CN114908394A - Hard anodic oxidation process of aluminum alloy oxide film - Google Patents
Hard anodic oxidation process of aluminum alloy oxide film Download PDFInfo
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- CN114908394A CN114908394A CN202110172910.8A CN202110172910A CN114908394A CN 114908394 A CN114908394 A CN 114908394A CN 202110172910 A CN202110172910 A CN 202110172910A CN 114908394 A CN114908394 A CN 114908394A
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- 230000003647 oxidation Effects 0.000 title claims abstract description 120
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 120
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 91
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000010410 layer Substances 0.000 claims abstract description 48
- 238000009834 vaporization Methods 0.000 claims abstract description 41
- 230000008016 vaporization Effects 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 26
- 239000000919 ceramic Substances 0.000 claims abstract description 24
- 239000002245 particle Substances 0.000 claims abstract description 21
- 239000011229 interlayer Substances 0.000 claims abstract description 14
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 40
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 38
- 239000011812 mixed powder Substances 0.000 claims description 27
- 238000005507 spraying Methods 0.000 claims description 20
- 239000000853 adhesive Substances 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 8
- 238000003860 storage Methods 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 5
- 230000008030 elimination Effects 0.000 claims description 5
- 238000003379 elimination reaction Methods 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 235000011089 carbon dioxide Nutrition 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000005491 wire drawing Methods 0.000 claims description 3
- 238000007743 anodising Methods 0.000 claims 8
- 238000003475 lamination Methods 0.000 abstract description 23
- 239000000758 substrate Substances 0.000 abstract description 21
- 238000006748 scratching Methods 0.000 abstract description 4
- 230000002393 scratching effect Effects 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 description 16
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- 238000009826 distribution Methods 0.000 description 4
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- 229910052751 metal Inorganic materials 0.000 description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 229910001586 aluminite Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- WPPDFTBPZNZZRP-UHFFFAOYSA-N aluminum copper Chemical compound [Al].[Cu] WPPDFTBPZNZZRP-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 1
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- 238000006056 electrooxidation reaction Methods 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- 238000010301 surface-oxidation reaction Methods 0.000 description 1
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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
- C25D11/12—Anodising more than once, e.g. in different baths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical Kinetics & Catalysis (AREA)
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- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention discloses a hard anodic oxidation process of an aluminum alloy oxide film, belonging to the field of oxidation treatment of aluminum oxide surfaces, by arranging the vaporization bubble balls and matching with the operation of multiple times of anodic oxidation, an oxidation bottom layer and a plurality of oxidation interlayers can be formed on the surface of the aluminum alloy substrate in sequence, and finally forming an oxidation lamination taking the nano ceramic particles as a base on the surface of the aluminum alloy base material, so that the hardness of the formed oxidation lamination is gradually increased from outside to inside, and the compactness of the oxidation lamination is gradually enhanced from inside to outside, the compactness of the oxide film is effectively ensured, simultaneously the hardness of the oxide film is obviously improved, further the occurrence of scratching in the prior art is effectively avoided, even if the scratching phenomenon occurs, the oxidation lamination can still play a good role in protecting the internal aluminum alloy.
Description
Technical Field
The invention relates to the field of aluminum oxide surface oxidation treatment, in particular to a hard anodic oxidation process of an aluminum alloy oxide film.
Background
The raw aluminum is generally called electrolytic aluminum in market supply, and is a raw material for producing aluminum materials and aluminum alloy materials. The aluminum is a metal with low strength and good plasticity, and is prepared into an alloy for improving the strength or the comprehensive performance except for applying partial pure aluminum. The structure and performance of the aluminum can be changed by adding an alloy element into the aluminum, and the aluminum alloy is suitable for being used as various processing materials or casting parts. The alloy elements frequently added include copper, magnesium, zinc and silicon
Aluminum alloys are mainly classified into wrought aluminum alloys and cast aluminum alloys. The wrought aluminum alloy has high strength and large specific strength and is suitable for plastic forming. The wrought aluminum alloy is further divided into: industrial pure aluminum, aluminum alloys that are not heat-treated for strengthening, aluminum alloys that are heat-treated for strengthening; the cast aluminum alloy is suitable for filling casting molds in a molten state to obtain the aluminum alloy of casting blanks with certain shapes and sizes. The cast aluminum alloy comprises the following components: aluminum silicon alloy, aluminum copper alloy, aluminum magnesium alloy, aluminum zinc alloy.
The aluminum oxidation includes natural oxidation, electrochemical oxidation, chemical oxidation, alkaline oxidation, acid oxidation and anodic oxidation, and means oxidation treatment methods of aluminum and aluminum alloys. Anodic oxidation of aluminum: aluminum is an active metal, the standard potential is-1.66 v, an oxide film with the thickness of about 0.01-0.1 micron can be naturally formed in the air, and the oxide film is amorphous, thin, porous and poor in corrosion resistance. However, when aluminum or its alloy is placed in a suitable electrolyte, and an aluminum product is used as an anode, an oxide film is formed on the surface of the aluminum product by applying an electric current, which is called anodic oxidation. By selecting different types and concentrations of electrolyte and controlling the technological conditions during oxidation, anodic oxide films with different properties and thicknesses of dozens to hundreds of microns can be obtained, and the corrosion resistance, the wear resistance, the decoration performance and the like of the anodic oxide films are obviously improved and enhanced.
With the rapid development of the field of electronic and communication equipment, people have higher and higher requirements on the quality of electronic products, and the trend of full metallization of the electronic product body material is obvious, wherein the aluminum alloy shell is matched with anodic oxidation treatment to be one of the current mainstream modes. The anodic oxide film obtained by the conventional aluminum alloy common anodic oxidation treatment process has the advantages of good adsorbability and convenience in dyeing, so that the requirement on high decoration is met, but the hardness of the oxide film is low, and the oxide film is easy to be damaged, scratched and scratched, so that the appearance is influenced, and the consumer experience is influenced.
Disclosure of Invention
1. Technical problem to be solved
Aiming at the problems in the prior art, the invention aims to provide a hard anodic oxidation process of an aluminum alloy oxide film, which can form an oxidation bottom layer and a plurality of oxidation interlayers on the surface of an aluminum alloy substrate in sequence by arranging a vaporization bubble ball and matching with a plurality of times of anodic oxidation operations, and further finally form an oxidation lamination layer taking nano ceramic particles as a bottom on the surface of the aluminum alloy substrate, so that the hardness of the formed oxidation lamination layer is gradually increased from outside to inside, and the compactness of the oxidation lamination layer is gradually enhanced from inside to outside.
2. Technical scheme
In order to solve the above problems, the present invention adopts the following technical solutions.
A hard anodic oxidation process of an aluminum alloy oxide film comprises the following steps:
s1, firstly, carrying out wire drawing treatment on the surface of the aluminum alloy base material;
s2, uniformly spraying vaporization bubble balls on the surface of the aluminum alloy base material to form a hard powder layer on the surface of the aluminum alloy;
s3, placing the aluminum alloy base material with the hard powder layer into an oxidation tank containing anodic oxidation electrolyte, and simultaneously, taking a lead plate as a cathode, switching on a power supply to start primary anodic oxidation to form an oxidation bottom layer;
s4, taking out the aluminum alloy base material subjected to primary anodic oxidation, cleaning and airing, spraying the vaporization bubble spheres on the oxidation bottom layer again, and repeating the step S3 to perform secondary anodic oxidation to form an oxidation interlayer;
and S5, repeating the step S4 for multiple times, and oxidizing for multiple times to form an oxidized stack.
Furthermore, the vaporization bubble ball comprises a heat dissipation ball shell, a powder storage air hole is formed in the heat dissipation ball shell, a powder adhesive is injected into the powder storage air hole, a mixed powder of nano ceramic particles and aluminum powder is filled in the cavity of the heat dissipation ball shell, when the vaporization bubble ball is sprayed on the aluminum alloy substrate, the powder adhesive and the mixed powder simultaneously fall on the upper surface of the aluminum alloy substrate due to vaporization of the high-temperature heat dissipation ball shell, so that the mixed powder is fixed on the aluminum alloy substrate conveniently, the mixed powder is not prone to falling off when anodic oxidation is carried out, meanwhile, the heat dissipation ball shell can effectively protect the mixed powder from contacting with air before spraying, and further the condition of advanced oxidation is effectively avoided.
Furthermore, the heat-eliminating spherical shell is prepared from solid dry ice, and the filling degree of the mixed powder of the nano ceramic particles and the aluminum powder in the inner cavity of the heat-eliminating spherical shell is not higher than 90%.
Further, when the mixed powder in the vaporization bubble ball in S2 is all nano ceramic particles, the aluminum alloy substrate below the vaporization bubble ball can be seen by naked eyes after the spraying in S2, so that when the next step is carried out, the hard powder layer is not easy to influence the formation of an oxide film on the aluminum alloy substrate, the formed oxide film can surround the hard powder layer, the hard powder layer can be embedded in the oxide film, certain fixation is obtained, the hardness of the aluminum alloy oxide film is obviously improved, and the problem of poor protection effect on the aluminum alloy is caused.
Further, the oxidation temperature in S3 is controlled at-7-8 ℃, during the anodic oxidation process of S3, the voltage is controlled to be gradually increased to the final voltage, and the process of voltage change is maintained within 5-10 min.
Furthermore, the temperature of the aluminum alloy substrate when the vaporization bubble balls are sprayed is not lower than 100 ℃ in the S2-S4 process, and the powder spraying is carried out under the condition that the inert gas is used as the protective atmosphere, so that the powder is not easy to oxidize in the high-temperature spraying process, and further, the oxide layer can be uniformly distributed on the surface of the aluminum alloy substrate when the anodic oxidation is carried out, and the formed oxide layer is better.
Furthermore, the mixing volume ratio of the nano ceramic particles and the aluminum powder in the vaporization bubble spheres in S4 is 1:0.3-5, so that when anodic oxidation is carried out again, the nano ceramic particles are reduced and the aluminum powder is increased, and the distribution and content of a compact oxide film in a formed oxide interlayer are increased.
Furthermore, the repetition frequency of the step S4 is not more than 3 times, each time S4 is repeated, the content of aluminum powder is increased by 20-30%, the hardness of the formed oxidation lamination is gradually increased from outside to inside along with the multiple times of anodic oxidation operation, and the compactness of the oxidation lamination is gradually enhanced from inside to outside.
Furthermore, when S4 is repeated, when the hardness of the formed oxidation interlayer is 3-5 times of that of the aluminum oxide layer, the last operation of repeating S4 is performed, so that the oxidation lamination finally formed by the process is effectively guaranteed to have higher hardness compared with the prior art, and when the last operation is repeated, all mixed powder in the vaporization bubble ball is aluminum powder, the outermost layer of the oxidation lamination is a compact oxide layer, and the protection effect on the internal aluminum alloy is further effectively guaranteed.
3. Advantageous effects
Compared with the prior art, the invention has the advantages that:
(1) according to the scheme, through the arrangement of the vaporization bubble balls and the cooperation of multiple times of anodic oxidation, an oxidation bottom layer and multiple layers of oxidation interlayers can be sequentially formed on the surface of the aluminum alloy substrate, and finally an oxidation lamination layer taking nano ceramic particles as a bottom is formed on the surface of the aluminum alloy substrate, so that the hardness of the formed oxidation lamination layer is gradually increased from outside to inside, and the compactness of the oxidation lamination layer is gradually enhanced from inside to outside.
(2) The vaporization bubble ball includes the heat and eliminates the spherical shell, the inside division of heat elimination spherical shell has the powder storage gas pocket, the inside injection of powder storage gas pocket has the powder adhesive, the heat is eliminated the spherical shell inner chamber and is filled the mixed powder of nano-ceramic granule and aluminium powder, when spouting the vaporization bubble ball on the aluminium alloy base plate, because the vaporization of high temperature heat elimination spherical shell, make the powder adhesive and fall on the aluminium alloy substrate upper surface simultaneously with mixed powder, thereby be convenient for mix the fixed of powder on the aluminium alloy substrate, make difficult quilt when carrying out anodic oxidation drop, the heat is eliminated the spherical shell simultaneously and can effectively be protected mixed powder and contact with the air before the spraying, and then effectively avoid its condition of oxidation in advance to take place.
(3) The heat-eliminating spherical shell is prepared from solid dry ice, and the filling degree of the mixed powder of the nano ceramic particles and the aluminum powder in the inner cavity of the heat-eliminating spherical shell is not higher than 90%.
(4) When all mixed powder in the vaporization bubble balls in the S2 is nano ceramic particles, the aluminum alloy base material below the vaporization bubble balls can be seen by naked eyes after spraying in the S2, so that when the next step is carried out, the hard powder layer is not easy to influence the formation of an oxide film on the aluminum alloy base material, the formed oxide film can surround the hard powder layer, the hard powder layer can be embedded in the oxide film to obtain certain fixation, the hardness of the aluminum alloy oxide film is obviously improved, and the problem of poor protection effect on aluminum alloy is caused.
(5) The oxidation temperature in S3 is controlled at-7-8 deg.C, and during the anodic oxidation process in S3, the voltage is gradually increased to the final voltage, and the voltage variation process is maintained within 5-10 min.
(6) S2-S4 when the vaporization bubble ball is sprayed, the temperature of the aluminum alloy base material is not lower than 100 ℃, and the powder is sprayed under the condition that inert gas is used as protective atmosphere, so that the powder is not easy to oxidize during high-temperature spraying, and further, the oxide layer can be uniformly distributed on the surface of the aluminum alloy base material when anodic oxidation is carried out, and the formed oxide layer is better.
(7) The mixing volume ratio of the nano ceramic particles and the aluminum powder in the vaporization bubble spheres in S4 is 1:0.3-5, so that when anodic oxidation is carried out again, the nano ceramic particles are reduced and the aluminum powder is increased, and the distribution and content of a compact oxidation film in a formed oxidation interlayer are increased.
(8) The repetition frequency of the step S4 is not more than 3, each time S4 is repeated, the content of aluminum powder is increased by 20-30%, the hardness of the formed oxidation lamination is gradually increased from outside to inside along with the progress of multiple anodic oxidation operations, and the compactness of the oxidation lamination is gradually enhanced from inside to outside.
(9) When the step S4 is repeated, when the hardness of the formed oxidation interlayer is 3-5 times of that of the aluminum oxide layer, the last step S4 is repeated, so that the oxidation lamination formed finally by the process is effectively guaranteed to have higher hardness compared with the prior art, and when the last step is repeated, all mixed powder in the vaporization bubble ball is aluminum powder, the outermost layer of the oxidation lamination is a compact oxide layer, and the protection effect on the internal aluminum alloy is further effectively guaranteed.
Drawings
FIG. 1 is a schematic flow chart of the present invention;
FIG. 2 is a schematic view of the structure of the vaporization bubble of the present invention;
FIG. 3 is a schematic diagram showing the structure of the process of the vaporization bubble of the present invention when it is sprayed on an aluminum alloy substrate.
The reference numbers in the figures illustrate:
1 heat eliminates spherical shell, 2 powder storage air hole.
Detailed Description
The drawings in the embodiments of the invention will be incorporated below; the technical scheme in the embodiment of the invention is clearly and completely described; obviously; the described embodiments are only some of the embodiments of the present invention; but not all embodiments, are based on the embodiments of the invention; all other embodiments obtained by a person skilled in the art without making any inventive step; all fall within the scope of protection of the present invention.
In the description of the present invention, it should be noted that the terms "upper", "lower", "inner", "outer", "top/bottom", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience of description and simplification of description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus should not be construed as limiting the present invention. Furthermore, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance.
In the description of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "disposed," "sleeved/connected," "connected," and the like are to be construed broadly, e.g., "connected," which may be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in a specific case to those of ordinary skill in the art.
Example 1:
referring to fig. 1, in which a represents an aluminum alloy substrate, b represents an oxide underlayer formed by a first anodization, c represents an oxide interlayer formed by a repeated anodization, and d represents an oxide layer formed by a last anodization, a hard anodization process of an aluminum alloy oxide film includes the following steps:
s1, firstly, carrying out wire drawing treatment on the surface of the aluminum alloy base material;
s2, uniformly spraying vaporization bubble balls on the surface of the aluminum alloy base material to form a hard powder layer on the surface of the aluminum alloy;
s3, placing the aluminum alloy base material with the hard powder layer into an oxidation tank containing anodic oxidation electrolyte, and simultaneously, taking a lead plate as a cathode, switching on a power supply to start primary anodic oxidation to form an oxidation bottom layer;
s4, taking out the aluminum alloy base material subjected to primary anodic oxidation, cleaning and airing, spraying the vaporization bubble spheres on the oxidation bottom layer again, and repeating the step S3 to perform secondary anodic oxidation to form an oxidation interlayer;
s5, S4 is repeated several times, and oxidation is performed several times to form an oxide stack.
Referring to fig. 2, in the figure, e represents the mixed powder, the vaporization bubble includes a heat-dissipating spherical shell 1, a powder-storing air hole 2 is formed in the heat-dissipating spherical shell 1, a powder adhesive is injected into the powder-storing air hole 2, the mixed powder of the nano ceramic particles and the aluminum powder is filled in the inner cavity of the heat-dissipating spherical shell 1, the heat-dissipating spherical shell 1 is prepared by solid dry ice, the filling degree of the mixed powder of the nano ceramic particles and the aluminum powder in the inner cavity of the heat-dissipating spherical shell 1 is not higher than 90%, referring to fig. 3, when the vaporized bubble ball is sprayed on the aluminum alloy substrate, the powder adhesive and the mixed powder simultaneously fall on the upper surface of the aluminum alloy substrate due to the vaporization of the high-temperature heat-eliminating spherical shell 1, thereby facilitating the fixation of the mixed powder on the aluminum alloy base material, leading the mixed powder not to be easily dropped off during the anodic oxidation, meanwhile, the heat-eliminating spherical shell 1 can effectively protect the mixed powder from contacting with air before spraying, and further effectively avoid the condition of advanced oxidation.
When all mixed powder in the vaporization bubble spheres in S2 is nano ceramic particles, and simultaneously the aluminum alloy base material below the vaporization bubble spheres can be seen by naked eyes after spraying in S2, so that the hard powder layer is not easy to influence the aluminum alloy base material to form an oxide film in the next step, and simultaneously the formed oxide film can be formed around the hard powder layer, so that the hard powder layer can be embedded in the oxide film to obtain certain fixation, and the problem that the aluminum alloy oxide film has low hardness and poor protection effect on the aluminum alloy is solved, wherein the oxidation temperature in S3 is controlled to be-7-8 ℃, the voltage is controlled to be gradually increased until the final voltage in the process of carrying out anodic oxidation of S3, the process of voltage change is maintained within 5-10min, the temperature of the aluminum alloy base material in the process of spraying the vaporization bubble spheres in S2-S4 is not lower than 100 ℃, and the vaporization bubble spheres are convenient to be vaporized by heat, and then be convenient for the release of the mixture of nano ceramic granule and aluminite powder and powder adhesive, and the powder spraying is gone on under inert gas as protective atmosphere's the condition for the powder is difficult for taking place the oxidation when high temperature spraying, and then effectively guarantees when carrying out anodic oxidation, and the oxide layer can be even distribution on aluminum alloy substrate surface, makes the oxide layer that forms better.
The mixing volume ratio of the nano ceramic particles and the aluminum powder in the vaporization bubble spheres in S4 is 1:0.3-5, so that when anodic oxidation is carried out again, the nano ceramic particles are reduced, the aluminum powder is increased, the distribution and the content of a compact oxidation film in a formed oxidation interlayer are increased, the repetition frequency of the step S4 is not more than 3 times, the content of the aluminum powder is increased by 20-30% when S4 is repeated, the formed oxidation lamination has gradually increased hardness from outside to inside along with the progress of multiple anodic oxidation operations, and the compactness of the oxidation lamination from inside to outside is gradually enhanced, compared with the prior art, the hardness of the oxidation film is obviously improved while the compactness of the oxidation film is effectively ensured, the scratching condition in the prior art is effectively avoided, and even if the scratching phenomenon occurs, the oxidation lamination still can play a good protection role on the internal aluminum alloy, when S4 is repeated, when the hardness of the formed oxidation interlayer is 3-5 times of that of the aluminum oxide layer, the last operation of repeating S4 is carried out, so that the oxidation lamination finally formed by the process is effectively guaranteed to have higher hardness compared with the prior art, and when the last operation is repeated, all mixed powder in the vaporization bubble ball is aluminum powder, the outermost layer of the oxidation lamination is a compact oxide layer, and the protection effect on the internal aluminum alloy is further effectively guaranteed.
Through the setting of vaporization bubble ball, cooperation many times anodic oxidation's operation, can form oxidation bottom and multilayer oxidation intermediate layer in proper order on aluminum alloy substrate surface, and then finally form the oxidation stromatolite of using nano ceramic granule as the bottoming on aluminum alloy substrate surface, make the oxidation stromatolite that forms increase gradually from outside to inside hardness, and the compactness of oxidation stromatolite from inside to outside strengthens gradually, compare in prior art, when effectively guaranteeing oxidation film compactness, show the hardness that improves the oxidation film, and then effectively avoid the circumstances of scratch scotch to take place among the prior art, and even take place scratch scotch phenomenon, this oxidation stromatolite still can play good guard action to the aluminum alloy of inside.
The above; but are merely preferred embodiments of the invention; the scope of the invention is not limited thereto; those skilled in the art can appreciate that the present invention is not limited to the specific embodiments disclosed herein; the technical scheme and the improved concept of the invention are equally replaced or changed; are intended to be covered by the scope of the present invention.
Claims (9)
1. A hard anodic oxidation process of an aluminum alloy oxide film is characterized in that: the method comprises the following steps:
s1, firstly, carrying out wire drawing treatment on the surface of the aluminum alloy base material;
s2, uniformly spraying vaporization bubble balls on the surface of the aluminum alloy base material to form a hard powder layer on the surface of the aluminum alloy;
s3, placing the aluminum alloy base material with the hard powder layer into an oxidation tank containing anodic oxidation electrolyte, and simultaneously, taking a lead plate as a cathode, switching on a power supply to start primary anodic oxidation to form an oxidation bottom layer;
s4, taking out the aluminum alloy base material subjected to primary anodic oxidation, cleaning and airing, spraying vaporization bubble balls on the oxidation bottom layer again, and repeating S3 to perform secondary anodic oxidation to form an oxidation interlayer;
s5, S4 is repeated several times, and oxidation is performed several times to form an oxide stack.
2. The hard anodizing process of an aluminum alloy oxide film according to claim 1, wherein: the vaporization bubble ball comprises a heat elimination ball shell 1), a powder storage air hole 2) is formed in the heat elimination ball shell 1) in a chiseled mode, a powder adhesive is injected into the powder storage air hole 2), and the inner cavity of the heat elimination ball shell 1) is filled with mixed powder of nano ceramic particles and aluminum powder.
3. The hard anodizing process of an aluminum alloy oxide film according to claim 2, wherein: the heat-eliminating spherical shell 1) is prepared from solid dry ice, and the filling degree of the mixed powder of the nano ceramic particles and the aluminum powder in the inner cavity of the heat-eliminating spherical shell 1) is not higher than 90%.
4. The hard anodizing process of an aluminum alloy oxide film according to claim 1, wherein: all the mixed powder in the vaporization bubble in the S2 is nano ceramic particles, and the aluminum alloy base material below the vaporization bubble can be seen by naked eyes after spraying in the S2.
5. The hard anodizing process of an aluminum alloy oxide film according to claim 1, wherein: and the oxidation temperature in the S3 is controlled to be-7-8 ℃, the voltage is controlled to be gradually increased until the final voltage in the anodic oxidation process of the S3, and the voltage change process is maintained within 5-10 min.
6. The hard anodizing process of an aluminum alloy oxide film according to claim 1, wherein: and the temperature of the aluminum alloy base material of S2-S4 is not lower than 100 ℃ when the vaporization bubble ball is sprayed, and the powder spraying is carried out under the condition that inert gas is used as protective atmosphere.
7. The hard anodizing process of an aluminum alloy oxide film according to claim 1, wherein: the mixing volume ratio of the nano ceramic particles in the vaporization bubble spheres to the aluminum powder in S4 is 1: 0.3-5.
8. The process of claim 7, wherein the hard anodizing of the aluminum alloy oxide film comprises: the repetition frequency of the step S4 is not more than 3 times, and the content of the aluminum powder is increased by 20-30% every time S4 is repeated.
9. The hard anodizing process of an aluminum alloy oxide film according to claim 6, wherein: when the hardness of the formed oxide interlayer is 3-5 times of that of the aluminum oxide layer in the repetition of S4, the last repetition of S4 is performed, and the mixed powder in the vaporized bubble is all aluminum powder in the last repetition.
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| DE102007052575A1 (en) * | 2007-11-03 | 2009-05-07 | Märzhäuser Wetzlar GmbH & Co. KG | Protective layer of hard-anodized microscopic aluminum workpieces, comprises a composite-lacquer reinforced with a filler, and a hard-anodized layer that is colored black |
| US20140150819A1 (en) * | 2012-12-05 | 2014-06-05 | Lam Research Corporation | Method of wet cleaning aluminum chamber parts |
| KR20170122883A (en) * | 2016-04-27 | 2017-11-07 | (주)티티에스 | Surface treated products deposited ceramic film layer with granule shape |
| US20190275779A1 (en) * | 2018-03-08 | 2019-09-12 | Mitsubishi Heavy Industries, Ltd. | Additive manufacturing method |
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| DE102007052575A1 (en) * | 2007-11-03 | 2009-05-07 | Märzhäuser Wetzlar GmbH & Co. KG | Protective layer of hard-anodized microscopic aluminum workpieces, comprises a composite-lacquer reinforced with a filler, and a hard-anodized layer that is colored black |
| US20140150819A1 (en) * | 2012-12-05 | 2014-06-05 | Lam Research Corporation | Method of wet cleaning aluminum chamber parts |
| KR20170122883A (en) * | 2016-04-27 | 2017-11-07 | (주)티티에스 | Surface treated products deposited ceramic film layer with granule shape |
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