CN113355714A - Method for anodizing and sealing and glazing oxide film of aluminum or aluminum alloy part - Google Patents
Method for anodizing and sealing and glazing oxide film of aluminum or aluminum alloy part Download PDFInfo
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- CN113355714A CN113355714A CN202110692498.2A CN202110692498A CN113355714A CN 113355714 A CN113355714 A CN 113355714A CN 202110692498 A CN202110692498 A CN 202110692498A CN 113355714 A CN113355714 A CN 113355714A
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- 238000007789 sealing Methods 0.000 title claims abstract description 72
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 52
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910000838 Al alloy Chemical group 0.000 title claims abstract description 50
- 238000007743 anodising Methods 0.000 title claims description 17
- 239000000919 ceramic Substances 0.000 claims abstract description 76
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000005498 polishing Methods 0.000 claims abstract description 40
- 230000003647 oxidation Effects 0.000 claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 34
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011265 semifinished product Substances 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 26
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 16
- 238000005238 degreasing Methods 0.000 claims abstract description 10
- YXJYBPXSEKMEEJ-UHFFFAOYSA-N phosphoric acid;sulfuric acid Chemical compound OP(O)(O)=O.OS(O)(=O)=O YXJYBPXSEKMEEJ-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 239000012535 impurity Substances 0.000 claims description 15
- 238000007590 electrostatic spraying Methods 0.000 claims description 14
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- 238000001962 electrophoresis Methods 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
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- 150000002500 ions Chemical class 0.000 claims description 6
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- 238000004587 chromatography analysis Methods 0.000 claims 1
- 239000010409 thin film Substances 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 11
- 230000007797 corrosion Effects 0.000 abstract description 11
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/12—Anodising more than once, e.g. in different baths
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/16—Pretreatment, e.g. desmutting
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/20—Electrolytic after-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/18—After-treatment, e.g. pore-sealing
- C25D11/24—Chemical after-treatment
- C25D11/246—Chemical after-treatment for sealing layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/16—Polishing
- C25F3/18—Polishing of light metals
- C25F3/20—Polishing of light metals of aluminium
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The invention discloses a closed glazing method for anodic oxidation and oxide film of aluminum or aluminum alloy parts, which comprises the steps of degreasing a semi-finished product of aluminum or aluminum alloy, and then carrying out electrochemical polishing in sulfuric acid-phosphoric acid binary mixed acid to enable the surface of the semi-finished product of aluminum or aluminum alloy to generate ceramic color basic ground color and oxidize the surface to generate a ceramic color oxide film layer; and an organic hole sealing film layer is arranged on the outer side of the ceramic color oxide film layer. According to the method provided by the embodiment of the application, surface acidification ceramic color treatment is carried out when the anodic oxide film layer is generated, and the organic hole sealing film layer is arranged outside the oxide film layer and provides glossiness and stronger corrosion resistance for the surface of the part. The ceramic color oxidation film layer is an oxidation film layer generated by the reoxidation of a reaction product of an aluminum or aluminum alloy semi-finished product in sulfuric acid and phosphoric acid binary mixed acid. Through the parts treated by the method, the comprehensive corrosion resistance of the parts is greatly improved, and the stability is excellent.
Description
Technical Field
The invention relates to the technical field of electrolytic machining and aluminum alloy surface treatment, in particular to a method for anodizing and sealing and polishing an oxide film of an aluminum or aluminum alloy part.
Background
Currently, in many vehicles, high-gloss, matt or satin-gloss decorative and structural parts made of aluminum or aluminum profiles are used in the interior and exterior areas, which parts are not only highly decorative but also very protective. The high decorative surface is realized by different pretreatment processes before oxidation, such as mechanical polishing, sand blasting, wire drawing, electrolytic polishing, etching and the like; in order to provide the highly decorative surface with good protection, the anodic oxide film on the surface thereof must be subjected to sealing treatment after anodic oxidation.
However, the common aluminum or aluminum alloy decorative strip for the automobile in the prior art has single appearance color, texture derived from the natural color of metal, poor gloss of common sealing treatment after oxidation, and poor corrosion resistance and weather resistance, and cannot meet increasingly severe appearance and performance requirements of the market.
Disclosure of Invention
The invention provides a method for anodizing and sealing and glazing an oxide film of an aluminum or aluminum alloy part.
The invention provides the following scheme:
a method for anodizing and sealing and glazing an oxide film of an aluminum or aluminum alloy part comprises the following steps:
degreasing the semi-finished product of the aluminum or the aluminum alloy, and then performing electrochemical polishing in sulfuric acid phosphoric acid binary mixed acid to enable the surface of the semi-finished product of the aluminum or the aluminum alloy to generate a ceramic color basic ground color and oxidize the ceramic color basic ground color to generate a ceramic color oxidation film layer;
and an organic hole sealing film layer is arranged on the outer side of the ceramic color oxide film layer.
Preferably: the degreasing treatment comprises the following steps:
the semi-finished product of the aluminum or the aluminum alloy is washed for 5 to 7 minutes by a phosphatized alkaline degreasing agent at the temperature of between 40 and 60 ℃.
Preferably: the electrochemical polishing in the sulfuric acid-phosphoric acid binary mixed acid comprises the following steps:
and (3) electrifying the mixed dibasic acid of phosphoric acid and sulfuric acid at the temperature of between 60 and 65 ℃ and carrying out electrochemical polishing for 4 to 6 minutes at the voltage of between 40 and 44 volts, and then powering off and continuously keeping the mixed dibasic acid in the groove for 4 to 6 minutes.
Preferably: the concentration of the sulfuric acid is 300g/L-420 g/L; the concentration of the phosphoric acid is 650g/L-830 g/L.
Preferably: and after the ceramic color oxide film layer is subjected to impurity removal treatment, an organic hole sealing film layer is arranged on the outer side of the ceramic color oxide film layer.
Preferably: the impurity removal treatment comprises:
etching the semi-finished product of the aluminum or the aluminum alloy which generates the ceramic color oxide film layer for 30 to 40 seconds at the temperature of between 28 and 32 ℃ by using a sodium hydroxide solution with the concentration of between 20 and 35 g/L;
removing ash and light at 15-20 ℃ for 100-140 seconds by using sulfuric acid with the concentration of 170-200 g/L;
anodizing with 180-210 g/L sulfuric acid at 15-20 deg.c and 12-15V for 1500 sec;
washing with room-temperature first pure water for 2-3 minutes, wherein the pH value of the first pure water is 3.0-6.0;
washing with hot water to further remove impurity ions, wherein the temperature of the hot water is 75-85 ℃, the pH value of the hot water is 4.0-6.0, and the washing time is 5-7 minutes;
and washing the substrate for 2 to 4 minutes by using second pure water at room temperature, wherein the pH value of the second pure water is 5.0 to 7.0.
Preferably: the outside of ceramic look oxidation rete is provided with organic hole sealing rete, includes:
and arranging an organic hole sealing film layer on the outer side of the ceramic color oxide film layer by adopting an electrodeposition process or an electrostatic spraying process.
Preferably: arranging an organic hole sealing film layer on the outer side of the ceramic color oxide film layer by adopting an electrodeposition process, wherein the organic hole sealing film layer comprises a light extinction electrophoresis paint layer; the electrodeposition process comprises:
immersing the part on which the ceramic color oxide film layer is formed into an electrophoretic paint liquid in a first electrophoretic tank for electro-deposition hole sealing and glazing; the temperature of the electrophoretic paint liquid in the first electrophoresis tank is 18-21 ℃, the voltage is 120-170V, the electrodeposition time is 120-720 seconds, the mass percentage of the solid part of the electrophoretic paint liquid is 9-11%, the pH value is 8.2-8.6, and the conductivity is 650-950 mu s/cm;
immersing the part subjected to the electro-deposition hole sealing and glazing treatment into a reverse osmosis tank to clean the surface of the part and recover paint liquid, wherein the pH value of tank liquid in the reverse osmosis tank is 8.5-10;
curing and baking the part coating film at the baking temperature of 180-205 ℃ for 20-35 minutes.
Preferably: arranging an organic hole sealing film layer on the outer side of the ceramic color oxide film layer by adopting an electrodeposition process, wherein the organic hole sealing film layer comprises a high-light electrophoretic paint layer; the electrodeposition process comprises:
dipping the part with the ceramic color oxide film layer into the electrophoretic paint liquid in a second electrophoretic tank for electro-deposition hole sealing and glazing; the temperature of the electrophoretic paint liquid in the second electrophoretic tank is 18-21 ℃, the voltage is 90-150 volts, the electrodeposition time is 100-500 seconds, the mass percentage of the solid part of the electrophoretic paint liquid is 7-9%, and the pH value is 7.8-8.6; the conductivity is 550-;
immersing the part subjected to the electro-deposition hole sealing and polishing treatment into a reverse osmosis tank to clean the surface of the part and recover paint liquid, wherein the pH value of tank liquid in the reverse osmosis tank is 8.0-9.5;
curing and baking the part coating film at the baking temperature of 180-205 ℃ for 20-35 minutes.
Preferably: an organic hole sealing film layer is arranged on the outer side of the ceramic color oxide film layer by adopting an electrostatic spraying process, and the electrostatic spraying process comprises the following steps:
conveying the parts with the ceramic color oxide film layer to a thermostatic passage with the temperature of 16-22 ℃ for surface drying for 16-20 minutes by a chain, wherein the particle size in the thermostatic passage is less than 10 mu m and the particle amount is less than 4.5mg/m3；
Then, carrying out electrostatic spraying on the part with the ceramic color oxide film layer in a dust-free room, wherein the temperature in the dust-free room is 15-22 ℃, the humidity in a paint spraying room is 55 +/-5%, and the thickness of the sprayed part film is 1-5 mu m;
sending the part into a leveling chamber, and leveling for 80-120 seconds at the temperature of 18-24 ℃;
curing and baking the part film, wherein the baking temperature is 180-220 ℃, and the baking time is 20-35 minutes.
According to the specific embodiment provided by the invention, the invention discloses the following technical effects:
in one implementation mode, the method can comprise the steps of degreasing a semi-finished product of aluminum or aluminum alloy, and then carrying out electrochemical polishing in sulfuric acid-phosphoric acid binary mixed acid to enable the surface of the semi-finished product of aluminum or aluminum alloy to generate a ceramic color basic ground color and oxidize the surface to generate a ceramic color oxide film layer; and an organic hole sealing film layer is arranged on the outer side of the ceramic color oxide film layer. According to the method provided by the embodiment of the application, surface acidification ceramic color treatment is carried out when the anodic oxide film layer is generated, and the organic hole sealing film layer is arranged outside the oxide film layer and provides glossiness and stronger corrosion resistance for the surface of the part. The ceramic color oxidation film layer is an oxidation film layer generated by the reoxidation of a reaction product of an aluminum or aluminum alloy semi-finished product in sulfuric acid and phosphoric acid binary mixed acid. The comprehensive corrosion resistance of the parts is greatly improved through the treated parts, and the process parts can easily pass neutral salt spray NSS 480H and can be longer to 960H by taking a conventional salt spray test as an example; the surface can pass through CASS environment for at least 48h, and the stability is excellent.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a pictorial representation of a part formed in accordance with example 1 of the present invention;
figure 2 is a cross-sectional view of a part formed in accordance with example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
The embodiment of the invention provides a method for anodizing and sealing and glazing an oxide film of an aluminum or aluminum alloy part, which comprises the following steps:
degreasing the semi-finished product of the aluminum or the aluminum alloy, and then performing electrochemical polishing in sulfuric acid phosphoric acid binary mixed acid to enable the surface of the semi-finished product of the aluminum or the aluminum alloy to generate a ceramic color basic ground color and oxidize the ceramic color basic ground color to generate a ceramic color oxidation film layer;
and an organic hole sealing film layer is arranged on the outer side of the ceramic color oxide film layer.
According to the method provided by the embodiment of the application, surface acidification ceramic color treatment is carried out when the anodic oxide film layer is generated, and the organic hole sealing film layer is arranged outside the oxide film layer and provides glossiness and stronger corrosion resistance for the surface of the part. The ceramic color oxidation film layer is an oxidation film layer generated by the reoxidation of a reaction product of an aluminum or aluminum alloy semi-finished product in sulfuric acid and phosphoric acid binary mixed acid. The comprehensive corrosion resistance of the parts is greatly improved through the treated parts, and the process parts can easily pass neutral salt spray NSS 480H and can be longer to 960H by taking a conventional salt spray test as an example; the surface can pass through CASS environment for at least 48h, and the stability is excellent.
In the method provided by the embodiment of the application, the semi-finished product of the aluminum or the aluminum alloy is firstly degreased, and specifically, the semi-finished product of the aluminum or the aluminum alloy is washed for 5 to 7 minutes by using a phosphatized alkaline degreasing agent at the temperature of between 40 and 60 ℃. The aluminum or aluminum alloy semi-finished product is degreased, so that lipid substances on the surface of the aluminum or aluminum alloy semi-finished product subjected to degreasing can be eliminated, the surface is clean and tidy during subsequent treatment, and the production quality of an oxide film layer is improved.
Electrochemical polishing can be carried out after degreasing, in the prior industry, the electrochemical polishing is carried out by using single acid mainly by adopting an Alzak process, fluoboric acid is mainly used, but the fluoboric acid and decomposition products thereof are toxic, the production and transportation cost is higher than that of common sulfuric acid-phosphoric acid mixed liquor, and the application of the fluoboric acid and the decomposition products thereof in industrial production is not much. The method provided by the embodiment of the application adopts the sulfuric acid phosphoric acid binary mixed acid, so that the chromic anhydride component containing harmful substance hexavalent chromium can be reduced on the basis of a typical Barter process of world electrochemical polishing, the environmental protection and the harmless treatment of tank liquor are facilitated, the reduction of the current density and voltage of the process in the electrochemical polishing of sulfuric acid is kept, the process energy is saved, the electrolytic polishing is carried out at a higher temperature within a certain range, and the occurrence of pitting corrosion can be inhibited; the phosphoric acid can ensure the effective dissolution of aluminum and oxides thereof on the surface of the part, and the brightness of the polished surface is ensured while the leveling effect is achieved. Specifically, the electrochemical polishing in a sulfuric acid phosphoric acid binary mixed acid comprises the following steps: and (3) electrifying the mixed dibasic acid of phosphoric acid and sulfuric acid at the temperature of between 60 and 65 ℃ and carrying out electrochemical polishing for 4 to 6 minutes at the voltage of between 40 and 44 volts, and then powering off and continuously keeping the mixed dibasic acid in the groove for 4 to 6 minutes. The concentration of the sulfuric acid is 300g/L-420 g/L; the concentration of the phosphoric acid is 650g/L-830 g/L.
In order to further improve the quality of a product manufactured and formed by the method provided by the application, after the ceramic color oxide film layer is subjected to impurity removal treatment, an organic hole sealing film layer is arranged on the outer side of the ceramic color oxide film layer.
Specifically, the impurity removal treatment includes:
etching the semi-finished product of the aluminum or the aluminum alloy which generates the ceramic color oxide film layer for 30 to 40 seconds at the temperature of between 28 and 32 ℃ by using a sodium hydroxide solution with the concentration of between 20 and 35 g/L;
removing ash and light at 15-20 ℃ for 100-140 seconds by using sulfuric acid with the concentration of 170-200 g/L;
anodizing with 180-210 g/L sulfuric acid at 15-20 deg.c and 12-15V for 1500 sec;
washing with room-temperature first pure water for 2-3 minutes, wherein the pH value of the first pure water is 3.0-6.0;
washing with hot water to further remove impurity ions, wherein the temperature of the hot water is 75-85 ℃, the pH value of the hot water is 4.0-6.0, and the washing time is 5-7 minutes;
and washing the substrate for 2 to 4 minutes by using second pure water at room temperature, wherein the pH value of the second pure water is 5.0 to 7.0.
Impurities such as a phosphoric acid film on the surface of the oxidation film layer can be effectively removed through the impurity removing treatment, and the possibility of graying the surface of the part is reduced.
Further, the outside at ceramic look oxidation film layer is provided with organic hole sealing rete, includes:
and arranging an organic hole sealing film layer on the outer side of the ceramic color oxide film layer by adopting an electrodeposition process or an electrostatic spraying process. The electrodeposition layer may be a film layer formed by mixing acrylic resin and amino resin.
In practical application, a plurality of organic hole sealing film layers can be arranged according to actual needs, for example, in one implementation mode, the organic hole sealing film layer can be arranged on the outer side of the ceramic color oxide film layer by adopting an electrodeposition process, and the organic hole sealing film layer comprises a light extinction electrophoresis paint layer; the electrodeposition process comprises:
immersing the part on which the ceramic color oxide film layer is formed into an electrophoretic paint liquid in a first electrophoretic tank for electro-deposition hole sealing and glazing; the temperature of the electrophoretic paint liquid in the first electrophoresis tank is 18-21 ℃, the voltage is 120-170V, the electrodeposition time is 120-720 seconds, the mass percentage of the solid part of the electrophoretic paint liquid is 9-11%, the pH value is 8.2-8.6, and the conductivity is 650-950 mu s/cm;
immersing the part subjected to the electro-deposition hole sealing and glazing treatment into a reverse osmosis tank to clean the surface of the part and recover paint liquid, wherein the pH value of tank liquid in the reverse osmosis tank is 8.5-10;
curing and baking the part coating film at the baking temperature of 180-205 ℃ for 20-35 minutes. The method can realize the formation of the extinction electrophoresis paint layer outside the oxide film layer.
In one implementation manner, the embodiment of the present application may provide that an organic hole sealing film layer is disposed on an outer side of the ceramic color oxide film layer by using an electrodeposition process, where the organic hole sealing film layer includes a high-photoelectrophoresis paint layer; the electrodeposition process comprises:
dipping the part with the ceramic color oxide film layer into the electrophoretic paint liquid in a second electrophoretic tank for electro-deposition hole sealing and glazing; the temperature of the electrophoretic paint liquid in the second electrophoretic tank is 18-21 ℃, the voltage is 90-150 volts, the electrodeposition time is 100-500 seconds, the mass percentage of the solid part of the electrophoretic paint liquid is 7-9%, and the pH value is 7.8-8.6; the conductivity is 550-;
immersing the part subjected to the electro-deposition hole sealing and polishing treatment into a reverse osmosis tank to clean the surface of the part and recover paint liquid, wherein the pH value of tank liquid in the reverse osmosis tank is 8.0-9.5;
curing and baking the part coating film at the baking temperature of 180-205 ℃ for 20-35 minutes. The method can realize the formation of the high-light electrophoretic paint layer outside the oxide film layer.
In the prior art, only a single oxidation film layer is arranged on the surfaces of aluminum and aluminum alloy, and the oxidation film hole sealing treatment is carried out after the aluminum alloy is anodized, including cold sealing, medium-temperature sealing and heat sealing, the process method is a composite film layer, and an additional physical isolation layer (an organic hole sealing film layer) is applied on the oxidation film hole layer, so that the process method has the same sealing effect on the oxidation film hole layer, and can also be considered as a sealing substitution technology, and the process method is more reliable than the process method which only depends on sealing hundreds of millions of oxidation micropores on the surface of a part because the film layer with a physical structure completely covers the surface of the part; meanwhile, the principle of the additional physical film layer is determined to be an insulating material due to the component property of the additional physical film layer, so that the corrosion phenomenon can be eliminated by cutting off the transmission of electrons. Compared with the prior art, the composite ceramic coating has unique ceramic color, uniform color and rich appearance texture, and has good corrosion resistance and weather resistance due to the composite film layer.
In an implementation manner, an embodiment of the present application may further provide that an electrostatic spraying process is adopted to dispose an organic hole sealing film layer on the outer side of the ceramic color oxide film layer, where the electrostatic spraying process includes:
conveying the parts with the ceramic color oxide film layer to a thermostatic passage with the temperature of 16-22 ℃ for surface drying for 16-20 minutes by a chain, wherein the particle size in the thermostatic passage is less than 10 mu m and the particle amount is less than 4.5mg/m3；
Then, carrying out electrostatic spraying on the part with the ceramic color oxide film layer in a dust-free room, wherein the temperature in the dust-free room is 15-22 ℃, the humidity in a paint spraying room is 55 +/-5%, and the thickness of the sprayed part film is 1-5 mu m;
sending the part into a leveling chamber, and leveling for 80-120 seconds at the temperature of 18-24 ℃;
curing and baking the part film, wherein the baking temperature is 180-220 ℃, and the baking time is 20-35 minutes.
The surface can be treated by acidifying ceramic color before the anodic oxide film is adopted, and an inorganic silicification film layer is sprayed outside the oxide film layer, wherein the inorganic hole sealing film layer provides glossiness and stronger corrosion resistance for the surface. The ceramic color oxidation film is an oxidation film layer generated by reoxidation of a reaction product of aluminum in a sulfuric acid phosphoric acid binary mixed acid, and an inorganic silicification paint layer is electrostatically sprayed. Compared with the prior art, the anti-abrasion.
The scheme provided by the present application is described in detail by the following specific examples, and various raw materials required in the examples may be commercially available products.
Example 1
A method for anodizing ceramic color appearance and sealing (matte) an oxide film of an aluminum or aluminum alloy part for an automobile comprises the following steps of degreasing a semi-finished product of aluminum or aluminum alloy before anodizing, performing electrochemical polishing to refine and polish surface textures, generating ceramic color base ground color on the surface, oxidizing to generate a ceramic color oxide film, and sealing and polishing the ceramic color oxide film, wherein the method comprises the following specific steps:
firstly, washing the semi-finished product for 5-7 min by using an alkaline phosphating degreasing agent at the temperature of 40-60 ℃; eliminating lipid substances to make the surface clean and tidy;
secondly, conducting electrochemical polishing for 4min to 6min in binary mixed acid taking phosphoric acid (650g/L to 830g/L) and sulfuric acid (320g/L to 420g/L) at the temperature of 60 ℃ to 65 ℃ as main bodies by using voltage of 40V to 44V, eliminating textures and carrying out mirror surface treatment. Forming a composite film layer of an oxide film, namely, generating white; then quickly cutting off the power and continuing to form ceramic color on the surface of the semi-finished product in 4-6 min;
thirdly, removing the membrane for 30 to 40 seconds at the temperature of between 28 and 32 ℃ by using 20 to 35g/L of sodium hydroxide solution; removing impurities such as phosphoric acid films and the like, and reducing the grey;
fourthly, 170g/L to 200g/L of sulfuric acid is used for ash removal and light extraction for 100s to 140s at the temperature of 15 ℃ to 20 ℃;
fifthly, anodizing with 180g/L-210g/L sulfuric acid at 15-20 ℃ and 12-15V for 1200-1500 s;
sixthly, washing the mixture for 2 to 3 minutes by pure water at room temperature, wherein the pH value of the pure water is 3.0 to 6.0;
seventhly, hot water washing is carried out to further remove impurity ions, the temperature of the hot water is 75-85 ℃, the pH value of the hot water is 4.0-6.0, and the washing time is 5min-7 min;
then flushing the mixture for 2 to 4 minutes by pure water at room temperature, wherein the pH value of the pure water is 5.0 to 7.0;
ninthly, hole sealing and glazing treatment are carried out on the part: immersing the machined part in electrophoresis tank liquor (which can comprise extinction electrophoresis paint, related common additives and the like) (adopting AG-300KAI of Guanxi province) to carry out electro-deposition hole sealing and glazing, wherein the parameters of the tank liquor are applied at the temperature of 18-21 ℃, the voltage of 120V-170V, the electro-deposition time is controlled at 120-720 s, the solid content of the tank liquor is controlled at 9-11%, and the pH value is controlled at 8.2-8.6; the conductivity is controlled at 650-
R immersing the treated part in reverse osmosis tank to clean the surface of part and recover paint liquid, pH value of tank liquid is 8.5-10;
Example 2
A ceramic color appearance anode oxidation and oxide film closed glazing (high) method for automobile aluminum or aluminum alloy parts is to degrease semi-finished products of aluminum or aluminum alloy before anode oxidation, generate ceramic color base ground color on the surface during electrochemical polishing for refining and polishing surface textures, then oxidize to generate ceramic color oxide film, and then perform closed glazing treatment, and the method comprises the following steps:
firstly, washing the semi-finished product for 5-7 min by using an alkaline phosphating degreasing agent at the temperature of 40-60 ℃;
secondly, conducting electrochemical polishing for 4-6 min in binary mixed acid taking phosphoric acid (650g/L-830g/L) and sulfuric acid (320g/L-420g/L) at the temperature of 60-65 ℃ as main bodies at the voltage of 40V-44V, and then quickly cutting off the power and continuing to carry out the operation in the tank for 4-6 min;
thirdly, removing the membrane for 30 to 40 seconds at the temperature of between 28 and 32 ℃ by using 20 to 35g/L of sodium hydroxide solution;
fourthly, 170g/L to 200g/L of sulfuric acid is used for ash removal and light extraction for 100s to 140s at the temperature of 15 ℃ to 20 ℃;
fifthly, anodizing with 180g/L-210g/L sulfuric acid at 15-20 ℃ and 12-15V for 1200-1500 s;
sixthly, washing the mixture for 2 to 3 minutes by pure water at room temperature, wherein the pH value of the pure water is 3.0 to 6.0;
seventhly, hot water washing is carried out to further remove impurity ions, the temperature of the hot water is 75-85 ℃, the pH value of the hot water is 4.0-6.0, and the washing time is 5min-7 min;
then flushing the mixture for 2 to 4 minutes by pure water at room temperature, wherein the pH value of the pure water is 5.0 to 7.0;
ninthly, hole sealing and glazing treatment are carried out on the part: immersing the pre-processed part into electrophoresis tank liquor (adopting AG-210 of Guangxi) for electro-deposition hole sealing and glazing, wherein the application temperature of the tank liquor parameters is 18-21 ℃, the voltage is 90-150V, the electro-deposition time is controlled at 100-500 s, the solid content of the tank liquor is controlled at 7-9%, and the pH value is controlled at 7.8-8.6; the conductivity is controlled at 550-;
r immersing the treated part in reverse osmosis tank to clean the surface of part and recover paint liquid, pH value of tank liquid is 8.0-9.5;
Example 3
A ceramic color appearance anode oxidation and oxide film closed glazing (high) method for automobile aluminum or aluminum alloy parts is to degrease semi-finished products of aluminum or aluminum alloy before anode oxidation, generate ceramic color base ground color on the surface during electrochemical polishing for refining and polishing surface textures, then oxidize to generate ceramic color oxide film, and then perform closed glazing treatment, and the method comprises the following steps:
firstly, washing the semi-finished product for 5-7 min by using an alkaline phosphating degreasing agent at the temperature of 40-60 ℃;
secondly, conducting electrochemical polishing for 2min to 6min in binary mixed acid taking phosphoric acid (650g/L to 830g/L) and sulfuric acid (320g/L to 420g/L) at the temperature of 60 ℃ to 65 ℃ as main bodies at the voltage of 40V to 44V, and then quickly cutting off the power and continuing to carry out the operation for 4min to 6min in the tank;
thirdly, removing the membrane for 30 to 40 seconds at the temperature of between 28 and 32 ℃ by using 20 to 35g/L of sodium hydroxide solution;
fourthly, 170g/L to 200g/L of sulfuric acid is used for ash removal and light extraction for 100s to 140s at the temperature of 15 ℃ to 20 ℃;
fifthly, anodizing with 180g/L-210g/L sulfuric acid at 15-20 ℃ and 12-15V for 1200-1500 s;
sixthly, washing the mixture for 2 to 3 minutes by pure water at room temperature, wherein the pH value of the pure water is 3.0 to 6.0;
seventhly, hot water washing is carried out to further remove impurity ions, the temperature of the hot water is 70-80 ℃, the pH value of the hot water is 4.0-6.0, and the washing time is 5-7 min;
then flushing the mixture for 2 to 4 minutes by pure water at room temperature, wherein the pH value of the pure water is 5.0 to 7.0;
ninthly, performing electrostatic spraying on the part to realize sealing and glazing treatment: conveying the processed preamble to a constant temperature channel with 16-22 ℃ for surface drying for 16-20 min by using a chain, and controlling the particle size in the channel to be less than 10 mu m and the particle amount to be less than 4.5mg/m3；
R & lt 10mg/m of the above parts in a clean room (particle size below 5 μm)3) Electrostatic spraying (the varnish adopts 3700 of a Meiji chart), the temperature in a spraying room is 15-22 ℃, the humidity in a spraying room is 55 +/-5%, and the thickness of the sprayed part film is 1-5 mu m;
It will be appreciated that the method provided by the above example, after a closed glazing process, gives a different texture gloss to the surface of an aluminium or aluminium alloy part, where the electrophoresis requires recycling of the paint and no recycling of the spray.
For experimental verification of the components in the above examples, the experimental conditions are shown in table 1:
TABLE 1 test items
The test results are shown in Table 2
TABLE 2
The extinction electrophoretic paint provided in the embodiment 1 has white ceramic appearance glossiness, sufficient surface appearance texture and certain frosted feeling; the high-gloss paint surface provided in the example 2 is ceramic white in appearance, bright in surface gloss and obvious in reflection, and can be understood as matte sport paint and bright paint on a vehicle body; example 3 provides a high light transmission paint, which has visual side test performance comparable to examples 1 and 2, but some host factory standards do not require CASS performance for inorganic coatings.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (10)
1. A method for anodizing and sealing and polishing an oxide film of an aluminum or aluminum alloy part is characterized by comprising the following steps:
degreasing the semi-finished product of the aluminum or the aluminum alloy, and then performing electrochemical polishing in sulfuric acid phosphoric acid binary mixed acid to enable the surface of the semi-finished product of the aluminum or the aluminum alloy to generate a ceramic color basic ground color and oxidize the ceramic color basic ground color to generate a ceramic color oxidation film layer;
and an organic hole sealing film layer is arranged on the outer side of the ceramic color oxide film layer.
2. The method for closed polishing of anodic oxidation and oxide film of aluminum or aluminum alloy member according to claim 1, wherein said degreasing treatment comprises:
the semi-finished product of the aluminum or the aluminum alloy is washed for 5 to 7 minutes by a phosphatized alkaline degreasing agent at the temperature of between 40 and 60 ℃.
3. The method for closed polishing of anodic oxidation and oxide film of aluminum or aluminum alloy component according to claim 1, wherein said electrochemical polishing in sulfuric-phosphoric acid dibasic mixed acid comprises:
and (3) electrifying the mixed dibasic acid of phosphoric acid and sulfuric acid at the temperature of between 60 and 65 ℃ and carrying out electrochemical polishing for 4 to 6 minutes at the voltage of between 40 and 44 volts, and then powering off and continuously keeping the mixed dibasic acid in the groove for 4 to 6 minutes.
4. The method for closed polishing of anodic oxidation and oxide film of aluminum or aluminum alloy member according to claim 3, wherein the concentration of sulfuric acid is 300g/L-420 g/L; the concentration of the phosphoric acid is 650g/L-830 g/L.
5. The method for anodizing and sealing an oxide film of an aluminum or aluminum alloy member according to claim 1, wherein an organic sealing film layer is formed on an outer side of the ceramic color oxide film layer after removing impurities from the ceramic color oxide film layer.
6. The method for closed polishing of anodic oxidation and oxide film of aluminum or aluminum alloy member according to claim 5, wherein said impurity removing treatment comprises:
etching the semi-finished product of the aluminum or the aluminum alloy which generates the ceramic color oxide film layer for 30 to 40 seconds at the temperature of between 28 and 32 ℃ by using a sodium hydroxide solution with the concentration of between 20 and 35 g/L;
removing ash and light at 15-20 ℃ for 100-140 seconds by using sulfuric acid with the concentration of 170-200 g/L;
anodizing with 180-210 g/L sulfuric acid at 15-20 deg.c and 12-15V for 1500 sec;
washing with room-temperature first pure water for 2-3 minutes, wherein the pH value of the first pure water is 3.0-6.0;
washing with hot water to further remove impurity ions, wherein the temperature of the hot water is 75-85 ℃, the pH value of the hot water is 4.0-6.0, and the washing time is 5-7 minutes;
and washing the substrate for 2 to 4 minutes by using second pure water at room temperature, wherein the pH value of the second pure water is 5.0 to 7.0.
7. The method for anodizing and sealing and polishing an oxide film of an aluminum or aluminum alloy part according to claim 1, wherein an organic sealing film layer is disposed on an outer side of the ceramic color oxide film layer, and the method comprises:
and arranging an organic hole sealing film layer on the outer side of the ceramic color oxide film layer by adopting an electrodeposition process or an electrostatic spraying process.
8. The method for closed polishing of anodic oxidation and oxide film of aluminum or aluminum alloy component according to claim 7, wherein an organic hole sealing film layer is disposed outside the ceramic color oxide film layer by electrodeposition process, the organic hole sealing film layer comprising an extinction electrophoresis paint layer; the electrodeposition process comprises:
immersing the part on which the ceramic color oxide film layer is formed into an electrophoretic paint liquid in a first electrophoretic tank for electro-deposition hole sealing and glazing; the temperature of the electrophoretic paint liquid in the first electrophoresis tank is 18-21 ℃, the voltage is 120-170V, the electrodeposition time is 120-720 seconds, the mass percentage of the solid part of the electrophoretic paint liquid is 9-11%, the pH value is 8.2-8.6, and the conductivity is 650-950 mu s/cm;
immersing the part subjected to the electro-deposition hole sealing and glazing treatment into a reverse osmosis tank to clean the surface of the part and recover paint liquid, wherein the pH value of tank liquid in the reverse osmosis tank is 8.5-10;
curing and baking the part coating film at the baking temperature of 180 ℃ and 205 ℃ for 20-35 minutes.
9. The method for closed polishing of anodic oxidation and oxide film of aluminum or aluminum alloy component according to claim 7, wherein an electrodeposition process is used to dispose an organic hole sealing film layer on the outer side of the ceramic color oxide film layer, wherein the organic hole sealing film layer comprises a high photoelectrophoresis paint layer; the electrodeposition process comprises:
dipping the part with the ceramic color oxide film layer into the electrophoretic paint liquid in a second electrophoretic tank for electro-deposition hole sealing and glazing; the temperature of the electrophoretic paint liquid in the second electrophoresis tank is 18-21 ℃, the voltage is 90-150 volts, the electrodeposition time is 100-750 mu s/cm, the mass percentage of the solid part of the electrophoretic paint liquid is 7-9%, the pH value is 7.8-8.6, and the conductivity is 550-750 mu s/cm;
immersing the part subjected to the electro-deposition hole sealing and polishing treatment into a reverse osmosis tank to clean the surface of the part and recover paint liquid, wherein the pH value of tank liquid in the reverse osmosis tank is 8.0-9.5;
curing and baking the part coating film at the baking temperature of 180 ℃ and 205 ℃ for 20-35 minutes.
10. The method for closed polishing of anodic oxidation and oxide film of aluminum or aluminum alloy component according to claim 7, wherein an organic hole sealing film layer is disposed outside the ceramic color oxide film layer by electrostatic spraying process, the electrostatic spraying process comprising:
conveying the part with the ceramic color oxide film layer to a constant-temperature channel with the temperature of 16-22 ℃ for 16-20 minutes by using a chain, and carrying out thin film chromatography on the surface of the constant-temperature channel, wherein the granularity in the constant-temperature channel is less than 10 mu m, and the grain quantity is less than 4.5 mg/m;
then, carrying out electrostatic spraying on the part with the ceramic color oxide film layer in a dust-free room, wherein the temperature in the dust-free room is 15-22 ℃, the humidity in a paint spraying room is 55 +/-5%, and the thickness of the sprayed part film is 1-5 mu m;
sending the part into a leveling chamber, and leveling for 80-120 seconds at the temperature of 18-24 ℃;
curing and baking the part film, wherein the baking temperature is 180-220 ℃, and the baking time is 20-35 minutes.
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