CN113150653A - High-strength corrosion-resistant aluminum alloy and processing technology thereof - Google Patents
High-strength corrosion-resistant aluminum alloy and processing technology thereof Download PDFInfo
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- CN113150653A CN113150653A CN202110691800.2A CN202110691800A CN113150653A CN 113150653 A CN113150653 A CN 113150653A CN 202110691800 A CN202110691800 A CN 202110691800A CN 113150653 A CN113150653 A CN 113150653A
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- 238000005260 corrosion Methods 0.000 title claims abstract description 90
- 230000007797 corrosion Effects 0.000 title claims abstract description 90
- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 88
- 238000005516 engineering process Methods 0.000 title claims abstract description 9
- 238000012545 processing Methods 0.000 title claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 51
- 239000011248 coating agent Substances 0.000 claims abstract description 50
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 46
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 38
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 38
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 38
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 23
- 239000003822 epoxy resin Substances 0.000 claims abstract description 18
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 18
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910045601 alloy Inorganic materials 0.000 claims description 21
- 239000000956 alloy Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- 239000012188 paraffin wax Substances 0.000 claims description 17
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 15
- 238000005507 spraying Methods 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 239000000908 ammonium hydroxide Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 7
- JQZGUQIEPRIDMR-UHFFFAOYSA-N 3-methylbut-1-yn-1-ol Chemical compound CC(C)C#CO JQZGUQIEPRIDMR-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 239000006255 coating slurry Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000002844 melting Methods 0.000 claims description 5
- 230000008018 melting Effects 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
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- 239000012535 impurity Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 6
- 230000006870 function Effects 0.000 abstract description 6
- 230000007246 mechanism Effects 0.000 abstract description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 abstract description 4
- 230000007123 defense Effects 0.000 abstract description 4
- 230000005012 migration Effects 0.000 abstract description 4
- 238000013508 migration Methods 0.000 abstract description 4
- 229910052761 rare earth metal Inorganic materials 0.000 abstract description 3
- 230000008439 repair process Effects 0.000 abstract description 3
- 239000003112 inhibitor Substances 0.000 description 8
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- 239000013078 crystal Substances 0.000 description 3
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- 238000012360 testing method Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
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- 229920000642 polymer Polymers 0.000 description 2
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- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
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- 230000004044 response Effects 0.000 description 1
- 239000001022 rhodamine dye Substances 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
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- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Paints Or Removers (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention discloses a high-strength corrosion-resistant aluminum alloy and a processing technology thereof. The high-strength corrosion-resistant aluminum alloy is prepared by coating an aluminum alloy substrate doped with rare earth element gallium with a surface corrosion-resistant coating with self-repairing and indicating functions. (1) Epoxy resin is used as a first line of defense of corrosion resistance of the aluminum alloy; (2) using SiO2The photothermal effect of nano TiN particles in @ methylbutinol @ TiN generates an aluminum alloy self-repairing mechanism, and simultaneously releases methylbutinolAs a second defense line for protecting the aluminum alloy from corrosion; (3) the prepared polyacrylate @ paraffin @ rhodamine has crack indicating performance and is convenient to repair manually in time; (4) and the nano TiN particles falling to the interface of the coating and the aluminum alloy substrate are utilized to effectively inhibit the migration of atoms on the surface of the aluminum alloy substrate.
Description
Technical Field
The invention relates to the technical field of aluminum alloy, in particular to high-strength corrosion-resistant aluminum alloy and a processing technology thereof.
Background
With the development of economic society, aluminum alloys have been widely used in industrial fields such as automobile construction due to their advantages of low density, good ductility, low cost, etc., but they are limited due to their disadvantages of poor strength, poor wear resistance, etc. For example, the steel is used for doors and windows, automobile shells and the like, when the manufactured equipment needs to be blown by wind and rain and is added with the problem of atmospheric environment, the problem of corrosion easily occurs, and the problems of mechanical property reduction and breakage are caused by long-term accumulation. And the corrosion resistance of the aluminum alloy can be obviously enhanced by utilizing the surface coating. The corrosion resistance of the aluminum alloy can be enhanced by using the corrosion inhibitor, and the corrosion can be caused by scratching of the coating and exposure of the aluminum alloy, so that a self-repairable surface corrosion-resistant coating is needed. Meanwhile, the aluminum alloy has no indication function under the general condition, and if the aluminum alloy has the color indication function when being damaged by external force, the coating can be timely supplemented to prolong the service life.
Therefore, the research on how to encapsulate the corrosion inhibitor in the surface corrosion-resistant coating to form a corrosion-resistant two-layer protection and increase the service life of the aluminum alloy, and the high-strength corrosion-resistant aluminum alloy with the self-repairing and indicating functions is necessary.
Disclosure of Invention
The invention aims to provide a high-strength corrosion-resistant aluminum alloy and a processing technology thereof, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a high-strength corrosion-resistant aluminum alloy comprises an aluminum alloy substrate and a surface corrosion-resistant coating; the surface corrosion-resistant coating comprises the following raw materials: 40-70 parts by weight of epoxy resin and SiO2@ methylbutinol @ TiN 5-10 parts, polyacrylate @ paraffin @ rhodamine 1-5 parts and imidazole 20-30 parts.
Preferably, the raw materials of the aluminum alloy base material comprise the following components: according to weight percentage, 0.8 percent of Cr, 1.5 percent of Mg, 2 percent of Si, 0.2 percent of Fe, 0.49 percent of Cu, 0.8 percent of Mn, 0.3 percent of Ga, and the balance of Al and inevitable impurities.
Preferably, the surface corrosion-resistant coating is 1-30 mm.
Preferably, the SiO2The particle size of @ methylbutinol @ TiN is 100-200 nm.
Preferably, the SiO2The @ methylbutinol @ TiN raw material comprises the following components: 10-20 parts of nano TiN particles, 8-14 parts of methyl butynol, 22-58 parts of tetraethyl silicate, 4-10 parts of ammonium hydroxide and 2-6 parts of polyacrylate.
Preferably, the polyacrylate @ paraffin @ rhodamine comprises the following components: 30-66 parts of acrylate, 20-40 parts of paraffin and 10-20 parts of rhodamine.
The processing technology of the high-strength corrosion-resistant aluminum alloy is characterized by comprising the following steps of:
s1: preparing a surface corrosion-resistant coating:
（1）SiO2preparation of @ methylbutinol @ TiN: ultrasonically dispersing the weighed nano TiN particles and polyacrylate in deionized water to form TiN dispersion liquid for later use; sequentially adding 4/5 tetraethyl silicate and ammonium hydroxide into a mixed solution containing deionized water and ethanol, setting the stirring speed at 200-400 rmp at 25-55 ℃, sequentially adding TiN dispersion liquid and methylbutinol, and reacting for 6-8 days; adding the rest 1/5 tetraethyl silicate, and reacting for 1 hour at the set temperature of 60-80 ℃; centrifuging, washing and drying to obtain SiO2@ methylbutynol @ TiN for use;
(2) preparation of polyacrylate @ paraffin @ rhodamine: melting the weighed paraffin, spraying the rhodamine water solution into the molten paraffin for 10-20 seconds at the spraying speed of 0.1-0.2 mm/min, and solidifying and cooling to obtain the paraffin @ rhodamine for later use; ultrasonically dispersing acrylate and a crosslinking agent in deionized water in sequence, setting the stirring speed to be 140-200 rmp, stirring for 1-2 hours, adding paraffin @ rhodamine, setting the stirring speed to be 200-400 rmp, reacting at 55-65 ℃, reacting for 20-36 hours, filtering, and washing to obtain polyacrylate @ paraffin @ rhodamine for later use;
(3) preparing a surface corrosion-resistant coating: weighing SiO2The @ methylbutinol @ TiN, polyacrylate @ paraffin @ rhodamine and epoxy resin are dispersed in deionized water at a set speed of 200-400 rmp, stirred for 4-6 hours, added with imidazole and stirred for 30-60 minutes to obtain surface corrosion-resistant coating slurry for later use;
s2: preparing high-strength corrosion-resistant aluminum alloy: mechanically polishing an alloy sheet by using a metallographic paper, ultrasonically cleaning the alloy sheet by using acetone, ethanol and deionized water for 10-30 minutes, drying the alloy sheet, transferring the alloy sheet to a rotary coating machine, spraying the slurry of the surface corrosion-resistant coating on the surface of an aluminum alloy substrate at a set rotating speed of 200-300 rmp, and curing the aluminum alloy substrate at 30 ℃ for 18-24 hours; and curing for 6-8 hours at 60 ℃ to obtain the high-strength corrosion-resistant aluminum alloy.
Preferably, in step (1) of S1, the mass fraction of the nano TiN particles in the TiN dispersion is 5 to 10 wt%.
In the technical scheme, an aluminum alloy substrate doped with rare earth element gallium (Ga) is coated with a surface corrosion-resistant coating with self-repairing and indicating functions to prepare the high-strength corrosion aluminum alloy. The method comprises the following specific steps:
gallium has a thinning effect in the crystal grain forming process, and can remove gas and harmful impurities of the aluminum alloy, reduce the generation of cracks and obviously enhance the strength of the aluminum alloy, so that the Ga-doped aluminum alloy substrate is selected as a main body. Performing surface treatment on the aluminum alloy substrate, and mechanically polishing the alloy sheet by using a metallographic machine to remove an oxide or hydroxide layer on the surface; and ultrasonically cleaning the coating by using acetone, ethanol and deionized water to remove grease so as to better coat the surface corrosion-resistant coating.
The self-repairing surface corrosion-resistant coating is prepared to solve the problems of corrosion of aluminum alloy and surface scratch. Specifically, the method comprises the following steps: the epoxy resin is an excellent chemical and oil resistant polymer, and a three-dimensional structure of the epoxy resin can be doped with substances to enhance various properties of substances. Therefore, the epoxy resin is used as a main body and is doped with SiO2@ methylbutinol @ TiN is used for self-repairing; doped polyacrylate @ paraffin @ rhodamine is used for the indication.
With respect to SiO2@ methylbutynol @ TiN: first, the epoxy coating is a coating with shape memory, which can be used to cover the exposed surface of the aluminum alloy under the scratch again under the trigger mechanism; secondly, TiN is absorptive to light and can be successfully converted into heat energy, so that the light-heat composite material has a remarkable photo-thermal effect; third, the SiO prepared2A container having a micro-porous-mesoporous structure that can act as a corrosion inhibitor; fourth, methylbutynol is a typical inhibitor of acid attack, is soluble in water, and can spread as a film on the metal surface, protecting the metal. Thus, we added nano TiN particles to tetraethyl silicate solution to make SiO2In the nucleation process, the coating grows by taking the crystal as a nucleation center; reuse of SiO2In (1)The methylbutinol is absorbed by the pore canal, and the corrosion inhibitor is encapsulated in the pore canal to form SiO2@ methylbutinol @ TiN. When external damage occurs, the corrosion inhibitor is released to protect the aluminum alloy for the second time. The self-repairing mechanism is as follows: when the epoxy resin is uniformly spread on the surface of the aluminum alloy and external stimulation appears, a certain part of the cured epoxy resin is damaged, the nano TiN particles convert absorbed light into heat energy by utilizing light radiation, firstly, the polymer generates thermal behavior by utilizing the rise of temperature to extend and coat the aluminum alloy, and secondly, the start of a photo-thermal response mechanism promotes the SiO2And (3) the methylbutinol in the pore channels diffuses slowly in general, so that the methylbutinol can form a film on the surface of the aluminum alloy to protect the aluminum alloy from being corroded. In addition, after the cracks are generated, the nano TiN particles fall to the interface of the coating and the aluminum alloy substrate, and the migration of atoms on the surface of the aluminum alloy substrate is effectively inhibited.
For doped polyacrylate @ paraffin @ rhodamine: the microcapsule is used for indicating function, and is a microcapsule which takes rhodamine as a center and is wrapped with inner shell paraffin and polyacrylate outer shell. Rhodamine is a common dye, and when a surface film layer is damaged, an orange color development phenomenon appears, and an orange color appearance part is a place where cracks appear, and the size of an area is the area subjected to damage. The film-forming property of the coating can be better improved by the adhesion of polyacrylate, and the hydrophobicity of the surface corrosion-resistant coating can be improved by the hydrophobicity. And the paraffin wax arranged between the polyacrylate layer and the rhodamine is used for preventing the rhodamine dye from leaking.
Compared with the prior art, the invention has the following beneficial effects: the invention takes epoxy resin as a main body and is doped with SiO2@ methylbutinol @ TiN for repair; the doped polyacrylate @ paraffin @ rhodamine is used as a coating, so that the aluminum alloy is effectively protected from being corroded. (1) Epoxy resin is used as a first line of defense of corrosion resistance of the aluminum alloy; (2) using SiO2The photothermal effect of nano TiN particles in @ methylbutinol @ TiN generates an aluminum alloy self-repairing mechanism, and the methylbutinol is released to protect the corrosion-resistant second defense line of the aluminum alloy most; (3) the prepared polyacrylate @ paraffin @ rhodamine has crack indicating performance and is convenient to repair manually in time; (4) by droppingAnd the nano TiN particles on the interface of the coating and the aluminum alloy substrate effectively inhibit the migration of atoms on the surface of the aluminum alloy substrate.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all 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.
Example 1:
s1: preparing a surface corrosion-resistant coating:
（1）SiO2preparation of @ methylbutinol @ TiN: ultrasonically dispersing the weighed nano TiN particles and polyacrylate in deionized water to form TiN dispersion liquid for later use; 4/5 tetraethyl silicate and ammonium hydroxide are weighed and sequentially added into a mixed solution containing deionized water and ethanol, the stirring speed is set to be 200rmp at 25 ℃, TiN dispersion liquid and methylbutinol are sequentially added, and the reaction is carried out for 6 days; adding the rest 1/5 tetraethyl silicate, and setting the temperature at 60 ℃ for reaction for 1 hour; centrifuging, washing and drying to obtain SiO2@ methylbutynol @ TiN for use;
(2) preparation of polyacrylate @ paraffin @ rhodamine: melting the weighed paraffin, spraying the rhodamine water solution into the molten paraffin for 10 seconds at the spraying speed of 0.1mm/min, and solidifying and cooling to obtain the paraffin @ rhodamine for later use; ultrasonically dispersing acrylate and a crosslinking agent in deionized water in sequence, setting the stirring speed to be 140rmp, stirring for 1 hour, adding paraffin @ rhodamine, setting the stirring speed to be 200rmp, setting the reaction temperature to be 55 ℃, setting the reaction time to be 20 hours, filtering, and washing to obtain polyacrylate @ paraffin @ rhodamine for later use;
(3) preparing a surface corrosion-resistant coating: weighing SiO2@ methyl butynol @ TiN, polyacrylate @ paraffin @ rhodamine and epoxy resin are added into deionized water at the set speed of 200rmp, stirred for 4 hours, added with imidazole and stirred for 30 minutes to obtain surface corrosion-resistant coating slurry for later use;
s2: preparing high-strength corrosion-resistant aluminum alloy: mechanically polishing an alloy sheet by using a metallographic paper machine, ultrasonically cleaning the alloy sheet for 10 minutes by using acetone, ethanol and deionized water, drying the alloy sheet, transferring the alloy sheet to a rotary coating machine, spraying the slurry of the surface corrosion-resistant coating on the surface of an aluminum alloy substrate at a set rotating speed of 200rmp, and curing the aluminum alloy substrate for 18 hours at the temperature of 30 ℃; curing for 6 hours at 60 ℃ to obtain the high-strength corrosion-resistant aluminum alloy.
In this embodiment, the raw materials of the surface corrosion-resistant coating include the following components: 40 parts of epoxy resin and SiO by weight2@ methylbutinol @ TiN 5 parts, polyacrylate @ paraffin @ rhodamine 1 part and imidazole 20 parts.
The polyacrylate @ paraffin @ rhodamine comprises the following components: 30 parts of acrylic ester, 20 parts of paraffin and 10 parts of rhodamine.
The SiO2The @ methylbutinol @ TiN raw material comprises the following components: 10 parts of nano TiN particles, 8 parts of methyl butynol, 22 parts of tetraethyl silicate, 4 parts of ammonium hydroxide and 2 parts of polyacrylate.
SiO2The particle size of @ methylbutinol @ TiN is 100 nm; the mass fraction of the nano TiN particles in the TiN dispersion liquid is 5 wt%.
Example 2:
s1: preparing a surface corrosion-resistant coating:
（1）SiO2preparation of @ methylbutinol @ TiN: ultrasonically dispersing the weighed nano TiN particles and polyacrylate in deionized water to form TiN dispersion liquid for later use; 4/5 tetraethyl silicate and ammonium hydroxide are weighed and sequentially added into a mixed solution containing deionized water and ethanol, the stirring speed is set to be 400rmp at 55 ℃, TiN dispersion liquid and methylbutinol are sequentially added, and the reaction is carried out for 8 days; adding the rest 1/5 tetraethyl silicate, and setting the temperature at 80 ℃ for reaction for 1 hour; centrifuging, washing and drying to obtain SiO2@ methylbutynol @ TiN for use;
(2) preparation of polyacrylate @ paraffin @ rhodamine: melting the weighed paraffin, spraying the rhodamine water solution into the molten paraffin for 20 seconds at the spraying speed of 0.2mm/min, and solidifying and cooling to obtain the paraffin @ rhodamine for later use; ultrasonically dispersing acrylate and a crosslinking agent in deionized water in sequence, setting the stirring speed to be 200rmp, stirring for 2 hours, adding paraffin @ rhodamine, setting the stirring speed to be 400rmp, setting the reaction temperature to be 65 ℃, setting the reaction time to be 36 hours, filtering, and washing to obtain polyacrylate @ paraffin @ rhodamine for later use;
(3) preparing a surface corrosion-resistant coating: weighing prepared SiO2@ methyl butynol @ TiN, polyacrylate @ paraffin @ rhodamine and epoxy resin are added into deionized water at the set speed of 400rmp, stirred for 6 hours, added with imidazole and stirred for 60 minutes to obtain surface corrosion-resistant coating slurry for later use;
s2: preparing high-strength corrosion-resistant aluminum alloy: mechanically polishing an alloy sheet by using a metallographic paper machine, ultrasonically cleaning the alloy sheet for 30 minutes by using acetone, ethanol and deionized water, drying the alloy sheet, transferring the alloy sheet to a rotary coating machine, spraying the slurry of the surface corrosion-resistant coating on the surface of an aluminum alloy substrate at the set rotating speed of 300rmp, and curing the aluminum alloy substrate for 24 hours at the temperature of 30 ℃; curing for 8 hours at 60 ℃ to obtain the high-strength corrosion-resistant aluminum alloy.
In this embodiment, the raw materials of the surface corrosion-resistant coating include the following components: 70 parts of epoxy resin and SiO by weight2@ methylbutinol @ TiN 10 parts, polyacrylate @ paraffin @ rhodamine 5 parts and imidazole 30 parts.
The polyacrylate @ paraffin @ rhodamine comprises the following components: 66 parts of acrylate, 40 parts of paraffin and 20 parts of rhodamine.
The SiO2The @ methylbutinol @ TiN raw material comprises the following components: 20 parts of nano TiN particles, 14 parts of methylbutynol, 58 parts of tetraethyl silicate, 10 parts of ammonium hydroxide and 6 parts of polyacrylate by weight.
SiO2The particle size of @ methylbutinol @ TiN is 200 nm; the mass fraction of the nano TiN particles in the TiN dispersion liquid is 10 wt%.
Example 3:
s1: preparing a surface corrosion-resistant coating:
（1）SiO2preparation of @ methylbutinol @ TiN: ultrasonically dispersing the weighed TiN nano-particles and polyacrylate in deionized water to formForming TiN dispersion liquid for later use; 4/5 tetraethyl silicate and ammonium hydroxide are weighed and sequentially added into a mixed solution containing deionized water and ethanol, the stirring speed is set to be 300rmp at the temperature of 30 ℃, TiN dispersion liquid and methylbutinol are sequentially added, and the reaction is carried out for 7 days; adding the rest 1/5 tetraethyl silicate, and setting the temperature at 70 ℃ for reaction for 1 hour; centrifuging, washing and drying to obtain SiO2@ methylbutynol @ TiN for use;
(2) preparation of polyacrylate @ paraffin @ rhodamine: melting the weighed paraffin, spraying the rhodamine water solution into the molten paraffin for 15 seconds at the spraying speed of 0.15mm/min, and solidifying and cooling to obtain the paraffin @ rhodamine for later use; ultrasonically dispersing acrylate and a crosslinking agent in deionized water in sequence, setting the stirring speed to be 170rmp, stirring for 1.5 hours, adding paraffin @ rhodamine, setting the stirring speed to be 300rmp, the reaction temperature to be 60 ℃, the reaction time to be 30 hours, filtering, washing to obtain polyacrylate @ paraffin @ rhodamine for later use;
(3) preparing a surface corrosion-resistant coating: weighing prepared SiO2@ methyl butynol @ TiN, polyacrylate @ paraffin @ rhodamine and epoxy resin are added into deionized water at the set speed of 300rmp, stirred for 5 hours, added with imidazole and stirred for 40 minutes to obtain surface corrosion-resistant coating slurry for later use;
s2: preparing high-strength corrosion-resistant aluminum alloy: mechanically polishing an alloy sheet by using a metallographic paper machine, ultrasonically cleaning the alloy sheet for 20 minutes by using acetone, ethanol and deionized water, drying the alloy sheet, transferring the alloy sheet to a rotary coating machine, spraying the slurry of the surface corrosion-resistant coating on the surface of an aluminum alloy substrate at a set rotating speed of 250rmp, and curing the aluminum alloy substrate for 21 hours at the temperature of 30 ℃; curing for 7 hours at 60 ℃ to obtain the high-strength corrosion-resistant aluminum alloy.
In this embodiment, the raw materials of the surface corrosion-resistant coating include the following components: 55 parts of epoxy resin and SiO by weight2@ methylbutinol @ TiN 8 parts, polyacrylate @ paraffin @ rhodamine 3 parts and imidazole 25 parts.
The polyacrylate @ paraffin @ rhodamine comprises the following components: 46 parts of acrylate, 30 parts of paraffin and 15 parts of rhodamine.
Said SiO2The @ methylbutinol @ TiN raw material comprises the following components: by weight, 15 parts of nano TiN particles, 11 parts of methylbutynol, 40 parts of tetraethyl silicate, 7 parts of ammonium hydroxide and 4 parts of polyacrylate.
SiO2The particle size of @ methylbutinol @ TiN is 150 nm; the mass fraction of the nano TiN particles in the TiN dispersion liquid is 7 wt%.
Example 4: selecting a common aluminum alloy substrate, and the rest is the same as the embodiment 3;
example 5: without addition of SiO2@ methylbutinol @ TiN, otherwise the same as in example 3;
example 6: the same procedure as in example 3 was repeated except that polyacrylate @ paraffin @ rhodamine was not added;
example 7: the same procedure as in example 3 was repeated except that TiN was not added;
experiment: the strength of the high-strength corrosion-resistant aluminum alloy prepared in the embodiment 1-8 is detected at normal temperature and normal pressure according to GB/T228-2002 test standards; the corrosion resistance of the aluminium alloys was characterized in terms of the number of days of rusting in a 12% sodium chloride environment by performing a salt spray test according to the test standard GBB/T10125-1997 and the results are shown in Table 1:
TABLE 1
| Examples | Tensile strength/Mpa | Yield strength/Mpa | Elongation/percent | Salt spray time/day |
| Example 1 | 518 | 360 | 12 | 132 |
| Example 2 | 531 | 371 | 15 | 141 |
| Example 3 | 523 | 366 | 13 | 136 |
| Example 4 | 342 | 286 | 7.3 | 132 |
| Example 5 | 512 | 353 | 11 | 93 |
| Example 6 | 510 | 352 | 10 | 127 |
| Example 7 | 511 | 352 | 11 | 95 |
The data in examples 1-3 show that the prepared aluminum alloy has high strength and excellent corrosion resistance, the tensile strength is more than 500 MPa, and the salt spray time is more than 130 days. Meanwhile, the color of 1-3 dyes on the metal surface can be seen, and the scheme is optimized as embodiment 2.
Comparing the data of example 4 with example 3, it can be seen that the tensile strength, yield strength and elongation are greatly reduced because the rare earth metal gallium has a refining effect on crystal grains, which significantly enhances the strength of the aluminum alloy, and in addition, compared with the common aluminum alloy substrate, the tensile strength is 302 Mpa, and the mechanical properties of the aluminum alloy are enhanced by coating a surface corrosion-resistant coating.
Comparing example 5 with example 3, it can be found that the data in terms of mechanical properties are reduced to a very small extent, because the nano TiN particles can effectively inhibit the migration of atoms on the surface of the aluminum alloy substrate, and increase the strength of the aluminum alloy. The salt spray time is greatly reduced because of doping SiO2The @ methylbutinol @ TiN can be used for repairing coatings, releasing corrosion inhibitors and enhancing the corrosion resistance of aluminum alloys, and the polyacrylate @ paraffin @ rhodamine indicator is arranged in the aluminum alloy, so that the area of the repaired dye is small, on one hand, pitting corrosion occurs, and on the other hand, the self-repairing mechanism can be repaired in time. Compared with example 7, the mechanical data is not much different from that of example 5, the key of the problem lies in the salt spray time, and although the corrosion inhibitor is still protected, the salt spray time is shortened because the nano TiN particles cannot be repaired in time due to lack of starting of the photothermal effect.
Comparing the data of example 6 with example 3, all the data are slightly reduced, but the difference is not obvious, which indicates that the polyacrylate @ paraffin @ rhodamine generates synergistic action with other substances to assist in enhancing the mechanical and corrosion resistance properties. The greatest difference is that the position of the crack or corrosion cannot be indicated.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A high-strength corrosion-resistant aluminum alloy is characterized in that: the high-strength corrosion-resistant aluminum alloy raw material comprises an aluminum alloy base material and a surface corrosion-resistant coating; the surface corrosion-resistant coating comprises the following raw materials: 40-70 parts by weight of epoxy resin and SiO2@ methylbutinol @ TiN 5-10 parts, polyacrylate @ paraffin @ rhodamine 1-5 parts and imidazole 20-30 parts.
2. A high strength corrosion resistant aluminum alloy according to claim 1 wherein: the aluminum alloy base material comprises the following components: according to weight percentage, 0.8 percent of Cr, 1.5 percent of Mg, 2 percent of Si, 0.2 percent of Fe, 0.49 percent of Cu, 0.8 percent of Mn, 0.3 percent of Ga, and the balance of Al and inevitable impurities.
3. A high strength corrosion resistant aluminum alloy according to claim 1 wherein: the surface corrosion-resistant coating is 1-30 mm.
4. A high strength corrosion resistant aluminum alloy according to claim 1 wherein: the SiO2The particle size of @ methylbutinol @ TiN is 100-200 nm.
5. A high strength corrosion resistant aluminum alloy according to claim 1 wherein: the SiO2The @ methylbutinol @ TiN raw material comprises the following components: 10-20 parts of nano TiN particles, 8-14 parts of methylbutynol and silicic acid tetra22-58 parts of ethyl ester, 4-10 parts of ammonium hydroxide and 2-6 parts of polyacrylate.
6. A high strength corrosion resistant aluminum alloy according to claim 1 wherein: the polyacrylate @ paraffin @ rhodamine comprises the following components: 30-66 parts of acrylate, 20-40 parts of paraffin and 10-20 parts of rhodamine.
7. A processing technology of high-strength corrosion-resistant aluminum alloy is characterized by comprising the following steps:
s1: preparing a surface corrosion-resistant coating:
（1）SiO2preparation of @ methylbutinol @ TiN: ultrasonically dispersing the weighed nano TiN particles and polyacrylate in deionized water to form TiN dispersion liquid for later use; sequentially adding 4/5 tetraethyl silicate and ammonium hydroxide into a mixed solution containing deionized water and ethanol, setting the stirring speed at 200-400 rmp at 25-55 ℃, sequentially adding TiN dispersion liquid and methylbutinol, and reacting for 6-8 days; adding the rest 1/5 tetraethyl silicate, and reacting for 1 hour at the set temperature of 60-80 ℃; centrifuging, washing and drying to obtain SiO2@ methylbutynol @ TiN for use;
(2) preparation of polyacrylate @ paraffin @ rhodamine: melting the weighed paraffin, spraying the rhodamine water solution into the molten paraffin for 10-20 seconds at the spraying speed of 0.1-0.2 mm/min, and solidifying and cooling to obtain the paraffin @ rhodamine for later use; ultrasonically dispersing acrylate and a crosslinking agent in deionized water in sequence, setting the stirring speed to be 140-200 rmp, stirring for 1-2 hours, adding paraffin @ rhodamine, setting the stirring speed to be 200-400 rmp, reacting at 55-65 ℃, reacting for 20-36 hours, filtering, and washing to obtain polyacrylate @ paraffin @ rhodamine for later use;
(3) preparing a surface corrosion-resistant coating: weighing SiO2The @ methylbutinol @ TiN, polyacrylate @ paraffin @ rhodamine and epoxy resin are dispersed in deionized water at a set speed of 200-400 rmp, stirred for 4-6 hours, added with imidazole and stirred for 30-60 minutes to obtain surface corrosion-resistant coating slurry for later use;
s2: preparing high-strength corrosion-resistant aluminum alloy: mechanically polishing an alloy sheet by using a metallographic paper, ultrasonically cleaning the alloy sheet by using acetone, ethanol and deionized water for 10-30 minutes, drying the alloy sheet, transferring the alloy sheet to a rotary coating machine, spraying the slurry of the surface corrosion-resistant coating on the surface of an aluminum alloy substrate at a set rotating speed of 200-300 rmp, and curing the aluminum alloy substrate at 30 ℃ for 18-24 hours; and curing for 6-8 hours at 60 ℃ to obtain the high-strength corrosion-resistant aluminum alloy.
8. The processing technology of the high-strength corrosion-resistant aluminum alloy according to claim 7, characterized in that: in the step (1) of S1, the mass fraction of the nano TiN particles in the TiN dispersion liquid is 5-10 wt%.
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