water.
Embodiment 1
This embodiment illustrates the surface treatment method of magnesium alloy provided by the invention.
1, pre-treatment
(1) degreasing
To AZ91D magnesium alloy pressure-casting goods (Biyadi Co Ltd's production) carry out degreasing, goods are immersed in 55 ℃ the degreasing fluid of forming by sodium lauryl sulphate 5 grams per liters and peregal O-25 50 grams per liters and take out after 15 minutes, clean up with the twice water degreasing fluid that product surface is remaining then.
(2) electrolytic degreasing
With the above-mentioned goods that carried out degreasing as negative electrode, stainless steel is put into current density as anode is 7 amperes/square decimeter the cell body that fills the WH-68 alloy electrolytic degreasing liquid that Shenzhen good prosperous grinding Science and Technology Ltd. produces, negative electrode is connected with negative electricity with the positive pole of power supply respectively with anode, take out after 10 minutes at electrolytic degreasing under 50 ℃ the temperature, clean cleaning article with 70 ℃ of hot water immediately, clean up with the flowing water degreasing fluid that product surface is residual again.
(3) pickling
The above-mentioned goods that carried out electrolytic degreasing are put into 30 ℃ being taken out after 3 seconds by 10 milliliters of/liter acid solution soak times of forming with 8 milliliters/liter in hydrofluoric acid of sulfuric acid, use twice water cleaning article then, remove the residual acid of product surface.
(4) alkali cleaning
The sodium hydroxide that the above-mentioned goods that carried out pickling are put into 75 ℃ sodium hydroxide 8 grams per liters soaked 7 minutes, used twice water cleaning article then, removed the residual alkali of product surface.
2, anodic oxidation
Goods after the above-mentioned pre-treatment are immersed in the anodic oxidation solution as anode, simultaneously with stainless steel as negative electrode, negative electrode is connected with negative electricity with the positive pole of power supply respectively with anode.As anodic oxidation solution, adjusting current density was 2 amperes/square decimeter, 10 ℃ of following anodic oxidations 10 minutes by the solution of forming of mangaic acid aluminium potassium 50 grams per liters, Sodium Fluoride 80 grams per liters, sodium hydroxide 120 grams per liters and sodium phosphate 50 grams per liters in employing.Recording magnesium alloy product surface, to form thickness be 5 microns anodic oxide coating.The NMT-1950 type baking box of producing with Shenzhen Nai Meite company after the anodic oxidation toasted 2 hours down at 150 ℃.
3, electrophoretic painting
Carried out anodised goods and immersed in the electrocoating paint above-mentioned as negative electrode, simultaneously with stainless steel as anode, negative electrode is connected with negative electricity with the positive pole of power supply respectively with anode.The pH that adopts Japanese clear water Co., Ltd. to produce was 4.5 SM electrocoating paint, and adjusting voltage is 50 volts, 20 ℃ of following electrophoretic paintings 10 seconds.Recording magnesium alloy product surface, to form thickness be 5 microns electrophoretic paint layer.The NMT-1950 type baking box of producing with Shenzhen Nai Meite company behind the electrophoretic painting toasted 45 minutes down at 160 ℃.
Embodiment 2
This embodiment illustrates the surface treatment method of magnesium alloy provided by the invention.
1, pre-treatment
(1) degreasing
To AZ91D magnesium alloy pressure-casting goods (Biyadi Co Ltd's production) carry out degreasing, goods are immersed in 50 ℃ the degreasing fluid of forming by sodium lauryl sulphate 1 grams per liter and peregal O-25 10 grams per liters and take out after 10 minutes, clean up with the twice water degreasing fluid that product surface is remaining then.
(2) electrolytic degreasing
With the above-mentioned goods that carried out degreasing as negative electrode, stainless steel is put into current density as anode is 3 amperes/square decimeter the cell body that fills the WH-68 alloy electrolytic degreasing liquid that Shenzhen good prosperous grinding Science and Technology Ltd. produces, negative electrode is connected with negative electricity with the positive pole of power supply respectively with anode, take out after 5 minutes at electrolytic degreasing under 40 ℃ the temperature, clean cleaning article with 50 ℃ of hot water immediately, clean up with the flowing water degreasing fluid that product surface is residual again.
(3) pickling
The above-mentioned goods that carried out electrolytic degreasing are put into 10 ℃ being taken out after 1 second by 5 milliliters of/liter acid solution soak times of forming with 10 milliliters/liter in hydrofluoric acid of sulfuric acid, use twice water cleaning article then, remove the residual acid of product surface.
(4) alkali cleaning
The sodium hydroxide that the above-mentioned goods that carried out pickling are put into 50 ℃ sodium hydroxide 5 grams per liters soaked 3 minutes, used twice water cleaning article then, removed the residual alkali of product surface.
2, anodic oxidation
Goods after the above-mentioned pre-treatment are immersed in the anodic oxidation solution as anode, simultaneously with stainless steel as negative electrode, negative electrode is connected with negative electricity with the positive pole of power supply respectively with anode.As anodic oxidation solution, adjusting current density was 3 amperes/square decimeter, 15 ℃ of following anodic oxidations 20 minutes by the solution of forming of mangaic acid aluminium potassium 20 grams per liters, Sodium Fluoride 60 grams per liters, sodium hydroxide 100 grams per liters and sodium phosphate 30 grams per liters in employing.Recording magnesium alloy product surface, to form thickness be 8 microns anodic oxide coating.The NMT-1950 type baking box of producing with Shenzhen Nai Meite company after the anodic oxidation toasted 0.5 hour down at 100 ℃.
3, electrophoretic painting
Carried out anodised goods and immersed in the electrocoating paint above-mentioned as negative electrode, simultaneously with stainless steel as anode, negative electrode is connected with negative electricity with the positive pole of power supply respectively with anode.The pH that adopts Japanese clear water Co., Ltd. to produce was 4.2 SM electrocoating paint, and adjusting voltage is 20 volts, 20 ℃ of following electrophoretic paintings 20 seconds.Recording magnesium alloy product surface, to form thickness be 8 microns electrophoretic paint layer.The NMT-1950 type baking box of producing with Shenzhen Nai Meite company behind the electrophoretic painting toasted 30 minutes down at 120 ℃.
Embodiment 3
This embodiment illustrates the surface treatment method of magnesium alloy provided by the invention.
1, pre-treatment
(1) degreasing
To AZ91D magnesium alloy pressure-casting goods (Biyadi Co Ltd's production) carry out degreasing, goods are immersed in 60 ℃ the degreasing fluid of forming by sodium lauryl sulphate 10 grams per liters and peregal O-25 100 grams per liters and take out after 20 minutes, clean up with the twice water degreasing fluid that product surface is remaining then.
(2) electrolytic degreasing
With the above-mentioned goods that carried out degreasing as negative electrode, stainless steel is put into current density as anode is 10 amperes/square decimeter the cell body that fills the WH-68 alloy electrolytic degreasing liquid that Shenzhen good prosperous grinding Science and Technology Ltd. produces, negative electrode is connected with negative electricity with the positive pole of power supply respectively with anode, take out after 15 minutes at electrolytic degreasing under 70 ℃ the temperature, clean cleaning article with 100 ℃ of hot water immediately, clean up with the flowing water degreasing fluid that product surface is residual again.
(3) pickling
The above-mentioned goods that carried out electrolytic degreasing are put into 40 ℃ being taken out after 5 seconds by 15 milliliters of/liter acid solution soak times of forming with 10 milliliters/liter in hydrofluoric acid of sulfuric acid, use twice water cleaning article then, remove the residual acid of product surface.
(4) alkali cleaning
The sodium hydroxide that the above-mentioned goods that carried out pickling are put into 90 ℃ sodium hydroxide 10 grams per liters soaked 10 minutes, used twice water cleaning article then, removed the residual alkali of product surface.
2, anodic oxidation
Goods after the above-mentioned pre-treatment are immersed in the anodic oxidation solution as anode, simultaneously with stainless steel as negative electrode, negative electrode is connected with negative electricity with the positive pole of power supply respectively with anode.As anodic oxidation solution, adjusting current density was 4 amperes/square decimeter, 25 ℃ of following anodic oxidations 30 minutes by the solution of forming of mangaic acid aluminium potassium 60 grams per liters, Sodium Fluoride 90 grams per liters, sodium hydroxide 140 grams per liters and sodium phosphate 60 grams per liters in employing.Recording magnesium alloy product surface, to form thickness be 15 microns anodic oxide coating.The NMT-1950 type baking box of producing with Shenzhen Nai Meite company after the anodic oxidation toasted 3 hours down at 180 ℃.
3, electrophoretic painting
Carried out anodised goods and immersed in the electrocoating paint above-mentioned as negative electrode, simultaneously with stainless steel as anode, negative electrode is connected with negative electricity with the positive pole of power supply respectively with anode.The pH that adopts Japanese clear water Co., Ltd. to produce was 4.8 SM electrocoating paint, and adjusting voltage is 70 volts, 25 ℃ of following electrophoretic paintings 60 seconds.Recording magnesium alloy product surface, to form thickness be 10 microns electrophoretic paint layer.The NMT-1950 type baking box of producing with Shenzhen Nai Meite company behind the electrophoretic painting toasted 60 minutes down at 200 ℃.
Comparative Examples 1
This Comparative Examples illustrates the surface treatment method of existing magnesium alloy.
According to the method identical with embodiment 1 to AZ91D magnesium alloy pressure-casting goods (Biyadi Co Ltd's production) carry out surface treatment, different is, replaces anodic oxidation among the embodiment 1 with differential arc oxidation.
Differential arc oxidation carries out according to the method that embodiment among the patent CN 1908246A 1 describes.
Employing contains the solution of water glass 5 grams per liters, potassium hydroxide 11 grams per liters and Sodium Fluoride 7 grams per liters as electrolytic solution, placing electrolytic solution to carry out differential arc oxidation pending magnesium alloy product handles, make anode with magnesium alloy product, stainless steel plate is made negative electrode, control treating processes processing parameter is as shown in table 1, and recording the magnesium alloy product surface, to form thickness be 10 microns magnesium alloy ceramic layer;
Table 1
Embodiment 4
This embodiment illustrates the surface treatment method of zinc alloy provided by the invention.
According to the method identical with embodiment 1 to ZZnAID4 zinc alloy diecasting goods (Biyadi Co Ltd's production) carry out surface treatment, different is degreasing in the pre-treatment and anode oxidation method difference.
1, pre-treatment
(1) degreasing
ZZnAID4 zinc alloy diecasting goods are carried out degreasing, goods are immersed in 60 ℃ the degreasing fluid, ultrasonic 20 minutes, the brute force that adopts Shanghai base chemical industry (Shanghai) Co., Ltd. to produce was removed the solution of 50 milliliters/liter of La Shui (MTJ 6 models), sodium phosphate 20 grams per liters and yellow soda ash 15 grams per liters composition as degreasing fluid.Clean up with the twice water degreasing fluid that product surface is remaining then.
2, anodic oxidation
Goods after the pre-treatment are immersed in the anodic oxidation solution as anode, simultaneously with stainless steel as negative electrode, negative electrode is connected with negative electricity with the positive pole of power supply respectively with anode.Employing contains the solution of sodium hydroxide 20 grams per liters as anodic oxidation solution, and adjusting current density was 5 amperes/square decimeter, 70 ℃ of following anodic oxidations 5 minutes.The thickness tester of the Pocket-Surfix FN2.2 model of producing with German PHYNIX company records the magnesium alloy product surface, and to form thickness be 10 microns anodic oxide coating.The NMT-1950 type baking box of producing with Shenzhen Nai Meite company after the anodic oxidation toasted 2 hours down at 150 ℃.
Embodiment 5
This embodiment illustrates the surface treatment method of zinc alloy provided by the invention.
According to the method identical with embodiment 1 to ZZnAID4 zinc alloy diecasting goods (Biyadi Co Ltd's production) carry out surface treatment, different is degreasing in the pre-treatment and anode oxidation method difference.
1, pre-treatment
(1) degreasing
ZZnAID4 zinc alloy diecasting goods are carried out degreasing, goods are immersed in 50 ℃ the degreasing fluid, ultrasonic 5 minutes, the brute force that adopts Shanghai base chemical industry (Shanghai) Co., Ltd. to produce was removed the solution of 10 milliliters/liter of La Shui (MTJ 6 models), sodium phosphate 15 grams per liters and yellow soda ash 10 grams per liters composition as degreasing fluid.Clean up with the twice water degreasing fluid that product surface is remaining then.
2, anodic oxidation
Goods after the pre-treatment are immersed in the anodic oxidation solution as anode, simultaneously with stainless steel as negative electrode, negative electrode is connected with negative electricity with the positive pole of power supply respectively with anode.Employing contains the solution of sodium hydroxide 20 grams per liters as anodic oxidation solution, and adjusting current density was 10 amperes/square decimeter, 42 ℃ of following anodic oxidations 8 minutes.The thickness tester of the Pocket-Surfix FN2.2 model of producing with German PHYNIX company records the magnesium alloy product surface, and to form thickness be 15 microns anodic oxide coating.The NMT-1950 type baking box of producing with Shenzhen Nai Meite company after the anodic oxidation toasted 0.5 hour down at 100 ℃.
Embodiment 6
This embodiment illustrates the surface treatment method of zinc alloy provided by the invention.
According to the method identical with embodiment 3 to ZZnAID4 zinc alloy diecasting goods (Biyadi Co Ltd's production) carry out surface treatment, different is degreasing in the pre-treatment and anode oxidation method difference.
1, pre-treatment
(1) degreasing
ZZnAID4 zinc alloy diecasting goods are carried out degreasing, goods are immersed in 65 ℃ the degreasing fluid, ultrasonic 30 minutes, the brute force that adopts Shanghai base chemical industry (Shanghai) Co., Ltd. to produce was removed the solution of 100 milliliters/liter of La Shui (MTJ 6 models), sodium phosphate 30 grams per liters and yellow soda ash 25 grams per liters composition as degreasing fluid.Clean up with the twice water degreasing fluid that product surface is remaining then.
2, anodic oxidation
Goods after the pre-treatment are immersed in the anodic oxidation solution as anode, simultaneously with stainless steel as negative electrode, negative electrode is connected with negative electricity with the positive pole of power supply respectively with anode.Employing contains the solution of sodium hydroxide 30 grams per liters as anodic oxidation solution, and adjusting current density was 15 amperes/square decimeter, 45 ℃ of following anodic oxidations 10 minutes.The thickness tester of the Pocket-Surfix FN2.2 model of producing with German PHYNIX company records the magnesium alloy product surface, and to form thickness be 20 microns anodic oxide coating.The NMT-1950 type baking box of producing with Shenzhen Nai Meite company after the anodic oxidation toasted 2 hours down at 150 ℃.
Comparative Examples 2
This Comparative Examples illustrates the surface treatment method of existing zinc alloy.
According to the method identical with embodiment 4 to ZZnAID4 zinc alloy diecasting goods (Biyadi Co Ltd's production) carry out surface treatment, different is, replaces anodic oxidation among the embodiment 2 with differential arc oxidation.
Differential arc oxidation carries out according to the method that embodiment among the patent CN 1908246A 1 describes.
Employing contains the solution of water glass 5 grams per liters, potassium hydroxide 11 grams per liters and Sodium Fluoride 7 grams per liters as electrolytic solution, placing electrolytic solution to carry out differential arc oxidation pending magnesium alloy product handles, make anode with magnesium alloy product, stainless steel plate is made negative electrode, control treating processes processing parameter is as shown in table 2, and recording the magnesium alloy product surface, to form thickness be 7 microns magnesium alloy ceramic layer;
Table 2
Embodiment 7-12
This embodiment illustrates the performance after magnesium alloy after the surface treatment of embodiment 1-6 and Zinc-alloy carry out oil paint coating.
The electrostatic coating equipment paint sprayer NDL-Q2 that produces with the outstanding Electronics Co., Ltd. of the municipal intelligence in the Wuhan Resins, epoxy paint that the BASF AG of 20 micron thickness produces on magnesium alloy after the surface treatment of embodiment 1-6 and Zinc-alloy external coating respectively; Toasted 100 minutes down at 220 ℃ with the NMT-1950 type baking box that Shenzhen Nai Meite company produces oil paint coating processing back.
The solidity to corrosion test on magnesium alloy behind the oil paint coating and Zinc-alloy surface
The salt fog measuring method is for placing magnesium alloy after the surface treatment of embodiment 1-6 and Zinc-alloy respectively behind above-mentioned oil paint coating in the YWX/Q-250 type salt-mist corrosion tester of Wuxi City southern Jiangsu testing installation company limited production, at 35 ℃ is that the sodium chloride aqueous solution splash of 5 weight % is after 2 hours with concentration down, goods being placed the another one temperature after the taking-up is that 40 ℃, relative humidity are 80% climatic chamber again, observe alloy product, be recorded in how long the back product surface occurs unusual, time is long more, illustrates that the erosion resistance of rete is good more.The result is described in table 3 below.
The sticking power test of the rete that magnesium alloy behind the oil paint coating and Zinc-alloy surface form
On the surface behind the above-mentioned oil paint coating, mark the lattice number 100 (scratch depth is controlled at and guarantees film lower substrate metal exposed) that is spaced apart 1 millimeter of uniform size at magnesium alloy after the surface treatment of embodiment 1-6 and Zinc-alloy respectively with sharp blade, the lattice that the statistics film comes off is counted N1, to stick width be 24 millimeters scotch tape in the lattice zone of drawing on film, and guarantee to combine between adhesive tape and the film that grid is arranged tight.After 5 minutes, adhesive tape is uncovered, and added up the lattice that film comes off once more and count N2 with the power of a vertical face.Appraisal procedure is as follows: adopt centesimal system, and binding force of membrane mark=100-(N1+N2), the binding force of membrane mark is big more, illustrates that the sticking power of rete is good more.Evaluation result is described in table 3 below.
Comparative Examples 3-4
Magnesium alloy after the surface treatment of this Comparative Examples explanation Comparative Examples 1-2 and Zinc-alloy carry out the performance behind the oil paint coating.
According to the method identical with embodiment 7-12, earlier respectively the magnesium alloy after the surface treatment of Comparative Examples 1-2 and zinc alloy are carried out oil paint coating and handle, use magnesium alloy and the erosion resistance on the surface of Zinc-alloy behind oil paint coating and the sticking power of the rete that the surface forms after the surface treatment of the method test comparison example 1-2 identical then with implementing 7-12.The result is as shown in table 3 below.
Table 3
| Numbering | Erosion resistance (hour) | The binding force of membrane mark |
| Embodiment 1 | 240 | 98 |
| Embodiment 2 | 221 | 95 |
| Embodiment 3 | 260 | 99 |
| Embodiment 4 | 216 | 97 |
| Embodiment 5 | 203 | 95 |
| Embodiment 6 | 227 | 98 |
| Comparative Examples 1 | 96 | 74 |
| Comparative Examples 2 | 72 | 68 |
Data from table 3 as can be seen, the magnesium alloy product of embodiment occurs unusual 221-260 hour rear surface, Zinc-alloy occurs unusual 203-227 hour rear surface; The magnesium alloy product of Comparative Examples occurs unusual 96 hours rear surfaces, Zinc-alloy occurs unusual 72 hours rear surfaces, therefore, compare with existing method, the alloy material after adopting the surface treatment method of alloy material provided by the invention to handle is better through the erosion resistance of the rete that the surface behind the oil paint coating forms.
Data from table 3 it can also be seen that the binding force of membrane mark of the magnesium alloy product of embodiment is 95-99, and the binding force of membrane mark of Zinc-alloy is 95-98; The binding force of membrane mark of the magnesium alloy product of Comparative Examples is 74, the binding force of membrane mark of Zinc-alloy is 68, therefore, compare with existing method, the alloy material after adopting the surface treatment method of alloy material provided by the invention to handle is better through the sticking power of the rete that the surface behind the oil paint coating forms.
Claims (6)
1. the surface treatment method of an alloy material, this method comprises carries out electrophoretic painting to alloy material, it is characterized in that, this method is carried out anodic oxidation to alloy material earlier before also being included in electrophoretic painting, described anodised method is included under the anodic oxidation condition, and alloy material is put into anodic oxidation solution, is anode with the alloy material, the electro-conductive material high with chemical stability in anodic oxidation solution is negative electrode, and negative electrode is connected with negative electricity with the positive pole of power supply respectively with anode;
Described alloy material is a zinc alloy, contains the oxyhydroxide of 10-30 grams per liter in the described anodic oxidation solution;
Described oxyhydroxide is sodium hydroxide and/or potassium hydroxide.
2. method according to claim 1, wherein, described electro-conductive material is one or more in stainless steel, lead and the platinum rhodium; Described anodised condition comprises that current density is 5-15 ampere/square decimeter, and temperature is 40-45 ℃, and the time is 5-10 minute.
3. method according to claim 1, wherein, described electrophoretic painting is anode electro-coating or cathode electro-coating.
4. method according to claim 3, wherein, described cathode electro-coating is included under the electrophoretic painting condition, alloy material is put into electrocoating paint solution, with the electro-conductive material is anode, is negative electrode with the alloy material, and negative electrode is connected with negative electricity with the positive pole of power supply respectively with anode.
5. method according to claim 4, wherein, described electro-conductive material is a stainless steel; Described electrophoretic painting condition comprises that electrophoresis temperature is 20-25 ℃, and electrophoresis time is 10-60 second, and electrophoretic voltage is the 20-70 volt, and electrocoating paint pH value is 4.2-4.8.
6. method according to claim 1 wherein, before this method also is included in and carries out anodic oxidation, has the smeary alloy material to carry out degreasing and/or oil removing to the surface, and the alloy material of surperficial aerobic film is carried out pickling and alkali cleaning.
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| CN102758237A (en) * | 2012-07-31 | 2012-10-31 | 厦门建霖工业有限公司 | High-corrosion-resistance surface treatment method of zinc alloy by hexavalent chrome color emulation |
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| CN101831684B (en) * | 2010-05-28 | 2012-06-13 | 河海大学常州校区 | Microarc-oxidation electrophoretic-coating composite processing method of surface of Q 235 steel part |
| CN103305894B (en) * | 2012-03-09 | 2016-01-27 | 苏州汉扬精密电子有限公司 | Surface treatment method of Mg alloy |
| CN103668226B (en) * | 2012-09-13 | 2016-06-29 | 苏州汉扬精密电子有限公司 | Magnesium alloy high-corrosion-resissurface surface treatment method and products thereof |
| CN103243372B (en) * | 2013-04-24 | 2016-08-03 | 常熟市长发铝业有限公司 | A kind of electrodeposited paint film method |
| CN103243371B (en) * | 2013-05-16 | 2015-06-17 | 中国船舶重工集团公司第七二五研究所 | Preparation method of zinc anode oxidation film layer |
| CN103272749B (en) * | 2013-06-07 | 2015-01-07 | 山东国强五金科技有限公司 | Surface treatment method of zinc alloy die casting |
| CN103397368A (en) * | 2013-08-23 | 2013-11-20 | 国家电网公司 | Stainless steel coloring liquid and coloring method |
| CN105543936B (en) * | 2016-01-22 | 2017-11-07 | 浙江工业大学 | Zinc material anode oxidation and surface dyeing method |
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| CN111842086B (en) * | 2020-07-16 | 2022-07-12 | 太原理工大学 | Preparation method of composite coating for improving corrosion resistance and antibacterial property of magnesium alloy |
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