CN114032547A - Alloy surface composite coating and preparation method thereof - Google Patents

Alloy surface composite coating and preparation method thereof Download PDF

Info

Publication number
CN114032547A
CN114032547A CN202111324720.XA CN202111324720A CN114032547A CN 114032547 A CN114032547 A CN 114032547A CN 202111324720 A CN202111324720 A CN 202111324720A CN 114032547 A CN114032547 A CN 114032547A
Authority
CN
China
Prior art keywords
alloy
coating
parts
aluminum
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202111324720.XA
Other languages
Chinese (zh)
Other versions
CN114032547B (en
Inventor
谢发勤
李淑良
吴向清
王少青
胡娜
贺栋栋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northwestern Polytechnical University
Original Assignee
Northwestern Polytechnical University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Northwestern Polytechnical University filed Critical Northwestern Polytechnical University
Priority to CN202111324720.XA priority Critical patent/CN114032547B/en
Publication of CN114032547A publication Critical patent/CN114032547A/en
Application granted granted Critical
Publication of CN114032547B publication Critical patent/CN114032547B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
    • C23C24/085—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • C23C24/087—Coating with metal alloys or metal elements only
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • 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
    • C25D11/026—Anodisation with spark discharge
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C25D11/20—Electrolytic after-treatment

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention provides a preparation method of an alloy composite coating, and belongs to the technical field of coating preparation. According to the invention, a layer of insulating oxide film is generated on the surface of an alloy substrate through micro-arc oxidation treatment to form a barrier layer, and in the cathode deposition treatment process, the prefabricated barrier layer is broken down to generate arc discharge and generate huge energy, so that a ceramic coating (an aluminum oxide coating) which is well combined with the substrate is generated on the surface of a cathode; meanwhile, a layer-by-layer lapped covering layer is formed on the surface of a sample by using the chromium-free zinc-aluminum coating liquid with a specific composition, so that an external corrosive medium is prevented from entering a matrix, and the formed composite coating can play a role in physical shielding, sacrificial anode cathode protection and self-repairing on the alloy matrix, thereby improving the corrosion resistance of the alloy and not influencing the strength of the matrix.

Description

Alloy surface composite coating and preparation method thereof
Technical Field
The invention relates to the technical field of coating preparation, in particular to an alloy surface composite coating and a preparation method thereof.
Background
The aluminum alloy has the advantages of small density, high specific strength, good conductivity and the like, so that the aluminum alloy has wide application in the fields of aerospace, mechanical manufacturing, transportation and the like. The LY12 aluminum alloy is a typical duralumin alloy in the aluminum-copper-magnesium system, has good combination of properties, and is one of the most widely used duralumins. The alloy has high strength and certain heat resistance, but the corrosion resistance is poor, so that the application of the alloy is limited.
The Cathode Plasma Electrolytic Deposition (CPED) is a new surface treatment technology developed on the basis of common electrolytic technology, which adopts a workpiece as a cathode and can deposit different coatings, such as Al, on the surface of a substrate by adjusting the components of electrolyte2O3、ZrO3Ni or Cr.
The chromium-free zinc-aluminum coating is developed on the basis of the traditional Dacromet coating (Dacromet), and the traditional Dacromet coating contains hexavalent chromium and has great harm to human beings and the environment, so the chromium-free zinc-aluminum coating technology is produced. The chromium-free zinc-aluminum coating is an environment-friendly coating formed by dissolving flaky zinc powder and flaky aluminum powder in an organic solvent and deionized water, adding other components such as a binder and a passivator, and then sintering and curing at high temperature. The coating has the performances of no hydrogen embrittlement, excellent heat resistance and the like. The invention patent with the publication number of CN106752904A discloses a preparation technology of a composite coating of an organosilicon resin emulsion modified chromium-free Dacromet coating, which improves the porosity and the density of the Dacromet coating, but the corrosion resistance of the Dacromet coating needs to be further improved.
Disclosure of Invention
The invention aims to provide an alloy composite coating and a preparation method thereof, and the prepared composite coating has excellent corrosion resistance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of an alloy composite coating, which comprises the following steps:
sequentially carrying out micro-arc oxidation pretreatment and cathode deposition treatment on the alloy to obtain a treated alloy;
dipping the treated alloy in a coating solution, taking out, sequentially preheating and curing, and repeating the processes of dipping, preheating and curing to obtain an alloy composite coating;
the masking liquid comprises a first component, a second component and a third component; the masking liquid does not contain chromium;
the first component comprises the following components in parts by mass: 10-20 parts of polyethylene glycol, 5-10 parts of flaky aluminum powder, 203-6 parts of tween, 5-10 parts of a first silane coupling agent, 20-40 parts of flaky zinc powder and 10-20 parts of water;
the second component includes: 5-15 parts of methanol, 10-20 parts of water and 10-20 parts of a second silane coupling agent;
the third component includes: 0.5-1 part of sodium phosphomolybdate and 10-20 parts of water.
Preferably, the electrolyte used for the micro-arc oxidation pretreatment comprises the following components: 10-20 g/L of sodium silicate, 10-20 g/L of sodium hexametaphosphate and 1-5 g/L of sodium hydroxide; the solvent of the electrolyte is water.
Preferably, the micro-arc oxidation electrical parameters of the micro-arc oxidation pretreatment include: the pulse frequency is 600-900 Hz, the duty ratio is 10-50%, and the current density is 5-10A/dm2The temperature is 10-20 ℃, and the time is 2-10 min.
Preferably, the electrolyte used for the cathodic deposition treatment is an aluminum salt alcohol solution; the cathode deposition treatment takes graphite as an anode and takes the alloy subjected to micro-arc oxidation pretreatment as a cathode.
Preferably, the electrical parameters of the cathodic deposition process include: the pulse frequency is 20-900 Hz, the duty ratio is 30-60%, and the current density is 3-15A/dm2The temperature is 10-20 ℃, and the time is 5-15 min.
Preferably, the temperature of each preheating is independently 70-100 ℃ for 10-15 min.
Preferably, the temperature of each sintering is 260-320 ℃ independently, and the time is 30 min.
Preferably, the thickness of the alloy surface composite coating in the alloy composite coating is 10-30 μm.
Preferably, the first silane coupling agent and the second silane coupling agent are independently gamma-aminopropyltriethoxysilane or gamma-glycidoxypropyltrimethoxysilane.
The invention provides an alloy composite coating prepared by the preparation method in the technical scheme, which comprises an alloy substrate, and an aluminum oxide coating and a zinc-aluminum coating which are sequentially laminated on the surface of the alloy substrate.
The invention provides a preparation method of an alloy composite coating, which comprises the steps of generating an insulating oxide film on the surface of an alloy substrate through micro-arc oxidation treatment to form a barrier layer, and in the cathode deposition treatment process, breaking down the prefabricated barrier layer to generate arc discharge and generate huge energy, so that a ceramic coating (an aluminum oxide coating) well combined with the substrate is generated on the surface of a cathode; meanwhile, a layer-by-layer lapped covering layer is formed on the surface of a sample by using the chromium-free zinc-aluminum coating liquid with a specific composition, so that an external corrosive medium is prevented from entering a matrix, and the formed composite coating can play a role in physical shielding, sacrificial anode cathode protection and self-repairing on the alloy matrix, thereby improving the corrosion resistance of the alloy and not influencing the strength of the matrix.
Drawings
FIG. 1 is a surface topography of the aluminum alloy composite coating prepared in example 1 after being subjected to a salt spray test for 1200 h;
FIG. 2 is a surface topography of the treated aluminum alloy prepared in comparative example 1 after being subjected to a salt spray test for 100 hours;
FIG. 3 is a surface topography of the aluminum alloy composite coating prepared in comparative example 2 after 360h of a salt spray test;
FIG. 4 is a surface topography of the aluminum alloy composite coating prepared in comparative example 3 after being subjected to a salt spray test for 72 hours;
FIG. 5 is a surface topography map of the aluminum alloy composite coating prepared in example 2 after being subjected to a salt spray test for 1200 h;
FIG. 6 is a surface topography map of the aluminum alloy composite coating prepared in example 3 after being subjected to a salt spray test for 1200 h;
FIG. 7 is a surface topography of the aluminum alloy composite coating prepared in example 4 after being subjected to a salt spray test for 1200 h.
Detailed Description
The invention provides a preparation method of an alloy composite coating, which comprises the following steps:
sequentially carrying out micro-arc oxidation pretreatment and cathode deposition treatment on the alloy to obtain a treated alloy;
dipping the treated alloy in a coating solution, taking out, sequentially preheating and curing, and repeating the processes of dipping, preheating and curing to obtain an alloy composite coating;
the masking liquid comprises a first component, a second component and a third component; the masking liquid does not contain chromium;
the first component comprises the following components in parts by mass: 10-20 parts of polyethylene glycol, 20-40 parts of flaky zinc powder, 203-6 parts of tween, 5-10 parts of first silane coupling agent, 5-10 parts of flaky aluminum powder and 10-20 parts of water;
the second component includes: 5-15 parts of methanol, 10-20 parts of water and 10-20 parts of a second silane coupling agent;
the third component includes: 0.5-1 part of sodium phosphomolybdate and 10-20 parts of water.
In the present invention, unless otherwise specified, all the starting materials required for the preparation are commercially available products well known to those skilled in the art.
The alloy is subjected to micro-arc oxidation pretreatment and cathode deposition treatment in sequence to obtain the treated alloy. In the present invention, the alloy preferably includes steel, an aluminum alloy, or a titanium alloy. The type of the alloy is not particularly limited in the present invention, and commercially available alloys well known in the art can be used; in an embodiment of the invention, the alloy is specifically LY12 aluminum alloy.
Before the micro-arc oxidation treatment, the alloy is preferably subjected to surface treatment; the surface treatment preferably comprises the steps of sequentially polishing and deoiling the alloy; the sand paper used for polishing is preferably No. 80-600 sand paper; the invention removes surface oxide and other covering materials by polishing; the reagent used for the oil removal treatment is preferably absolute ethyl alcohol; the oil removal treatment is preferably carried out under an ultrasonic condition, and the oil removal treatment time is preferably 5-8 min. The process of the ultrasound is not particularly limited in the present invention, and may be performed according to a process well known in the art.
After the surface treatment is finished, the alloy is subjected to micro-arc oxidation pretreatment; the electrolyte used for the micro-arc oxidation pretreatment preferably comprises the following components: 10-20 g/L of sodium silicate, 10-20 g/L of sodium hexametaphosphate and 1-5 g/L of sodium hydroxide; the solvent of the electrolyte is preferably water; in the components of the electrolyte, the concentration of sodium silicate is preferably 12-16 g/L, the concentration of sodium hexametaphosphate is preferably 12-16 g/L, and the concentration of sodium hydroxide is preferably 1-3 g/L.
In the invention, the micro-arc oxidation pretreatment is preferably carried out in an electrolyte by using a MAO-20C type micro-arc oxidation power supply, wherein a stainless steel groove is preferably used as a cathode, the alloy is preferably used as an anode and the micro-arc oxidation pretreatment is preferably carried out in the electrolyte. The stainless steel tank is not particularly limited in the present invention, and any commercially available one well known in the art may be used.
In the present invention, the micro-arc oxidation electrical parameters of the micro-arc oxidation pretreatment preferably include: the pulse frequency is 600-900 Hz, the duty ratio is 10-50%, and the current density is 5-10A/dm2The temperature is 10-20 ℃, and the time is 2-10 min; the pulse frequency is preferably 650-850 Hz, and more preferably 700-800 Hz; the duty ratio is preferably 20-40%, and more preferably 25-35%; the current density is preferably 6-9A/dm2(ii) a The temperature is preferably 15-17 ℃; the time is preferably 3-5 min.
The invention forms a barrier layer on the surface of the alloy through micro-arc oxidation pretreatment, thereby forming an insulating oxide film and preparing for cathode deposition treatment.
After the micro-arc oxidation pretreatment is finished, the invention preferably carries out cathode deposition treatment on the treated alloy; the electrolyte used for the cathodic deposition treatment is preferably an aluminum salt alcohol solution; the aluminum salt in the aluminum salt alcoholic solution is preferably aluminum nitrate; the alcohol in the aluminum salt alcohol solution is preferably ethanol; the concentration of the aluminum salt in the aluminum salt alcohol solution is preferably 0.3 mol/L.
In the invention, the cathode deposition treatment preferably takes graphite as an anode and takes the alloy subjected to micro-arc oxidation pretreatment as a cathode; the cathodic deposition treatment is preferably carried out using MAO-20C type micro-arc oxidation power supply. The graphite is not particularly limited in the present invention, and any graphite known in the art can be used as the anode.
In the present invention, the electrical parameters of the cathodic deposition process preferably include: the pulse frequency is 20-900 Hz, the duty ratio is 30-60%, and the current density is 3-15A/dm2The temperature is 10-20 ℃, and the time is 5-15 min; the pulse frequency is preferably 30-100 Hz, and more preferably 40-50 Hz; the duty ratio is preferably 35-55%, and more preferably 40-50%; the current density is preferably 4 to 12A/dm2More preferably 8 to 10A/dm2(ii) a The temperature is preferably 15-17 ℃; the time is preferably 10 min.
The invention utilizes cathode deposition treatment to generate arc discharge on the surface of a cathode (alloy substrate) and remove an oxide film formed by micro-arc oxidation, thereby forming a compact alumina ceramic coating on the surface of the alloy substrate.
After the cathode deposition treatment is finished, deionized water is preferably adopted to clean the electrolyte remained on the surface of the alloy, and the alloy is dried to obtain the treated alloy. The washing and drying processes are not particularly limited in the present invention and may be performed according to a process well known in the art.
After the treated alloy is obtained, the treated alloy is dipped in coating liquid, and is taken out, then preheating and solidification are carried out in sequence, and the processes of dipping, preheating and solidification are repeated, so that the alloy composite coating is obtained.
In the present invention, the dope includes a first component, a second component and a third component; the coating liquid does not contain chromium.
In the present invention, the first component includes, in parts by mass: 10-20 parts of polyethylene glycol, 20-40 parts of flaky zinc powder, 5-10 parts of flaky aluminum powder, 203-6 parts of tween, 5-10 parts of a first silane coupling agent and 10-20 parts of water; the preferable proportion of the polyethylene glycol is 10-15 parts; the preferable part of the flaky zinc powder is 25-35 parts, and the more preferable part is 30 parts; the preferable proportion of the flaky aluminum powder is 6-8 parts; the preferred part of the Tween 20 is 4-5 parts; the water is preferably 15 parts; the first silane coupling agent is preferably gamma-aminopropyltriethoxysilane or gamma-glycidoxypropyltrimethoxysilane; the first silane coupling agent is preferably 6-8 parts. The specific specifications of the zinc flake powder and the aluminum flake powder are not particularly limited in the present invention, and commercially available products well known in the art may be used. The invention uses polyethylene glycol as wetting agent; tween 20 is used as a dispersing agent, so that the metal powder is uniformly dispersed in the aqueous solution. In the invention, the preparation process of the first component preferably comprises the steps of mixing the corresponding raw materials, and stirring at the speed of 200r/min for 3-5 h.
In the present invention, the second component includes: 5-15 parts of methanol, 10-20 parts of water and 10-20 parts of a second silane coupling agent; the methanol is preferably 10 parts; the water is preferably 15 parts; the second silane coupling agent is preferably gamma-aminopropyltriethoxysilane or gamma-glycidoxypropyltrimethoxysilane; the second silane coupling agent is preferably 10-15 parts. In the invention, the preparation process of the second component preferably comprises the steps of mixing the corresponding raw materials and stirring at the speed of 200r/min for 2-3 h. The mixing and stirring process of the first component and the second component is not particularly limited in the present invention, and may be performed according to a process well known in the art.
In the present invention, the third component includes: 0.5-1 part of sodium phosphomolybdate and 10-20 parts of water; the preferable amount of the sodium phosphomolybdate is 0.6-0.8 part; the water is preferably 15 parts. In the invention, the preparation process of the third component preferably comprises the steps of mixing the corresponding raw materials, and heating in a water bath at the temperature of 30-80 ℃ for 2-6 hours, wherein the temperature of the water bath is more preferably 40-60 ℃, and the heating time is more preferably 3-5 hours.
In the invention, the preparation method of the masking liquid preferably comprises the steps of mixing and stirring the second component and the third component for 2-5 hours, adding the first component, and mixing and stirring for 10-20 hours. The mixing and stirring process is not particularly limited in the present invention, and may be performed according to a process well known in the art.
The coating liquid used in the invention forms a zinc-aluminum coating layer which is overlapped layer by layer in the curing process, so that the external corrosive medium is prevented from entering the matrix, and meanwhile, as the zinc powder and the aluminum powder in the coating are more active, when the coating is damaged, the zinc-aluminum powder is preferentially corroded, so that the cathode protection of a sacrificial anode is generated on the alloy matrix.
After the coating liquid is obtained, the treated alloy is soaked in the coating liquid for 3-10 s, and then the treated alloy is taken out and stands until the coating liquid is leveled.
In the invention, the preheating is preferably carried out in an oven, the temperature of each preheating is preferably 70-100 ℃ independently, and the time is preferably 10-15 min; the temperature of each curing is preferably 260-320 ℃ independently, and the time is preferably 30 min. The invention has no special limit on the times of repeating the processes of dipping, preheating and curing, and the required coating thickness can be reached; in the embodiment of the present invention, the dipping, preheating and curing process is repeated 2 times.
In the preheating process, the temperature is low, and the water and the low-boiling-point organic solvent (methanol) in the coating liquid volatilize; in the sintering process, the silane coupling agent and the passivating agent (sodium phosphomolybdate) in the coating liquid completely react with the flaky zinc powder and the flaky aluminum powder to form a complete coating, the flaky zinc powder and the flaky aluminum powder in the coating liquid are in a layer-by-layer overlapped state under the action of the silane coupling agent, and the surface of the formed zinc-aluminum coating is silvery white, flat and smooth and has no cracks, so that an external corrosive medium is prevented from entering a matrix to protect the matrix.
After the sintering is finished, the obtained product is preferably cooled to room temperature to obtain the alloy composite coating. The cooling process is not particularly limited in the present invention, and may be performed according to a process well known in the art.
In the invention, the thickness of the alloy surface composite coating in the alloy composite coating is preferably 10-30 μm, and more preferably 18-23 μm.
The invention provides an alloy composite coating prepared by the preparation method in the technical scheme, which comprises an alloy substrate, and an aluminum oxide coating and a zinc-aluminum coating which are sequentially laminated on the surface of the alloy substrate.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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.
In the following examples, the alloy substrates used were each a LY12 aluminum alloy of 20mm by 30mm by 5mm gauge.
Example 1
(1) Pretreatment of a matrix: removing burrs and corrosion products on the surface of the aluminum alloy substrate by using No. 80-600 abrasive paper, and then ultrasonically cleaning for 5min by using absolute ethyl alcohol;
(2) micro-arc oxidation pretreatment: taking a stainless steel groove as a cathode, taking the aluminum alloy after the previous treatment as an anode, and treating by using an MAO-20C type micro-arc oxidation power supply;
the electrolyte comprises the following components: 10g/L of sodium silicate, 10g/L of sodium hexametaphosphate, 1g/L of sodium hydroxide and deionized water as a solvent;
the micro-arc oxidation pretreatment electrical parameters are as follows: pulse frequency 800Hz, duty ratio 20%, current density 9A/dm2The temperature is 15 ℃, and the treatment time is 2 min;
(3) cathode deposition treatment: graphite is used as an anode, the alloy after micro-arc oxidation and treatment is used as a cathode, and MAO-20C type micro-arc oxidation power supply is used for treatment;
the electrolyte used comprises the following components: 0.3mol/L of an ethanol solution of aluminum nitrate;
the used electricity parameters are: pulse frequency of 50Hz, duty ratio of 30 percent and current density of 5A/dm2At a temperature of 15 ℃; the time is 10 min;
(4) coating with zinc-aluminium coating
Preparation of a masking liquid:
a first component: 12.3g of polyethylene glycol, 5g of sheet aluminum powder, 203.3g of tween, 5.23g of silane coupling agent (gamma-glycidyl ether oxypropyl trimethoxy silane), 30g of sheet zinc powder and 15g of deionized water; mixing the raw materials, and stirring at a speed of 200r/min for 3 h;
a second component: 7.7g of methanol, 10g of deionized water and 10.47g of silane coupling agent (gamma-glycidoxypropyltrimethoxysilane); mixing the raw materials, and stirring at a speed of 200r/min for 3 h;
a third component: 0.72g of sodium phosphomolybdate and 10g of deionized water, and heating in a water bath at 40 ℃ for 4 hours after mixing;
mixing and stirring the second component and the third component for 3 hours, adding the first component, mixing and stirring for 16 hours to obtain a masking liquid;
immersing the aluminum alloy subjected to cathodic deposition treatment in the coating liquid for 3s, taking out the aluminum alloy, placing the aluminum alloy into a baking oven after the surface of a sample is leveled, preheating the aluminum alloy at 100 ℃ for 15min, sintering the aluminum alloy at 300 ℃ for 30min, and repeating the processes of dip coating, preheating and sintering again to obtain an aluminum alloy composite coating; the thickness of the composite coating on the alloy surface is 23 μm.
Example 2
(1) Pretreatment of a matrix: removing burrs and corrosion products on the surface of the aluminum alloy substrate by using No. 80-600 abrasive paper, and then ultrasonically cleaning for 5min by using absolute ethyl alcohol;
(2) micro-arc oxidation pretreatment: taking a stainless steel groove as a cathode, taking the aluminum alloy after the previous treatment as an anode, and treating by using an MAO-20C type micro-arc oxidation power supply;
the electrolyte comprises the following components: 10g/L of sodium silicate, 10g/L of sodium hexametaphosphate, 1g/L of sodium hydroxide and deionized water as a solvent;
the micro-arc oxidation pretreatment electrical parameters are as follows: pulse frequency 900Hz, duty ratio 20%, current density 10A/dm2At 15 ℃ for 5 min;
(3) cathode deposition treatment: treating graphite serving as an anode and an aluminum alloy subjected to micro-arc oxidation pretreatment serving as a cathode by using an MAO-20C type micro-arc oxidation power supply;
the electrolyte used comprises the following components: 0.3mol/L of an ethanol solution of aluminum nitrate;
the used electricity parameters are: pulse frequency of 50Hz, duty ratio of 30 percent and current density of 5.5A/dm2At a temperature of 15 ℃; the time is 8 min;
(4) coating with zinc-aluminium coating
Preparation of a masking liquid:
a first component: 12.3g of polyethylene glycol, 5g of sheet aluminum powder, 203.3g of tween, 5.23g of silane coupling agent (gamma-glycidyl ether oxypropyl trimethoxy silane), 30g of sheet zinc powder and 15g of deionized water; mixing the raw materials, and stirring at a speed of 200r/min for 3 h;
a second component: 7.7g of methanol, 10g of deionized water and 10.47g of silane coupling agent (gamma-glycidoxypropyltrimethoxysilane); mixing the raw materials, and stirring at a speed of 200r/min for 3 h;
a third component: 0.72g of sodium phosphomolybdate and 10g of deionized water, and heating in a water bath at 40 ℃ for 4 hours after mixing;
mixing and stirring the second component and the third component for 3 hours, adding the first component, mixing and stirring for 16 hours to obtain a masking liquid;
immersing the aluminum alloy subjected to cathodic deposition treatment in the coating liquid for 3s, taking out the aluminum alloy, placing the aluminum alloy into a baking oven after the surface of a sample is leveled, preheating the aluminum alloy at 100 ℃ for 15min, sintering the aluminum alloy at 300 ℃ for 30min, and repeating the processes of dip coating, preheating and sintering again to obtain an aluminum alloy composite coating; the thickness of the composite coating on the alloy surface is 20 mu m.
Example 3
(1) Pretreatment of a matrix: removing burrs and corrosion products on the surface of the aluminum alloy substrate by using No. 80-600 abrasive paper, and then ultrasonically cleaning for 5min by using absolute ethyl alcohol;
(2) micro-arc oxidation pretreatment: taking a stainless steel groove as a cathode, taking the aluminum alloy after the previous treatment as an anode, and treating by using an MAO-20C type micro-arc oxidation power supply;
the electrolyte comprises the following components: 10g/L of sodium silicate, 10g/L of sodium hexametaphosphate, 1g/L of sodium hydroxide and deionized water as a solvent;
the micro-arc oxidation pretreatment electrical parameters are as follows: pulse frequency 850Hz, duty ratio 20%, current density 8A/dm2At 15 ℃ for 3 min;
(3) cathode deposition treatment: treating graphite serving as an anode and an aluminum alloy subjected to micro-arc oxidation pretreatment serving as a cathode by using an MAO-20C type micro-arc oxidation power supply;
the electrolyte used comprises the following components: 0.3mol/L of an ethanol solution of aluminum nitrate;
the used electricity parameters are: pulse frequency of 50Hz, duty ratio of 30 percent and current density of 4.6A/dm2At a temperature of 15 ℃; the time is 8 min;
(4) coating with zinc-aluminium coating
Preparation of a masking liquid:
a first component: 12.3g of polyethylene glycol, 5g of sheet aluminum powder, 203.3g of tween, 5.23g of silane coupling agent (gamma-glycidyl ether oxypropyl trimethoxy silane), 30g of sheet zinc powder and 15g of deionized water; mixing the raw materials, and stirring at a speed of 200r/min for 3 h;
a second component: 7.7g of methanol, 10g of deionized water and 10.47g of silane coupling agent (gamma-glycidoxypropyltrimethoxysilane); mixing the raw materials, and stirring at a speed of 200r/min for 3 h;
a third component: 0.72g of sodium phosphomolybdate and 10g of deionized water, and heating in a water bath at 40 ℃ for 4 hours after mixing;
mixing and stirring the second component and the third component for 3 hours, adding the first component, mixing and stirring for 16 hours to obtain a masking liquid;
immersing the aluminum alloy subjected to cathodic deposition treatment in the coating liquid for 3s, taking out the aluminum alloy, placing the aluminum alloy into an oven after the surface of a sample is leveled, preheating the aluminum alloy at 100 ℃ for 15min, sintering the aluminum alloy at 300 ℃ for 30min, and repeating the processes of dip coating, preheating and sintering again after the completion to obtain the chromium-free zinc-aluminum composite coating of the aluminum alloy; the thickness of the composite coating on the alloy surface is 18 mu m.
Example 4
(1) Pretreatment of a matrix: removing burrs and corrosion products on the surface of the aluminum alloy substrate by using No. 80-600 abrasive paper, and then ultrasonically cleaning for 5min by using absolute ethyl alcohol;
(2) micro-arc oxidation pretreatment: taking a stainless steel groove as a cathode, taking the aluminum alloy after the previous treatment as an anode, and treating by using an MAO-20C type micro-arc oxidation power supply;
the electrolyte comprises the following components: 10g/L of sodium silicate, 10g/L of sodium hexametaphosphate, 1g/L of sodium hydroxide and deionized water as a solvent;
the micro-arc oxidation pretreatment electrical parameters are as follows: pulse frequency 700Hz, duty ratio 20%, current density 9A/dm2At 15 ℃ for 3 min;
(3) cathode deposition treatment: treating graphite serving as an anode and an aluminum alloy subjected to micro-arc oxidation pretreatment serving as a cathode by using an MAO-20C type micro-arc oxidation power supply;
the electrolyte used comprises the following components: 0.3mol/L of an ethanol solution of aluminum nitrate;
the used electricity parameters are: pulse frequency of 50Hz, duty ratio of 30 percent and current density of 4A/dm2At a temperature of 15 ℃; the time is 6 min;
(4) coating with zinc-aluminium coating
Preparation of a masking liquid:
a first component: 12.3g of polyethylene glycol, 5g of sheet aluminum powder, 203.3g of tween, 5.23g of silane coupling agent (gamma-glycidyl ether oxypropyl trimethoxy silane), 30g of sheet zinc powder and 15g of deionized water; mixing the components, and stirring at a speed of 200r/min for 3 h;
a second component: 7.7g of methanol, 10g of deionized water and 10.47g of silane coupling agent (gamma-glycidoxypropyltrimethoxysilane); mixing the components, and stirring at a speed of 200r/min for 3 h;
a third component: 0.72g of sodium phosphomolybdate and 10g of deionized water, and heating in a water bath at 40 ℃ for 4 hours after mixing;
mixing and stirring the second component and the third component for 3 hours, adding the first component, mixing and stirring for 16 hours to obtain a masking liquid;
immersing the aluminum alloy subjected to cathodic deposition treatment in the coating liquid for 3s, taking out the aluminum alloy, placing the aluminum alloy into an oven after the surface of a sample is leveled, preheating the aluminum alloy at 100 ℃ for 15min, sintering the aluminum alloy at 300 ℃ for 30min, and repeating the processes of dip coating, preheating and sintering again after the completion to obtain the chromium-free zinc-aluminum composite coating of the aluminum alloy; the thickness of the composite coating on the alloy surface is 19 mu m.
Comparative example 1
(1) Pretreatment of a matrix: removing burrs and corrosion products on the surface of the aluminum alloy substrate by using No. 80-600 abrasive paper, and then ultrasonically cleaning for 5min by using absolute ethyl alcohol;
(2) micro-arc oxidation pretreatment: taking a stainless steel groove as a cathode, taking the aluminum alloy after the previous treatment as an anode, and treating by using an MAO-20C type micro-arc oxidation power supply;
the electrolyte comprises the following components: 10g/L of sodium silicate, 10g/L of sodium hexametaphosphate, 1g/L of sodium hydroxide and deionized water as a solvent;
the micro-arc oxidation pretreatment electrical parameters are as follows: pulse of lightFrequency 800Hz, duty ratio 20%, current density 9A/dm2At 15 ℃ for 2 min;
(3) cathode deposition treatment: treating graphite serving as an anode and the aluminum alloy subjected to micro-arc oxidation and treatment serving as a cathode by using an MAO-20C type micro-arc oxidation power supply;
the electrolyte used comprises the following components: 0.3mol/L of an ethanol solution of aluminum nitrate;
the used electricity parameters are: pulse frequency of 50Hz, duty ratio of 30 percent and current density of 5A/dm2At a temperature of 15 ℃; the time is 10min, the treated aluminum alloy is obtained, and the thickness of the aluminum oxide ceramic coating formed on the surface of the alloy is 7 mu m.
Comparative example 2
Pretreatment of a matrix: removing burrs and corrosion products on the surface of the aluminum alloy substrate by using No. 80-600 abrasive paper, and then ultrasonically cleaning for 5min by using absolute ethyl alcohol;
coating with zinc-aluminium coating
Preparation of a masking liquid:
a first component: 12.3g of polyethylene glycol, 5g of sheet aluminum powder, 203.3g of tween, 5.23g of silane coupling agent (gamma-glycidyl ether oxypropyl trimethoxy silane), 30g of sheet zinc powder and 15g of deionized water; mixing the components, and stirring at a speed of 200r/min for 3 h;
a second component: 7.7g of methanol, 10g of deionized water and 10.47g of silane coupling agent (gamma-glycidoxypropyltrimethoxysilane); mixing the components, and stirring at a speed of 200r/min for 3 h;
a third component: 0.72g of sodium phosphomolybdate and 10g of deionized water, and heating in a water bath at 40 ℃ for 4 hours after mixing;
mixing and stirring the second component and the third component for 3 hours, adding the first component, mixing and stirring for 16 hours to obtain a masking liquid;
immersing the aluminum alloy subjected to cathodic deposition treatment in the coating liquid for 3s, taking out the aluminum alloy, placing the aluminum alloy into an oven after the surface of a sample is leveled, preheating the aluminum alloy at 100 ℃ for 15min, sintering the aluminum alloy at 300 ℃ for 30min, and repeating the processes of dip coating, preheating and sintering again after the completion to obtain the chromium-free zinc-aluminum composite coating of the aluminum alloy; the thickness of the composite coating on the alloy surface is 12 mu m.
Comparative example 3
Pretreatment of a matrix: removing burrs and corrosion products on the surface of the aluminum alloy substrate by using No. 80-600 abrasive paper, and then ultrasonically cleaning for 5min by using absolute ethyl alcohol;
coating with zinc-aluminium coating
Preparation of a masking liquid:
a first component: 12.3g of polyethylene glycol, 5g of sheet aluminum powder, 203.3g of tween, 5.23g of silane coupling agent (gamma-glycidyl ether oxypropyl trimethoxy silane), 30g of sheet zinc powder and 15g of deionized water; mixing the components, and stirring at a speed of 200r/min for 3 h;
a second component: 7.7g of methanol, 10g of deionized water and 10.47g of silane coupling agent (gamma-glycidoxypropyltrimethoxysilane); mixing the components, and stirring at a speed of 200r/min for 3 h;
a third component: 0.72g of sodium phosphomolybdate and 10g of deionized water, and heating in a water bath at 40 ℃ for 4 hours after mixing;
mixing and stirring the second component and the third component for 3 hours, adding the first component, mixing and stirring for 16 hours to obtain a masking liquid;
immersing the aluminum alloy subjected to cathodic deposition treatment in the coating liquid for 2-3 s, taking out, placing the sample into an oven after the surface of the sample is leveled, preheating at 100 ℃ for 15min, sintering at 280 ℃ for 25min, and repeating the processes of dip coating, preheating and sintering again after the completion to obtain an aluminum alloy composite coating; the thickness of the composite coating on the alloy surface is 13 mu m.
Performance testing
The aluminum alloy chromium-free zinc-aluminum composite coatings prepared in examples 1-4 and the treated aluminum alloy or aluminum alloy composite coatings prepared in comparative examples 1-3 are subjected to neutral salt spray tests, the execution standard is GBT1771-2007, test samples are placed in a salt spray test box at constant temperature (35 +/-2 ℃) and specific humidity (more than 95%), the to-be-tested surfaces of the test samples are enabled to face upwards, the natural environment is simulated, the inclination angle of 15-30 degrees is formed between a flat plate sample and the test surface relative to the vertical direction, meanwhile, the flat plate sample cannot contact the inner wall of the test box, the to-be-tested samples are not in contact, after the tests, macro morphology characterization is carried out on different samples, and the obtained results are respectively shown in figures 1-7.
FIG. 1 is a surface topography of the chromium-free zinc-aluminum composite coating of the aluminum alloy prepared in example 1 after a salt spray test for 1200 h; as can be seen from FIG. 1, after 1200h of salt spray corrosion, no significant corrosion was observed on the surface of the coating.
FIG. 2 is a surface topography of the treated aluminum alloy prepared in comparative example 1 after being subjected to a salt spray test for 100 hours; as can be seen from FIG. 2, the aluminum alloy surface undergoes 100h salt spray corrosion to generate obvious white rust.
FIG. 3 is a surface topography of the aluminum alloy chromium-free zinc-aluminum composite coating prepared in comparative example 2 after 360h of a salt spray test; as can be seen from FIG. 3, the aluminum alloy chromium-free zinc-aluminum composite coating of the comparative example 2 generates obvious white rust after 360h of salt spray corrosion.
FIG. 4 is a macro topography of the aluminum alloy chromium-free zinc-aluminum composite coating prepared in comparative example 3 after being subjected to a salt spray test for 72 h; as can be seen from fig. 4, the sample was bubbled after 72 hours.
FIG. 5 is a surface topography of the chromium-free zinc-aluminum composite coating of the aluminum alloy prepared in example 2 after a salt spray test for 1200 h; as can be seen from FIG. 5, after 1200h of salt spray corrosion, no obvious corrosion was observed on the surface of the coating.
FIG. 6 is a surface topography of the aluminum alloy chromium-free zinc-aluminum composite coating prepared in example 3 after being subjected to a salt spray test for 1200 h; as can be seen from FIG. 6, after 1200h of salt spray corrosion, the coating surface was not corroded.
FIG. 7 is a surface topography of the chromium-free zinc-aluminum composite coating of the aluminum alloy prepared in example 4 after a salt spray test for 1200 h; as can be seen from FIG. 7, after 1200h of salt spray corrosion, the coating surface was not corroded.
As can be seen from FIGS. 1 to 7, in the single zinc-aluminum coating (comparative example 2), white rust occurred in 360h of salt spray; a single cathode deposition coating (comparative example 1) has obvious white rust after 100h of salt spray; when the curing temperature of the zinc-aluminum coating is 280 ℃ and 25min (comparative example 3), the salt spray generates bubbling after 72 h; the composite coating (example 1) of the cathode deposition and the zinc-aluminum coating has no obvious corrosion on the surface after 1200h of salt spray and has excellent corrosion resistance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (10)

1. The preparation method of the alloy composite coating is characterized by comprising the following steps of:
sequentially carrying out micro-arc oxidation pretreatment and cathode deposition treatment on the alloy to obtain a treated alloy;
dipping the treated alloy in a coating solution, taking out, sequentially preheating and curing, and repeating the processes of dipping, preheating and curing to obtain an alloy composite coating;
the masking liquid comprises a first component, a second component and a third component; the masking liquid does not contain chromium;
the first component comprises the following components in parts by mass: 10-20 parts of polyethylene glycol, 20-40 parts of flaky zinc powder, 203-6 parts of tween, 5-10 parts of first silane coupling agent, 5-10 parts of flaky aluminum powder and 10-20 parts of water;
the second component includes: 5-15 parts of methanol, 10-20 parts of water and 10-20 parts of a second silane coupling agent;
the third component includes: 0.5-1 part of sodium phosphomolybdate and 10-20 parts of water.
2. The preparation method according to claim 1, wherein the electrolyte for the micro-arc oxidation pretreatment comprises the following components: 10-20 g/L of sodium silicate, 10-20 g/L of sodium hexametaphosphate and 1-5 g/L of sodium hydroxide; the solvent of the electrolyte is water.
3. The method for preparing according to claim 1 or 2, wherein the micro-arc oxidation electrical parameters of the micro-arc oxidation pretreatment comprise: the pulse frequency is 600-900 Hz, the duty ratio is 10-50%, and the current density is 5-10A/dm2The temperature is 10-20 ℃, and the time is 2-10 min.
4. The method according to claim 1, wherein the electrolyte used in the cathodic deposition treatment is an aluminum salt alcohol solution; the cathode deposition treatment takes graphite as an anode and takes the alloy subjected to micro-arc oxidation pretreatment as a cathode.
5. A method of manufacturing as claimed in claim 1 or 4, wherein the electrical parameters of the cathodic deposition process include: the pulse frequency is 20-900 Hz, the duty ratio is 30-60%, and the current density is 3-15A/dm2The temperature is 10-20 ℃, and the time is 5-15 min.
6. The method according to claim 1, wherein the preheating is carried out at a temperature of 70 to 100 ℃ for 10 to 15 min.
7. The preparation method according to claim 1, wherein the temperature of each sintering is 260-320 ℃ independently, and the time is 30 min.
8. The preparation method of claim 1, wherein the thickness of the alloy surface composite coating in the alloy composite coating is 10-30 μm.
9. The method according to claim 1, wherein the first silane coupling agent and the second silane coupling agent are independently γ -aminopropyltriethoxysilane or γ -glycidoxypropyltrimethoxysilane.
10. The alloy composite coating prepared by the preparation method of any one of claims 1 to 9, which is characterized by comprising an alloy substrate and an aluminum oxide coating and a zinc-aluminum coating which are sequentially laminated on the surface of the alloy substrate.
CN202111324720.XA 2021-11-10 2021-11-10 Alloy surface composite coating and preparation method thereof Active CN114032547B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202111324720.XA CN114032547B (en) 2021-11-10 2021-11-10 Alloy surface composite coating and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202111324720.XA CN114032547B (en) 2021-11-10 2021-11-10 Alloy surface composite coating and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114032547A true CN114032547A (en) 2022-02-11
CN114032547B CN114032547B (en) 2022-08-23

Family

ID=80143788

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111324720.XA Active CN114032547B (en) 2021-11-10 2021-11-10 Alloy surface composite coating and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114032547B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115678428A (en) * 2022-11-18 2023-02-03 安徽富乐德科技发展股份有限公司 Preparation method of ceramic coating on inner wall of rapid annealing furnace

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102911534A (en) * 2012-10-18 2013-02-06 王宏 Water base non-chrome zinc-aluminium coating and methods for preparing and using same
CN104372394A (en) * 2014-07-03 2015-02-25 西安工业大学 Preparation method for oxide ceramic layer
WO2016161559A1 (en) * 2015-04-07 2016-10-13 GM Global Technology Operations LLC A light metal or alloy matrix workpiece having tailor coated corrosion resistant layers and methods for making the same
CN107937961A (en) * 2017-11-08 2018-04-20 天津正天医疗器械有限公司 The aluminium alloy surface treatment method and pulse electrodeposition hole sealing device of differential arc oxidation combination pulse electrodeposition sealing of hole
CN109111775A (en) * 2018-07-27 2019-01-01 广东工业大学 A kind of Chrome-free Zn-Al coating and a kind of Chrome-free Zn-Al coating
CN111073507A (en) * 2019-10-12 2020-04-28 广东省测试分析研究所（中国广州分析测试中心） Water-based chromium-free zinc-aluminum anticorrosive paint and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102911534A (en) * 2012-10-18 2013-02-06 王宏 Water base non-chrome zinc-aluminium coating and methods for preparing and using same
CN104372394A (en) * 2014-07-03 2015-02-25 西安工业大学 Preparation method for oxide ceramic layer
WO2016161559A1 (en) * 2015-04-07 2016-10-13 GM Global Technology Operations LLC A light metal or alloy matrix workpiece having tailor coated corrosion resistant layers and methods for making the same
CN107937961A (en) * 2017-11-08 2018-04-20 天津正天医疗器械有限公司 The aluminium alloy surface treatment method and pulse electrodeposition hole sealing device of differential arc oxidation combination pulse electrodeposition sealing of hole
CN109111775A (en) * 2018-07-27 2019-01-01 广东工业大学 A kind of Chrome-free Zn-Al coating and a kind of Chrome-free Zn-Al coating
CN111073507A (en) * 2019-10-12 2020-04-28 广东省测试分析研究所（中国广州分析测试中心） Water-based chromium-free zinc-aluminum anticorrosive paint and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115678428A (en) * 2022-11-18 2023-02-03 安徽富乐德科技发展股份有限公司 Preparation method of ceramic coating on inner wall of rapid annealing furnace

Also Published As

Publication number Publication date
CN114032547B (en) 2022-08-23

Similar Documents

Publication Publication Date Title
CN104651908B (en) The preparation method and method for sealing of a kind of Mg alloy surface ceramic film
CN100464006C (en) Process for preparing magnesium alloy surface function gradient film
CN108165165B (en) Preparation method of neodymium iron boron magnet material surface composite anticorrosive coating
CN109402699A (en) A kind of aluminum alloy surface acid resistance corrosion function ceramic membrane preparation process
CN108560037B (en) A kind of Boron Containing Low Carbon Steel oxidation film layer and preparation method thereof
CN102234800A (en) Aluminum alloy rare earth passivating liquid taking chlorine salt as accelerator and use method thereof
CN114941164B (en) Preparation method of magnesium alloy surface dual-function composite coating
CN114032547B (en) Alloy surface composite coating and preparation method thereof
CN113088966A (en) Magnesium alloy composite coating and preparation method thereof
CN110129858B (en) Ionic liquid assisted magnesium-lithium alloy anodic oxidation film forming method
CN109161890B (en) SiO (silicon dioxide)2Micro-arc oxidation composite coating and preparation method thereof
CN108149232B (en) Environment-friendly passivation solution for aluminum or seven-series aluminum alloy and preparation method and treatment process thereof
CN111197176B (en) Electrochemical treatment method of copper foil and composite copper foil material
CN101914743A (en) Magnesium alloy surface treatment method
CN113737246A (en) Micro-arc oxidation treatment process for aluminum alloy surface
JP2008202118A (en) Method of modifying anodic oxide film
CN117186710A (en) Self-repairing anti-corrosion composite coating and preparation method thereof
CN109183094B (en) Preparation method of magnesium alloy surface high-emissivity coating
CN115896713A (en) Novel high-bonding-force high-temperature-resistant wear-resistant corrosion-resistant Al 2 O 3 /SiO 2 Composite coating and preparation method thereof
CN114774863B (en) Li-Al LDH film on magnesium alloy surface and rapid preparation method thereof
CN115142055B (en) Hydrophobic chemical conversion film forming liquid and aluminum alloy surface treatment method
CN113684511B (en) Electrochemical preparation method of high-temperature self-repairing coating and product thereof
Wu et al. Designing for the cerium‐based conversion coating with excellent corrosion resistance on Mg–4Y–2Al magnesium alloy
CN111074262A (en) Sintered NdFeB magnet surface vitrified film and preparation method thereof
Wei et al. Microstructure and corrosion resistance studies of PEO coated Mg alloys with a HF and US pretreatment

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant