CN108330476B - Aluminum alloy surface metal-organic framework film for washing-free ship - Google Patents
Aluminum alloy surface metal-organic framework film for washing-free ship Download PDFInfo
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- CN108330476B CN108330476B CN201711484033.8A CN201711484033A CN108330476B CN 108330476 B CN108330476 B CN 108330476B CN 201711484033 A CN201711484033 A CN 201711484033A CN 108330476 B CN108330476 B CN 108330476B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Abstract
The invention relates to the technical field of metal surface treatment, in particular to a washing-free marine aluminum alloy surface metal-organic framework film. The framework film is obtained by treating the surface of the marine aluminum alloy with a treatment liquid, wherein the treatment liquid is prepared from the following components in parts by weight: 0.1 to 4 weight percent of fluozirconic acid with the concentration of 45 percent, 0.5 to 3.5 weight percent of fluotitanic acid with the concentration of 50 percent, 0.2 to 1 weight percent of hydrofluoric acid with the concentration of 50 percent, 0.5 to 2.5 weight percent of silane coupling agent, 0.02 to 0.1 weight percent of phytic acid with the concentration of 50 percent, and the balance of water. According to the invention, the aluminum alloy is endowed with good corrosion resistance by coating the treatment liquid on the surface of the aluminum alloy, the treatment liquid takes fluozirconic acid and fluotitanic acid as main raw materials, organic matter components such as silane coupling agent, phytic acid and the like are added to act on the surface of the aluminum alloy, a chromium-free treatment process is adopted, the treatment liquid is safe and environment-friendly, the pollution to the environment is greatly reduced, and the prepared framework film is beneficial to improving the corrosion resistance of the surface of the aluminum alloy and the adhesiveness of the surface to powder coating.
Description
Technical Field
The invention relates to the technical field of metal surface treatment, in particular to a washing-free marine aluminum alloy surface metal-organic framework film.
Background
The aluminum alloy has good corrosion resistance, weldability and mechanical properties, and is widely applied to ship structure materials. However, because the oxidation film of the aluminum alloy is thin, the matrix can be corroded under the erosion action of seawater and humid ocean atmosphere, so that the appearance and the organic coating adhesion are affected. At present, the corrosion resistance of the aluminum alloy is improved by chemical treatment on the surface of the aluminum alloy, and most of the treatment liquids containing chromium such as chromic acid-chromate and the like are directly contacted with the surface of a metal material so as to precipitate a chromate film, or the chromate film is coated on the surface of the metal material and is precipitated after being dried so as to protect the surface of the aluminum alloy. However, hexavalent chromium is harmful to human body and environment, and not only is pollution generated in the treatment process, but also secondary pollution is caused to the environment when the treated product is used and discarded in the future due to hexavalent chromium in the conversion coating, so that the use of the hexavalent chromium chemical conversion treatment technology is more and more strictly limited.
Currently, various countries develop more effective and environment-friendly chromium-free metal surface treatment liquids, for example, chinese patent publication No. CN1123649C discloses a similar chromium-free surface treatment liquid, which is an acidic solution containing titanium, zirconium or a mixture thereof, phosphate and fluoride as main components, and having a pH value of 1.5-4.0. The solution is free from sediment and harmful chromium ions, but when the solution is sprayed on the surface of a metal material in a short time (15 to 30 seconds), the resulting coating is uneven, exhibiting unstable corrosion resistance and uneven adhesion to paint or coating. Chinese patent publication No. CN102409324A discloses a chromium-and phosphorus-free nano-scale chemical conversion solution, which is composed of titanium salt, zirconium salt, silicon compound, accelerator, pH adjuster, surfactant, etc., and is completely free of chromium ions and phosphates, but in the preparation of the nano-scale chemical conversion film, after chemical conversion, the impurities such as acid and alkali on the surface of the film need to be removed by a water washing step, which increases the industrial production cost, and the corrosion resistance of the conversion film lasts for a short time, and the application range is narrow.
Therefore, it is a technical problem to be solved in the art to provide a chromium-free aluminum alloy surface film layer with good corrosion resistance and adhesion.
Disclosure of Invention
The invention aims to provide a chromium-free metal-organic framework film with good corrosion resistance and good adhesion for a washing-free marine aluminum alloy surface, and simultaneously, the preparation process of the framework film is optimized, and the industrial production cost is reduced.
The invention adopts the following technical scheme:
the metal-organic framework film is obtained by treating the surface of the marine aluminum alloy with a treatment solution, wherein the treatment solution is prepared from the following components in parts by weight: 0.1 to 4 weight percent of fluozirconic acid with the concentration of 45 percent, 0.5 to 3.5 weight percent of fluotitanic acid with the concentration of 50 percent, 0.2 to 1 weight percent of hydrofluoric acid with the concentration of 50 percent, 0.5 to 2.5 weight percent of silane coupling agent, 0.02 to 0.1 weight percent of phytic acid with the concentration of 50 percent, and the balance of water.
Further, the pH value of the treatment liquid is 2-5.
Furthermore, the treatment solution is diluted by water in the using process, and the content of the treatment solution in the diluted solution is 2.5-4 wt%.
Further, the film forming process of the metal-organic framework film comprises the following steps:
(1) surface pretreatment of the aluminum alloy: polishing the surface of the aluminum alloy by using silicon carbide water sand paper until the surface roughness is below 10 mu m, soaking the aluminum alloy in an acid degreasing aqueous solution for 2 to 6 minutes, washing the aluminum alloy by using clear water, repeating the operation twice, and naturally airing or air-drying the aluminum alloy;
(2) chemical conversion treatment of aluminum alloy: soaking the aluminum alloy in the treatment solution, or directly spraying the treatment solution on the surface of the aluminum alloy, or coating the treatment solution on the surface of the aluminum alloy, wherein the treatment time is 40s-10 min;
(3) and (3) drying: and (3) directly and naturally airing or drying the aluminum alloy subjected to the chemical conversion treatment in the step (2).
Further, the treatment time of soaking the aluminum alloy in the treatment liquid in the step (2) is 2-10 min.
Further, the treatment time of directly spraying the treatment liquid on the surface of the aluminum alloy in the step (2) is 1-3min, and the spraying pressure is 0.08-0.18 KPa.
Further, the treatment time for coating the treatment solution on the surface of the aluminum alloy in the step (2) is 40-70 s.
Further, in the step (3), the drying temperature is 40-120 ℃, and the drying time is 10-15 min.
The metal-organic framework film of the invention endows the aluminum alloy with good corrosion resistance by coating the treatment liquid on the surface of the aluminum alloy. The treatment liquid takes fluozirconic acid and fluotitanic acid as main raw materials, organic matter components such as silane coupling agent, phytic acid and the like are added to act on the surface of the aluminum alloy, the formed skeleton film takes Zr-Ti composite inorganic matter as main film forming salt, and the silane coupling agent and the phytic acid are added to be auxiliary film forming substances, so that binary structure oxide taking Zr-Ti as main salt element and chromium-free passivation film combined with the organic matter can be rapidly generated on the surface of the aluminum alloy, and further the corrosion resistance of the surface of the aluminum alloy and the good adhesion of the aluminum alloy to powder coating are improved.
When the treatment liquid is used for treating the surface of the aluminum alloy, the aluminum alloy surface has different electric phases and impurity atoms according to a cathode film forming mechanismThe electrochemical reaction takes place with the formation of numerous galvanic cells in the surface micro-areas: metal dissolution in the micro-anode region: m-ze-→Mz+(M represents a metal element in the aluminum alloy), and H is generated in the micro-cathode region2And (3) precipitation: 2H++2e-→H2Or O2Reduction: o is2+2H2O+4e-→4OH-Thereby making the micro-cathode region OH-The ion concentration is increased, the pH value is increased, and favorable conditions are created for the deposition of the aluminum oxide, and the reaction equation is as follows:
2Al+6H++3ZrF6 2-+5H2O→2AlOF.3ZrOF2+10HF+3H2
2Al+6H++3TiF6 2-+5H2O→2AlOF.3TiOF2+10HF+3H2
the formation of the zirconium and titanium film layer improves the adhesive force between the passive film and the powder coating, increases the density of the skeleton film in a microcosmic aspect and improves the corrosion resistance of the skeleton film.
Meanwhile, organic components such as a silane coupling agent are added into the treatment liquid, unsaturated bonds in the organic raw materials can be combined with metal bonds hydrolyzed from fluozirconic acid and fluotitanic acid to form a chemical bond framework, a foundation is provided for deposition of aluminum oxide, and the corrosion resistance of the metal-organic framework film is effectively improved. Furthermore, due to the addition of organic components such as a silane coupling agent, the treatment liquid can be directly dried after being coated on the surface of the aluminum alloy, washing is not needed, the manufacturing process of a framework film is simplified, industrial water is reduced, the silane coupling agent solution can be uniformly reserved on the surface of a conversion film through washing-free, silane can be hydrolyzed in the curing process after powder or paint coating, bonding is carried out between organic resin and an inorganic interface, interface fusion is promoted, and the bonding force between the interfaces is promoted.
The washing-free marine aluminum alloy surface metal-organic framework film has the following beneficial effects:
(1) according to the water-free marine aluminum alloy surface metal-organic framework film, the treatment liquid is coated on the surface of the aluminum alloy to endow the aluminum alloy with good corrosion resistance, the treatment liquid takes fluozirconic acid and fluotitanic acid as main raw materials, organic matter components such as a silane coupling agent, phytic acid and the like are added to act on the surface of the aluminum alloy, a chromium-free treatment process is adopted, the water-free marine aluminum alloy surface metal-organic framework film is safe and environment-friendly, the pollution to the environment is reduced to the maximum extent, and the prepared framework film is beneficial to improving the corrosion resistance of the surface of the aluminum alloy and the adhesion of the aluminum alloy to powder.
(2) According to the water-free marine aluminum alloy surface metal-organic framework film, organic raw materials such as the silane coupling agent are adopted, the treatment liquid can be directly dried after being coated on the surface of the aluminum alloy, the silane coupling agent solution can be uniformly reserved on the surface of the conversion film, silane can be hydrolyzed in the curing process after powder or paint coating, bonding is carried out between organic resin and an inorganic interface, interface fusion is promoted, the bonding force between the interfaces is promoted, water washing is not needed, on one hand, the manufacturing process of the framework film is simplified, the production efficiency is improved, on the other hand, water resources are saved, and the production cost is reduced.
(3) The metal-organic framework film on the surface of the water-washing-free marine aluminum alloy can ensure that the three-level powder coating has excellent adhesion on the surface of the marine aluminum alloy material, has wider application range compared with the existing aluminum alloy surface chromium-free passivation film, can better adapt to the humid environment of the marine industry, and obviously improves the mechanical properties of the aluminum alloy material, such as corrosion resistance, adhesion of the powder coating, impact resistance, toughness and the like.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to specific embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The metallic materials used in the following examples:
the domestic aluminum-magnesium alloy section 6061 with the thickness of 1mm comprises the following main components: 0.35%, Mg: 0.8 to 0.9%, Si: 0.65 to 0.75%, Cu: 0.85-0.95%, Mn: 0.15-0.25% and the balance of Al.
The surface of the above-mentioned metal material was cleaned according to the acidic degreasing aqueous solution of patent CN201010206660.7 or CN201010543878.1 and then used for the surface treatment of the following examples.
Example 1
A metal-organic framework film for the surface of a non-washing marine aluminum alloy, which is obtained by treating the surface of the marine aluminum alloy with a treatment solution, wherein the treatment solution is prepared from the following components in percentage by weight: 0.1 wt% of fluorozirconic acid with the concentration of 45%, 1 wt% of fluotitanic acid with the concentration of 50%, 0.8 wt% of hydrofluoric acid with the concentration of 50%, 1 wt% of silane coupling agent, 0.05 wt% of phytic acid with the concentration of 50% and the balance of water, and the pH value of the treatment solution is adjusted to 2. The treatment solution is diluted by water in the using process, and the content of the treatment solution in the diluted solution is 4 wt%.
The film forming process of the skeleton film in this example is as follows:
(1) surface pretreatment of the aluminum alloy: cutting a sample piece from a 6061 large-size aluminum alloy section, polishing the sample piece by using silicon carbide water sand paper until the surface roughness is below 10 mu m, soaking the sample piece in an acid degreasing aqueous solution for 2 minutes, washing the sample piece by using clear water, repeating the operation twice, and naturally airing or air-drying the sample piece;
(2) chemical conversion treatment of aluminum alloy: soaking the aluminum alloy in the treatment solution for 4min, or directly spraying the treatment solution on the surface of the aluminum alloy at a spraying pressure of 0.08KPa for 3min, or coating the treatment solution on the surface of the aluminum alloy for 60 s;
(3) and (3) drying: and (3) directly and naturally airing the aluminum alloy subjected to the chemical conversion treatment in the step (2).
Example 2
A metal-organic framework film for the surface of a non-washing marine aluminum alloy, which is obtained by treating the surface of the marine aluminum alloy with a treatment solution, wherein the treatment solution is prepared from the following components in percentage by weight: 0.4 wt% of fluozirconic acid with the concentration of 45%, 2.5 wt% of fluotitanic acid with the concentration of 50%, 0.4 wt% of hydrofluoric acid with the concentration of 50%, 1.5 wt% of silane coupling agent, 0.02 wt% of phytic acid with the concentration of 50% and the balance of water. The pH of the treatment solution was adjusted to 3.6. The treatment solution is diluted by water in the using process, and the content of the treatment solution in the diluted solution is 3.2 wt%.
The film forming process of the skeleton film in this example is as follows:
(1) surface pretreatment of the aluminum alloy: cutting a sample piece from a 6061 large-size aluminum alloy section, polishing the sample piece by using silicon carbide water sand paper until the surface roughness is below 10 mu m, soaking the sample piece in an acid degreasing aqueous solution for 6 minutes, washing the sample piece by using clear water, repeating the operation twice, and naturally airing or air-drying the sample piece;
(2) chemical conversion treatment of aluminum alloy: soaking the aluminum alloy in the treatment solution for 6min, or directly spraying the treatment solution on the surface of the aluminum alloy at a spraying pressure of 0.12KPa for 1min, or coating the treatment solution on the surface of the aluminum alloy for 40 s;
(3) and (3) drying: and (3) directly drying the aluminum alloy subjected to the chemical conversion treatment in the step (2), wherein the drying temperature is 40 ℃, and the drying time is 15 min.
Example 3
A metal-organic framework film for the surface of a non-washing marine aluminum alloy, which is obtained by treating the surface of the marine aluminum alloy with a treatment solution, wherein the treatment solution is prepared from the following components in percentage by weight: 1.0 wt% of fluozirconic acid with the concentration of 45%, 2.4 wt% of fluotitanic acid with the concentration of 50%, 0.2 wt% of hydrofluoric acid with the concentration of 50%, 2.5 wt% of silane coupling agent, 0.1 wt% of phytic acid with the concentration of 50% and the balance of water. The pH of the treatment solution was adjusted to 5. The treatment solution is diluted by water in the using process, and the content of the treatment solution in the diluted solution is 2.5 wt%.
The film forming process of the skeleton film in this example is as follows:
(1) surface pretreatment of the aluminum alloy: cutting a sample piece from a 6061 large-size aluminum alloy section, polishing the sample piece by using silicon carbide water sand paper until the surface roughness is below 10 mu m, soaking the sample piece in an acid degreasing aqueous solution for 4 minutes, washing the sample piece by using clear water, repeating the operation twice, and naturally airing or air-drying the sample piece;
(2) chemical conversion treatment of aluminum alloy: soaking the aluminum alloy in the treatment solution for 2min, or directly spraying the treatment solution on the surface of the aluminum alloy, wherein the spraying pressure is 0.1KPa, and the treatment time is 2min, or coating the treatment solution on the surface of the aluminum alloy, and the treatment time is 50 s;
(3) and (3) drying: and (3) directly drying the aluminum alloy subjected to the chemical conversion treatment in the step (2), wherein the drying temperature is 120 ℃, and the drying time is 10 min.
Example 4
A metal-organic framework film for the surface of a non-washing marine aluminum alloy, which is obtained by treating the surface of the marine aluminum alloy with a treatment solution, wherein the treatment solution is prepared from the following components in percentage by weight: 1.2 wt% of fluorozirconic acid with a concentration of 45%, 0.5 wt% of fluotitanic acid with a concentration of 50%, 1 wt% of hydrofluoric acid with a concentration of 50%, 0.5 wt% of silane coupling agent, 0.08 wt% of phytic acid with a concentration of 50%, and the balance of water. The pH of the treatment solution was adjusted to 4. The treatment solution is diluted by water in the using process, and the content of the treatment solution in the diluted solution is 3 wt%.
The film forming process of the skeleton film in this example is as follows:
(1) surface pretreatment of the aluminum alloy: cutting a sample piece from a 6061 large-size aluminum alloy section, polishing the sample piece by using silicon carbide water sand paper until the surface roughness is below 10 mu m, soaking the sample piece in an acid degreasing aqueous solution for 6 minutes, washing the sample piece by using clear water, repeating the operation twice, and naturally airing or air-drying the sample piece;
(2) chemical conversion treatment of aluminum alloy: soaking the aluminum alloy in the treatment solution for 10min, or directly spraying the treatment solution on the surface of the aluminum alloy at a spraying pressure of 0.18KPa for 1.5min, or coating the treatment solution on the surface of the aluminum alloy for 70 s;
(3) and (3) drying: and (3) directly and naturally airing the aluminum alloy subjected to the chemical conversion treatment in the step (2).
The aluminum alloy materials obtained in examples 1 to 4 were electrostatically sprayed with the three-stage powder coating, followed by curing at a curing temperature of 210 ℃ for 15 min. Respectively carrying out acid salt spray tests on the cured materials,Constant temperature condensed water test and SO resistance2And testing and filiform corrosion testing, wherein the specific testing conditions are as follows:
(1) acid salt spray test
The test is according to ISO 9227: 2012, test equipment is Q-FOG/SSP1100, the test duration is 2000 hours, and the technical requirements are according to QUALICOAT 14 edition: the foaming rating is according to ISO 4628-2: 2 or less (S2); penetration area along the scribe: less than or equal to 16mm210 cm; single maximum penetration length along the cross-hatch: less than or equal to 4 mm.
(2) Constant temperature condensate water test
The test is according to ISO 6270-2: 2005, test equipment liebsich K300, test duration 2000 hours, specification according to QUALICOAT version 14: the foaming rating is according to ISO 4628-2: 2 or less (S2); single maximum penetration length along the cross-hatch: less than or equal to 1 mm.
(3) SO resistance2Testing
The test is based on DIN EN ISO 3231, test equipment A-SC KBG 400 Co. Liebsche, test duration 24cycles, technical requirements are based on QUALICOAT 14 edition: non-discolouring or foaming grades according to ISO 4628-2: 2 or less (S2); single maximum penetration length along the cross-hatch: less than or equal to 1 mm.
(4) Filiform corrosion test
The test was carried out according to DIN EN ISO 4623-2:2004, test equipment Climate Chamber Co Binder, test duration 1000 hours, technical requirements according to QUALICOAT version 14: maximum length of filiform corrosion: 4mm or less, average length of filiform corrosion: 2mm or less, the number of filiform corrosion: less than or equal to 20/10 cm.
The results of the tests performed in examples 1-4 are shown in tables 1-4.
Table 1 acid salt spray test results
TABLE 2 test results of constant temperature condensate water
TABLE 3 SO resistance2Test results
| Colour change or foaming rating | Single maximum penetration length/mm | |
| Example 1 | 0(S0) | 0 |
| Example 2 | 0(S0) | 0 |
| Example 3 | 0(S0) | 0 |
| Example 4 | 0(S0) | 0 |
TABLE 4 filiform corrosion test results
As can be seen from tables 1 to 4, the metal-organic framework film on the surface of the washing-free marine aluminum alloy provided by the invention has good corrosion resistance and high adhesion to the third-level powder coating, and the third-level powder coating has higher mechanical properties such as toughness and impact resistance compared with the first-level and second-level powder coatings, so that the metal-organic framework film on the surface of the washing-free marine aluminum alloy provided by the invention can play an excellent protection role on the marine aluminum alloy. Meanwhile, the metal-organic framework film on the surface of the water-free marine aluminum alloy is directly dried without being washed after chemical conversion in the film forming process, so that the production process is simplified, water resources are saved, and the production cost is reduced.
The present invention has been further described with reference to specific embodiments, but it should be understood that the detailed description should not be construed as limiting the spirit and scope of the present invention, and various modifications made to the above-described embodiments by those of ordinary skill in the art after reading this specification are within the scope of the present invention.
Claims (8)
1. The metal-organic framework film for the surface of the ship aluminum alloy without being washed is characterized by being obtained by treating the surface of the ship aluminum alloy with a treatment solution, wherein the treatment solution is prepared from the following components in parts by weight: 0.1 to 4 weight percent of fluozirconic acid with the concentration of 45 percent, 0.5 to 3.5 weight percent of fluotitanic acid with the concentration of 50 percent, 0.2 to 1 weight percent of hydrofluoric acid with the concentration of 50 percent, 0.5 to 2.5 weight percent of silane coupling agent, 0.02 to 0.1 weight percent of phytic acid with the concentration of 50 percent, and the balance of water.
2. The wash-free marine aluminum alloy surface metal-organic framework film according to claim 1, wherein the pH of the treatment liquid is 2 to 5.
3. The wash-free marine aluminum alloy surface metal-organic framework film according to claim 2, wherein the treatment solution is diluted with water during use, and the content of the treatment solution in the diluted solution is 2.5-4 wt%.
4. The aluminum alloy surface metal-organic framework film for the washing-free boat as recited in claim 3, wherein the film forming process of the framework film is as follows:
(1) surface pretreatment of the aluminum alloy: polishing the surface of the aluminum alloy by using silicon carbide water sand paper until the surface roughness is below 10 mu m, soaking the aluminum alloy in an acid degreasing aqueous solution for 2 to 6 minutes, washing the aluminum alloy by using clear water, repeating the operation twice, and naturally airing or air-drying the aluminum alloy;
(2) chemical conversion treatment of aluminum alloy: soaking the aluminum alloy in the treatment solution, or directly spraying the treatment solution on the surface of the aluminum alloy, or coating the treatment solution on the surface of the aluminum alloy, wherein the treatment time is 40s-10 min;
(3) and (3) drying: and (3) directly and naturally airing or drying the aluminum alloy subjected to the chemical conversion treatment in the step (2).
5. The aluminum alloy surface metal-organic framework film for the waterless marine washing as recited in claim 4, wherein the treatment time of immersing the aluminum alloy in the treatment liquid in the step (2) is 2 to 10 min.
6. The aluminum alloy surface metal-organic framework film for the washing-free boat as recited in claim 4, wherein the treatment time of directly spraying the treatment liquid on the aluminum alloy surface in the step (2) is 1-3min, and the spraying pressure is 0.08-0.18 KPa.
7. The wash-free marine aluminum alloy surface metal-organic framework film according to claim 4, wherein the treatment time for coating the treatment liquid on the aluminum alloy surface in the step (2) is 40 to 70 seconds.
8. The aluminum alloy surface metal-organic framework film for the wash-free boat as recited in claim 4, wherein the drying temperature in the step (3) is 40-120 ℃ and the drying time is 10-15 min.
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