CN114733737A - Composite coating and preparation method thereof - Google Patents
Composite coating and preparation method thereof Download PDFInfo
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- CN114733737A CN114733737A CN202210395127.2A CN202210395127A CN114733737A CN 114733737 A CN114733737 A CN 114733737A CN 202210395127 A CN202210395127 A CN 202210395127A CN 114733737 A CN114733737 A CN 114733737A
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- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
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- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
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- 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
- 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
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
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- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/20—Acidic compositions for etching aluminium or alloys thereof
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/22—Acidic compositions for etching magnesium or alloys thereof
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- B05D2202/00—Metallic substrate
- B05D2202/20—Metallic substrate based on light metals
- B05D2202/25—Metallic substrate based on light metals based on Al
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B05D2518/00—Other type of polymers
- B05D2518/10—Silicon-containing polymers
- B05D2518/12—Ceramic precursors (polysiloxanes, polysilazanes)
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Abstract
The invention relates to a composite coating and a preparation method thereof, belonging to the technical field of corrosion prevention of metal materials. The preparation method of the composite coating comprises the following steps: etching the surface of the metal substrate by using acid liquor, growing cluster-shaped hydrated alumina on the etched surface of the metal substrate to form a hydrated alumina layer, coating an organic silicon polymer precursor on the hydrated alumina layer, and finally performing heat treatment to pyrolyze part or all of the organic silicon polymer precursor to obtain the organic silicon polymer; the organosilicon polymer precursor is capable of pyrolyzing to form a hydrophobic silicon-based ceramic. Due to the rough structure of the cluster hydrated alumina and the low surface energy characteristic of the organic silicon polymer precursor, the prepared composite coating has super-hydrophobic performance, has a contact angle with water of 160 degrees, has good corrosion resistance, excellent thermal stability, acid and alkali resistance and salt resistance, and has potential application in seawater harsh environment.
Description
Technical Field
The invention relates to a composite coating and a preparation method thereof, belonging to the technical field of corrosion prevention of metal materials.
Background
Metal corrosion can be defined as the interaction of materials with various chemical components in the working environment, and chemical, electrochemical or biochemical reactions occur on the surface of the metal to cause the structural composition of the metal material to be damaged, thereby affecting the service performance of the metal material. The most common method is to apply a metal anti-corrosion coating on the surface of metal, and the anti-corrosion coating is mostly based on the barrier principle to realize metal corrosion prevention. The super-hydrophobic coating is an anti-corrosion coating with good anti-corrosion performance, and corrosive ions are difficult to reach the surface of the material due to the hydrophobic rough microstructure and the high static apparent contact angle, so that the anti-corrosion purpose is achieved. However, the stability and mechanical strength of the super-hydrophobic coating constructed on the metal surface are poor, and the service life of the super-hydrophobic coating is shortened.
Disclosure of Invention
The invention aims to provide a preparation method of a composite coating, which is used for solving the problems of poor stability and poor mechanical strength of a super-hydrophobic coating constructed on the surface of metal at present.
It is another object of the present invention to provide a composite coating.
In order to achieve the purpose, the preparation method of the composite coating adopts the technical scheme that:
a preparation method of a composite coating comprises the following steps: etching the surface of the metal substrate by using acid liquor, growing cluster-shaped hydrated alumina on the etched surface of the metal substrate to form a hydrated alumina layer, coating an organic silicon polymer precursor on the hydrated alumina layer, and finally performing heat treatment to pyrolyze part or all of the organic silicon polymer precursor to obtain the organic silicon polymer; the organosilicon polymer precursor is capable of pyrolyzing to form a hydrophobic silicon-based ceramic.
The preparation method of the composite coating comprises the steps of firstly etching the surface of the metal base material by adopting acid liquor, forming a multi-stage structure on the surface of the metal base material, further improving the binding force between hydrated alumina and the metal base material, then growing cluster-shaped hydrated alumina on the etched surface of the metal base material in situ, coating an organic silicon polymer precursor on the hydrated alumina, and finally carrying out heat treatment, so that the hydrated alumina can be converted into alumina ceramic, and the organic silicon polymer precursor can be partially or completely converted into ceramic material. Because the alumina ceramic and the organosilicon polymer precursor after the heat treatment are firmly combined together by covalent bonds, the composite coating prepared by the invention has good stability and stronger mechanical strength. Hydrophobic organic silicon polymer precursors are coated on the cluster hydrated alumina, and hydrophobic silicon-based ceramics can be formed after heat treatment, so that the composite coating is endowed with excellent hydrophobic performance. Due to the rough structure of the cluster hydrated alumina and the low surface energy characteristic of the organic silicon polymer precursor, the prepared composite coating has super-hydrophobic performance, has a contact angle with water of 160 degrees, has good corrosion resistance, excellent thermal stability, acid and alkali resistance and salt resistance, and has potential application in seawater harsh environment. The preparation method of the composite coating is simple in process and convenient for large-scale production and application.
Preferably, the metal substrate is aluminum or an aluminum alloy. Further, the aluminum alloy is aluminum magnesium alloy. The aluminum-magnesium alloy is used as the metal base material, and the beneficial effect of improving the binding force between the hydrated alumina layer and the base material is achieved.
Preferably, before the surface of the metal base material is etched, the surface to be etched of the metal base material is polished by sequentially using sandpaper with 800 meshes, 1000 meshes and 2000 meshes.
Preferably, after polishing treatment, the metal substrate is subjected to ultrasonic cleaning by sequentially using acetone, absolute ethyl alcohol and distilled water, then drying treatment is performed, and then the surface of the metal substrate is etched by using acid liquor. Preferably, the time for ultrasonically cleaning the metal base material by adopting acetone, absolute ethyl alcohol and distilled water is 5-10 min. Preferably, the temperature adopted by the drying treatment is 50-150 ℃, and the time of the drying treatment is 5-10 min.
The present invention is not limited to acid solutions, and acid solutions used for etching the surface of a metal substrate are all suitable for use in the present invention.
Preferably, the acid solution is hydrochloric acid. Preferably, the concentration of the hydrochloric acid is 1-3 mol/L. Preferably, the etching time is 1-20 min. The etching time is 1-20 min, and a multi-stage rough structure can be constructed on the etching surface of the metal substrate.
Preferably, the method for growing cluster-shaped hydrated alumina on the etched surface of the metal substrate comprises the following steps: and immersing the etched metal substrate into a hydrated alumina precursor liquid at the temperature of 150-250 ℃ for reaction for 10-48 h. Preferably, the hydrated alumina precursor liquid consists essentially of an aluminum source, a precipitant, and a solvent. Preferably, the aluminium source is an aluminium salt. Preferably, the precipitating agent is urea. Preferably, the solvent is water. Preferably, the aluminium salt is aluminium sulphate. Preferably, the mass ratio of the aluminum source to the precipitant to the solvent is (10-30): 6-20): 100.
Preferably, after the reaction is finished, the metal base material is cleaned and dried to obtain the metal base material with cluster-shaped hydrated alumina growing on the surface.
Preferably, the silicone polymer precursor is formed by dip-coating or spray-coating a liquid silicone coating solution on the hydrated alumina layer and curing. Preferably, the liquid organosilicon coating liquid mainly comprises one or two of polysiloxane or polysilazane, a curing agent and a solvent.
Preferably, the polysiloxane is polydimethylsiloxane. Preferably, the mass ratio of the polysiloxane to the curing agent is 10: 1. The silicone and curing agent may be used in an existing package, such as Dow Corning DC 184. Preferably, the liquid silicone coating liquid consists essentially of a solvent, an agent a and an agent B in DC 184; the agent A is a basic component, the agent B is a curing agent, and the basic component comprises polydimethylsiloxane; the mass ratio of the agent A to the agent B is 10: 1. Preferably, the polysilazane is an organic polysilazane. Preferably, the molecular weight of the organic polysilazane is 700-900. The organopolysilazane is commercially available, for example, IOTA 9108 from avita silicone oil limited, Anhui. Preferably, the curing temperature is 50-150 ℃, and the curing time is 1-5 h. After heat treatment, polysiloxane is partially converted into compact ceramic materials such as silicon dioxide, silicon carbon compound or silicon-oxygen-carbon with a micro-nano structure, and the ceramic materials are firmly combined together by a covalent bond and a hydrated alumina layer, so that the stability of the composite coating is improved.
Preferably, the solvent in the liquid silicone coating liquid is tetrahydrofuran. Preferably, in the liquid organosilicon coating liquid, the mass ratio of the polysiloxane to the solvent is 1 (5-50).
Preferably, the dip coating comprises the steps of: and (3) immersing the metal base material with the cluster-shaped hydrated alumina growing on the surface into the liquid organic silicon coating liquid, keeping for 1-10 min, and then taking the metal base material with the cluster-shaped hydrated alumina growing on the surface out of the liquid organic silicon coating liquid at a speed of 5-10 mm/min. Preferably, the spraying comprises the steps of: coating the liquid organic silicon coating liquid on the surface of the cluster hydrated alumina by using a spraying machine; the spraying machine is an air compressor, when spraying is conducted, the internal pressure of the air compressor is 0.1-0.6 MPa, the distance between a spray gun and the surface of the clustered hydrated alumina is 10-30 cm, and the spraying time is 1-10 s. For example, in the case of spraying, the internal pressure of the air compressor was 0.6MPa, the distance between the spray gun and the surface of the clustered hydrated alumina was 20cm, and the spraying time was 5 seconds.
Preferably, the temperature adopted by the heat treatment is 300-400 ℃, and the time of the heat treatment is 5-30 min.
The technical scheme adopted by the composite coating is as follows:
a composite coating prepared by the preparation method of the composite coating.
The composite coating takes clustered hydrated alumina as a bottom layer, then hydrophobic organic silicon polymer precursors are coated on the hydrated alumina, and then heat treatment is carried out, so that two corrosion-resistant barriers are constructed on the surface of the metal, and the corrosion resistance of the metal can be improved. The composite coating disclosed by the invention not only has super-hydrophobicity and anti-corrosion performance, but also has good stability.
Drawings
FIG. 1 is a schematic illustration of the static contact angle of a metal substrate to water in example 3;
FIG. 2 is a schematic illustration of the static contact angle of a chemically etched surface of a metal substrate against water in example 3;
FIG. 3 is a schematic representation of the static contact angle of the alumina ceramic coating to water in example 3;
FIG. 4 is a schematic representation of the static contact angle of the composite coating to water in example 3;
FIG. 5 is a scanning electron micrograph of the metal substrate, the chemically etched side of the metal substrate, and the alumina ceramic coating and composite coating on the metal substrate of example 15;
FIG. 6 is a schematic view of a method of an abrasion test in Experimental example 4;
FIG. 7 is a schematic illustration of the contact angle of the composite coating prepared in example 24 before ultrasonic treatment;
FIG. 8 is a schematic representation of the contact angle of the composite coating prepared in example 24 after sonication;
FIG. 9 is a graphical representation of the contact angle of the composite coating prepared in example 24 at different wear cycles;
FIG. 10 is a graphical representation of Tafel polarization test curves for the metal substrate and the metal substrate with the composite coating of example 24;
FIG. 11 is a Bode plot and Nyquist plot for the metal substrate and the metal substrate with the composite coating of example 24;
FIG. 12 is a graphical representation of the stability of the composite coatings prepared in example 15 at various pH conditions;
FIG. 13 is a schematic illustration of the contact angle of the composite coating prepared in example 24 at 15min of heat treatment;
FIG. 14 is a schematic representation of the contact angle of the composite coating prepared in example 24 at a heat treatment time of 30 min;
FIG. 15 is a schematic representation of the contact angle of the composite coating prepared in example 24 at a heat treatment time of 60 min;
fig. 16 is a schematic view of the contact angle of the composite coating prepared in example 24 at a heat treatment time of 90 min.
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples.
DC184 in embodiments of the present invention is manufactured by Dow Corning; the organic polysilazane is produced by Anhui Eyota Silicone oil Co., Ltd, and has a product model number of IOTA 9108.
The specific embodiment of the preparation method of the composite coating is as follows:
a method of making the composite coatings of examples 1-28, comprising the steps of:
(1) the method comprises the steps of polishing a metal sheet by using sand paper with the mesh number of 800 meshes, 1000 meshes and 2000 meshes in sequence, then ultrasonically cleaning the metal sheet by using acetone, absolute ethyl alcohol and distilled water in an ultrasonic cleaner in sequence, wherein the time for ultrasonically cleaning the metal sheet by using the acetone, the absolute ethyl alcohol and the distilled water is a min, then drying the cleaned metal sheet in an environment with the temperature of b ℃ for c min to obtain a metal base material, then etching the surface to be etched of the metal base material by using hydrochloric acid with the concentration of d mol/L for e min, and washing away acid liquor to obtain the chemically etched metal base material. The metal sheet is made of aluminum-magnesium alloy.
(2) Immersing the chemically etched metal base material into a hydrated alumina precursor solution g h with the temperature of f ℃ to deposit and grow cluster-shaped hydrated alumina on the etched surface of the metal base material, washing the metal base material with deionized water after deposition is finished, and drying the metal base material to obtain the metal base material deposited with the hydrated alumina layer.
(3) And (2) soaking the metal base material deposited with the hydrated alumina layer in a liquid organic silicon coating liquid for h min, taking the metal base material with the cluster-shaped hydrated alumina growing on the surface out of the liquid organic silicon coating liquid at the speed of i mm/min, curing at the temperature of j for k h, finally performing heat treatment at the temperature of l for m min, and cooling to obtain the metal base material containing the composite coating.
The preparation method of the composite coating of examples 1 to 28 includes steps of mixing a hydrated alumina precursor solution used in the preparation method with aluminum sulfate, urea and deionized water, and a liquid organosilicon coating solution with a solvent, a basic component of DC184 (dow corning) and a curing agent, wherein the solvent is tetrahydrofuran; the mass ratio of the basic component to the curing agent is 10: 1. The mass ratios of aluminum sulfate, urea and deionized water in the hydrated alumina precursor liquid used in each example and the mass ratios of DC184 (total mass of base component and curing agent) and solvent used in preparing the liquid silicone coating liquid are shown in table 1.
The ultrasonic cleaning time, drying temperature and time, hydrochloric acid concentration and chemical etching time used in step (1), the temperature of the hydrated alumina precursor liquid and the deposition growth time in step (2), and the dipping time, the pull rate, the curing temperature and time and the heat treatment temperature and time in step (3) of the preparation methods of the composite coatings of examples 1 to 28 are shown in table 2.
Table 1 compositions and proportions of hydrated alumina precursor liquid and liquid silicone coating liquid used in the preparation of the composite coatings of examples 1-28
TABLE 2 parameters used at each step in the preparation of the composite coatings of examples 1-28
Example 29
The preparation method of the composite coating of the embodiment comprises the following steps:
(1) the method comprises the steps of sequentially polishing a metal sheet by using sand paper with the meshes of 800 meshes, 1000 meshes and 2000 meshes, sequentially ultrasonically cleaning the metal sheet by using acetone, absolute ethyl alcohol and distilled water in an ultrasonic cleaner for 5min, drying the cleaned metal sheet in an environment with the temperature of 50 ℃ for 10min to obtain a metal base material, etching the surface to be etched of the metal base material by using hydrochloric acid with the concentration of 1mol/L for 20min, and washing away acid liquor to obtain the chemically etched metal base material. The metal sheet is made of aluminum-magnesium alloy.
(2) Immersing the chemically etched metal base material into a hydrated alumina precursor liquid with the temperature of 150 ℃ for 48h to deposit and grow cluster-shaped hydrated alumina on the etched surface of the metal base material, washing the metal base material with deionized water after deposition is finished, and drying the metal base material to obtain the metal base material deposited with the hydrated alumina layer.
(3) And (2) coating the liquid organic silicon coating liquid on the surface of the cluster hydrated alumina by adopting a spraying machine, wherein the spraying machine is an air compressor, when spraying is carried out, the internal pressure of the air compressor is 0.6MPa, the distance between a spray gun and the surface of the cluster hydrated alumina is 20cm, the spraying time is 5s, then the cluster hydrated alumina is solidified for 5h at 50 ℃, finally, the cluster hydrated alumina is subjected to heat treatment for 60min at 300 ℃, and the metal base material containing the composite coating is obtained after cooling.
The hydrated alumina precursor liquid adopted in the embodiment consists of aluminum sulfate, urea and deionized water, wherein the mass ratio of the aluminum sulfate to the urea to the deionized water is 10:6: 100; the liquid organosilicon coating liquid is formed by mixing a solvent, basic components in DC184 (Dow Corning) and a curing agent, wherein the solvent is tetrahydrofuran; the mass ratio of the base component to the curing agent was 10:1, and the mass ratio of DC184 (total mass of the base component and the curing agent) to the solvent used in preparing the liquid silicone coating liquid was 1.1: 50.
Example 30
The preparation method of the composite coating of this example differs from that of example 29 only in that the time of heat treatment in step (3) is 30min, the liquid silicone coating liquid used in step (3) consists of an organic polysilazane and a solvent, the solvent is tetrahydrofuran, and the mass ratio of the organic polysilazane to the solvent is 1: 50.
Example 31
The method of producing a composite coating layer of this example differs from the method of producing a composite coating layer of example 29 only in that the time for curing at 50 ℃ in step (3) is 1 hour, and the time for heat treatment at 300 ℃ is 30 minutes, and that the liquid silicone coating liquid used in step (3) is formed by mixing an organopolysiloxane coating liquid and a polydimethylsiloxane coating liquid in a mass ratio of 1:1, the organopolysiloxane coating liquid is formed by mixing an organopolysiloxane and tetrahydrofuran in a mass ratio of 1:50, and the polydimethylsiloxane coating liquid is formed by mixing DC184 (the total mass of the base component and the curing agent) and tetrahydrofuran in a mass ratio of 1.1: 50.
Experimental example 1
To test the hydrophobic properties of the coatings, the metal substrate, the chemically etched metal substrate, and the alumina ceramic coating and composite coating on the metal substrate of example 3 were tested for static contact angle to water using a contact angle tester, and the results are shown in fig. 1-4. The results show that the static contact angle of the metal substrate to water (fig. 1) is 57.3 °, the static contact angle of the chemically etched surface of the metal substrate to water (fig. 2) is reduced to 11.7 °, and the static contact angles of the alumina ceramic coating and the composite coating to water (fig. 3-4) are 3.4 ° and 160 °, respectively. The contact angle test result shows that the super-hydrophobic coating can be successfully prepared on the surface of the aluminum magnesium alloy by utilizing the scheme of the invention.
Experimental example 2
Scanning electron microscopy is adopted to respectively characterize the metal base material, the chemical etching surface of the metal base material, and the alumina ceramic coating and the composite coating on the metal base material in example 15, and the experimental result is shown in fig. 5. The results show that the surface of the metal substrate (fig. 5a) showed sandpaper marks, and was relatively smooth and flat; after chemical etching (fig. 5b), the surface of the metal substrate presents a step-like multi-level rough structure; the surface of the alumina ceramic coating (fig. 5c) exhibits a clustered crystalline structure; the surface topography of the composite coating is close to that of the alumina ceramic coating, but there is a significant covering of particulate particles on the cluster surface, which may be the result of partial decomposition of the polysiloxane. According to the scanning electron microscope result, the composite structure of the low surface energy and the rough surface of the surface endows the composite coating with excellent super-hydrophobicity, and is consistent with the contact angle test result.
Experimental example 3
The metal substrate, the chemically etched metal substrate, and the alumina ceramic coating and composite coating on the metal substrate of example 15 were characterized using an elemental analyzer and the results are shown in tables 3-6.
TABLE 3 elemental analysis results of the surface of the metal base material
| Elemental composition | Atomic mol% percent (%) | Atomic weight percent (%) |
| O | 2.506 | 1.500 |
| Mg | 2.475 | 2.250 |
| Al | 94.808 | 95.656 |
| Si | 0.009 | 0.111 |
| Cu | 0.119 | 0.282 |
| Zn | 0.082 | 0.201 |
| Total amount of | 100.000 | 100.000 |
TABLE 4 elemental analysis results of etched surface of metal substrate
| Elemental composition | Atomic mol% percent (%) | Atomic weight percent (%) |
| O | 4.171 | 2.517 |
| Mg | 2.606 | 2.389 |
| Al | 92.867 | 94.500 |
| Si | 0.029 | 0.031 |
| Cl | 0.212 | 0.284 |
| Cu | 0.050 | 0.120 |
| Zn | 0.065 | 0.160 |
| Total amount of | 100.000 | 100.000 |
TABLE 5 elemental analysis results for alumina ceramic coatings
| Elemental composition | Atomic mol% percent (%) | Atomic weight percent (%) |
| O | 37.976 | 26.596 |
| Mg | 0.783 | 0.833 |
| Al | 60.839 | 71.853 |
| Si | 0.262 | 0.322 |
| Cu | 0.045 | 0.125 |
| Zn | 0.095 | 0.271 |
| Total amount of | 100.000 | 100.000 |
TABLE 6 elemental analysis results of composite coatings
| Element(s)Composition (A) | Atomic mol% percent (%) | Atomic weight percent (%) |
| C | 7.405 | 3.759 |
| O | 21.793 | 14.739 |
| Al | 54.748 | 62.442 |
| Si | 16.054 | 19.060 |
| Total amount of | 100.000 | 100.000 |
The results show that the oxygen content (atomic mole percent) increased from 2.5% to 4.2% after chemical etching compared to aluminum magnesium alloy; while the oxygen content (atomic mole percent) in the alumina ceramic coating increased to 38.0% due to the formation of hydrated alumina (AlOOH); the content of carbon element and silicon element in the composite coating is obviously increased, and the content of aluminum element and oxygen element is reduced, which further proves the successful introduction of the polysiloxane coating. The elemental analysis results show that example 15 can successfully prepare a composite coating.
Experimental example 4
The stability of the composite coatings prepared in example 24 was tested using sonication and abrasion experiments, respectively. The conditions of the sonication were as follows: the power of the ultrasonic instrument is 100w, and the ultrasonic time is 30 min. The method of wear testing is shown in fig. 6 and comprises the following steps: the method comprises the steps of contacting the surface of a composite coating of a metal base material 3 with a composite coating with 1000-mesh abrasive paper 1, placing a weight 2 with the mass of 100g on the metal base material, dragging the metal base material 3 with the composite coating at a constant speed under a load condition to enable the abrasive paper 1 to continuously abrade the composite coating, taking the length of dragging relative to the abrasive paper 1 as 10cm as an abrasion cycle, and testing the contact angle of the surface of the composite coating after each cycle is finished.
The contact angles of the composite coating prepared in example 24 before and after the ultrasonic treatment are shown in fig. 7 and 8. The results show that the contact angle of the composite coating prepared in example 24 hardly changes before and after the ultrasonic treatment: the contact angle before the ultrasound is 160 degrees, and the contact angle after the ultrasound is still 160 degrees; the composite coating prepared in example 24 is shown to have excellent stability.
The results of the contact angles of the composite coatings prepared in example 24 at different wear cycles are shown in fig. 9. The result shows that after 15 cycles of abrasion, the contact angle of the composite coating still keeps above 150 degrees, and after 30 cycles of abrasion, the contact angle of the composite coating only drops to 147 degrees; the composite coating prepared in example 24 is shown to have excellent stability.
Experimental example 5
The corrosion protection performance of the composite coating prepared in example 24 was evaluated by means of a polarization curve. The method comprises the steps of measuring the intersection point of a cathode polarization curve and an anode polarization curve tangent, and obtaining corrosion parameters of metal, such as self-corrosion potential, corrosion current density I corr, polarization resistance and the like through computer fitting. When the corrosion resistance is tested, a five-mouth round flask is used as an electrolytic cell, and a three-electrode working system is adopted as a measurement system: the reference electrode was a Saturated Calomel Electrode (SCE), the counter electrode was a platinum electrode sheet, and the working electrode was the study electrode, i.e., the composite coated metal substrate (aluminum metal sheet with super-hydrophobic coating) prepared in example 24. The research electrode is arranged in a measuring system, Tafel polarization curve measurement is carried out, the step potential is set to be 1mv, and the scanning speed is set to be 1 mv/s. The results of fitting the Tafel polarization curves with the fitting software of the electrochemical workstation to obtain the corrosion curves of the study electrode and the comparison electrode (the metal substrate without the composite coating) are shown in fig. 10, wherein fig. 10a is a schematic view of the Tafel polarization curve of the metal substrate in example 24, fig. 10b is a schematic view of the Tafel polarization curve of the metal substrate with the composite coating in example 24, and the specific fitting parameters are shown in table 7.
TABLE 7 Corrosion parameters of Metal substrates and Metal substrates containing composite coatings
| Sample name | Corrosion potential (V) | Corrosion current density (A/cm)2) | Corrosion Rate (mm/y) |
| Metal substrate without composite coating | -0.8342 | 4.252×10-6 | 0.01391 |
| Metal substrate with composite coating | -0.2715 | 4.412×10-8 | 0.00001803 |
As can be seen from FIG. 10 and Table 7, the corrosion potential of the metal substrate without the composite coating was-0.8342 v, and the corrosion current density was 4.252X 10-6A/cm2(ii) a The corrosion potential of the metal substrate containing the composite coating is increased to-0.2715 v, and the corrosion current density is reduced to 4.412 multiplied by 10-8A/cm2(ii) a Obviously, after the super-hydrophobic composite coating is constructed on the surface of the metal base material, the corrosion potential is greatly increased and is increased by 67.5 percent compared with the corrosion potential of a blank metal base material; the corrosion current density dropped significantly, by about 2 orders of magnitude. The corrosion rate of the metal substrate is 0.01391 mm/y; while that of the metal substrate containing the composite coating is only 0.00001803 mm/y; the corrosion rate data further indicates that the composite coating prepared in example 24 can impart excellent corrosion resistance to a metal substrate.
Experimental example 6
The corrosion resistance of the composite coating prepared in example 24 was further evaluated by electrochemical impedance spectroscopy. The study electrode (the metal substrate containing the composite coating prepared in example 24) was mounted in a measurement system, and electrochemical impedance spectroscopy was performed, and the measurement was performed by a constant potential alternating current impedance method, wherein the frequency range was 0.01 to 106Hz, the amplitude of the alternating current signal was 10mV, and the number of frequency points was 5. The corrosion resistance of the coating can be evaluated by combining a Nyquist diagram of an electrochemical impedance spectrum with a Bode diagram, wherein the Bode diagram is a plan diagram which takes a phase angle theta as a vertical coordinate and takes a frequency logf as a horizontal coordinate; the Nyquist plot is a plot with the imaginary part (Z ") of the impedance as the ordinate and the real part (Z') of the impedance as the abscissa. FIG. 11 is a Bode plot and a Nyquist plot for the metal substrate of example 24 and the metal substrate with the composite coating, with specific fitting parameters shown in Table 8. In which fig. 11a and 11b are Bode plots of a metal substrate without a composite coating, fig. 11d and 11e are Bode plots of a metal substrate with a composite coating, fig. 11c is a Nyquist plot of a metal substrate without a composite coating, and fig. 11f is a Nyquist plot of a metal substrate with a composite coating.
TABLE 8 Corrosion parameters of Metal substrates and Metal substrates containing composite coatings
| Sample name | Polarization resistance omega | Impedance omega at 0.1Hz |
| Metal substrate without composite coating | 6898 | 3580 |
| Metal substrate with composite coating | 7289000 | 1510000 |
As can be seen from fig. 11 and table 8, the polarization resistance of the metal substrate without the composite coating was 6898 Ω, while the polarization resistance of the metal substrate with the composite coating was 7289000 Ω, which is far higher than that of the metal substrate without the composite coating, indicating that the composite coating can impart excellent corrosion resistance to the metal substrate. In addition, from the comparison of the low frequency band of the Bode plot (FIG. 11a), it can be seen that the impedance value of 3580 Ω at 0.1Hz of the metal substrate without the composite coating is much lower than the impedance value of 1510000 Ω at 0.1Hz of the metal substrate with the composite coating (FIG. 11 d). The polarization resistance and the impedance value are both surface, and the composite coating has excellent corrosion resistance.
The phase angle of the metal substrate without the composite coating at 10000Hz is close to 0, and the phase frequency diagram becomes negative, probably due to the corrosion of the surface and the formation of a punctate microbattery at the interface of the metal substrate. The metal substrate modified by the composite coating still has a linear trend, which shows that the corrosion resistance of the metal substrate in a high-frequency region is still stronger than that of the metal substrate without the modified coating, and the phase frequency value is in a positive value, which shows that the metal substrate has good shielding performance.
In addition, whether the metal substrate does not contain the composite coating or the metal substrate with the composite coating on the surface, a peak exists in the phase angle curve in the Bode phase angle fitting graph (fig. 11b and 11e), and a semicircle exists in the corresponding Nyquist fitting graph (fig. 11c and 11f), namely a capacitive reactance arc exists, and the impedance spectrum shows a time constant, so that the corrosion medium cannot penetrate through the coating and diffuse to the surface of the metal below the film, and the metal below the film cannot be corroded. When the electrolyte solution penetrates into the coating, a corrosion microbattery forms at the interface region between the coating and the metal, and the spectrum shows two time constants. However, only one time constant can be observed from the spectrum of the composite coating, which indicates that the coating is dense and has good shielding performance.
Experimental example 7
The acid and alkali stability of the metal substrate with the composite coating prepared in example 15 was tested using different pH solutions. The conditions for the acid and alkali resistance test are as follows: preparing solutions with different pH values by using hydrochloric acid and ammonium hydroxide, respectively placing the metal base material containing the composite coating in the solutions with different pH values, placing the metal base material at room temperature for 24 hours, taking out the metal base material, and testing the contact angle of the composite coating on the surface of the metal base material to water after drying.
The results of the alkali and acid resistance test of the metal substrate including the composite coating layer prepared in example 15 are shown in fig. 12 (the contact angle of the composite coating layer before the alkali and acid resistance test is 160 °). The results show that the contact angle of the composite coating on the surface of the metal base material before and after the acid and alkali resistance experiment is not greatly different, and the contact angle is about 160 degrees; when the pH is 14, the average value of the contact angle after the experiment is 150 degrees, the contact angle of the coating before the experiment is greatly different, probably because the silicon dioxide decomposed on the surface reacts with alkali and is peeled off, but the coating is still a super-hydrophobic coating; the acid and alkali resistance experiment shows that the composite coating prepared in example 15 has excellent acid and alkali resistance.
Experimental example 8
The metal substrates having the composite coatings prepared in example 24 were heat-treated at 350 ℃ for 15, 30, 60 and 90min, respectively, and then the heat-treated metal substrates were electrochemically tested by polarization curves according to the method of experimental example 5, and the contact angles of the heat-treated composite coatings to water were tested, with the experimental results shown in fig. 13 to 16 and table 9.
The results show that when the heat treatment time is 30min, the electrochemical and contact angle test results of the composite coating after heat treatment are hardly changed compared with the untreated composite coating; when the heat treatment time was increased to 60min, the contact angle data was almost unchanged, but the corrosion resistance was deteriorated. This is probably due to the fact that with increasing heat treatment time the polysiloxane decomposes to an increasing extent, affecting the compactness of the coating, resulting in a decrease in the corrosion resistance of the coating.
TABLE 9 Corrosion parameters and contact Angle to Water of the thermally treated composite coatings
| Heat treatment time (min) | Corrosion potential (V) | Corrosion current density (A/cm)2) | Contact angle (°) |
| 0 | -0.2715 | 4.412×10-8 | 160 |
| 15 | -0.2715 | 4.412×10-8 | 158.6 |
| 30 | -0.3086 | 8.385×10-7 | 157.9 |
| 60 | -0.5623 | 2.223×10-7 | 158.1 |
| 90 | -0.6273 | 5.201×10-7 | 163.6 |
Claims (10)
1. The preparation method of the composite coating is characterized by comprising the following steps: etching the surface of the metal substrate by using acid liquor, growing cluster-shaped hydrated alumina on the etched surface of the metal substrate to form a hydrated alumina layer, coating an organic silicon polymer precursor on the hydrated alumina layer, and finally performing heat treatment to pyrolyze part or all of the organic silicon polymer precursor to obtain the organic silicon polymer; the organosilicon polymer precursor is capable of pyrolyzing to form a hydrophobic silicon-based ceramic.
2. The method of preparing a composite coating according to claim 1, wherein the metal substrate is aluminum or an aluminum alloy.
3. The method for preparing the composite coating according to claim 2, wherein before etching the surface of the metal substrate, the surface to be etched of the metal substrate is polished by sequentially using sandpaper with 800 meshes, 1000 meshes and 2000 meshes.
4. The method for preparing a composite coating according to claim 1, wherein the acid solution is hydrochloric acid; the concentration of the hydrochloric acid is 1-3 mol/L; the etching time is 1-20 min.
5. The method for preparing the composite coating according to claim 1, wherein the method for growing cluster-shaped hydrated alumina on the etched surface of the metal substrate comprises the following steps: immersing the etched metal substrate into a hydrated alumina precursor liquid at the temperature of 150-250 ℃ for reaction for 10-48 h; the hydrated alumina precursor liquid mainly comprises an aluminum source, a precipitator and a solvent; the aluminum source is aluminum salt; the precipitator is urea; the solvent is water; the aluminum salt is aluminum sulfate; the mass ratio of the aluminum source to the precipitant to the solvent is (10-30): (6-20): 100.
6. The method of preparing a composite coating according to any one of claims 1 to 5, wherein the silicone polymer precursor is formed by dip-coating or spray-coating a liquid silicone coating liquid on the hydrated alumina layer and curing; the liquid organosilicon coating liquid mainly comprises one or two of polysiloxane or polysilazane, a curing agent and a solvent.
7. The method of preparing a composite coating according to claim 6, wherein the polysiloxane is polydimethylsiloxane, and the polysilazane is an organopolysiloxane; the mass ratio of the polysiloxane to the curing agent is 10: 1; the curing temperature is 50-150 ℃, and the curing time is 1-5 h.
8. The method of preparing a composite coating according to claim 6, wherein said dip coating comprises the steps of: immersing the metal substrate with the cluster-shaped hydrated alumina growing on the surface into the liquid organic silicon coating liquid, keeping for 1-10 min, and then taking the metal substrate with the cluster-shaped hydrated alumina growing on the surface out of the liquid organic silicon coating liquid at a speed of 5-10 mm/min;
the spraying comprises the following steps: spraying the liquid organic silicon coating liquid on the surface of the clustered hydrated alumina by using a spraying machine; the spraying machine is an air compressor, when spraying is conducted, the internal pressure of the air compressor is 0.1-0.6 MPa, the distance between a spray gun and the surface of the clustered hydrated alumina is 10-30 cm, and the spraying time is 1-10 s.
9. The method for preparing the composite coating according to any one of claims 1 to 5, wherein the heat treatment is performed at a temperature of 300 to 400 ℃ for 5 to 30 min.
10. A composite coating produced by the method of producing a composite coating according to any one of claims 1 to 9.
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