CN113355658B - Metal matrix surface anti-corrosion ceramic coating and preparation method thereof - Google Patents
Metal matrix surface anti-corrosion ceramic coating and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of anticorrosive coatings, and provides a preparation method of an anticorrosive ceramic coating on the surface of a metal substrate, which comprises the following steps: (1) preparing a gel coating: polishing the surface of a metal substrate to be smooth, coating aluminum-containing sol to form a sol coating, and drying to obtain a gel coating, wherein the thickness of the gel coating is 5-150 mu m; (2) first heat treatment: carrying out first heat treatment on the gel coating prepared in the step (1) in an inert atmosphere, and then cooling the gel coating to room temperature along with a furnace, wherein the treatment temperature is 500-600 ℃, and the treatment time is 60-360 min; (3) and (3) second heat treatment: and (3) carrying out secondary heat treatment on the coating obtained in the step (2) in an air atmosphere, and then cooling the coating to room temperature along with a furnace to obtain a final product, wherein the treatment temperature is 900-1200 ℃, and the treatment time is 30-240 min. The method saves energy consumption, is easy to realize, does not damage a substrate, and can prepare the anticorrosive coating with the transition layer. The invention also provides the anticorrosive ceramic coating prepared by the method.
Description
Technical Field
The invention relates to the field of anticorrosive coatings, in particular to an anticorrosive ceramic coating suitable for the surface of a supercritical water oxidation reaction kettle substrate and a preparation method thereof.
Background
Supercritical Water Oxidation (SCWO) is a treatment technology for treating organic waste by using Supercritical Water as a corrosion medium and oxygen or air as an oxidant. Compared with the traditional treatment technology, the supercritical water oxidation technology has the advantages of high treatment efficiency, economy, environmental protection, no secondary pollution and the like. The candidate materials of the equipment reactor in the supercritical water environment are mainly iron-based alloy, nickel-based alloy, titanium-based alloy and the like. However, in a supercritical water environment, the equipment reactor is in a strong oxidation and strong corrosion working environment caused by high temperature, high pressure and high solubility, and the alloy material is easy to oxidize and corrode, so that the service life of the reactor is rapidly reduced. Therefore, it is important to solve the corrosion problem of the reactor material in the supercritical water oxidation process.
Compared with metal-based materials, most ceramic materials have better chemical stability, so that the preparation of a proper ceramic coating on the surface of a metal matrix candidate material of a supercritical water reactor is an effective scheme for further improving the corrosion resistance of the supercritical water reactor, and more corrosion-resistant ceramic coating materials are applied to be Al 2 O 3 、ZrO 2 、 TiO 2 And the like, and the common coating preparation means comprises plasma spraying, electroplating, thermal spraying, powder embedding and the like.
However, the oxide ceramic coating and the metal substrate mostly have the problem of thermal mismatch, and the coating is easy to peel off during the cold and hot circulation process due to the difference of the thermal expansion coefficients of the oxide ceramic coating and the metal substrate. At present, the mainstream method for solving the problem is to form a gradient transition layer between the substrate and the coating, such as FeAl/Al 2 O 3 Or NiAl/Al 2 O 3 The FeAl or NiAl alloy transition layer in the coating system can effectively slow down Al 2 O 3 The thermal mismatch between the coating and the substrate improves the service life of the ceramic coating.
In the prior art, methods for preparing the transition layer are basically carried out by methods such as powder embedding, plasma spraying, thermal spraying and the like, and the methods generally need to be carried out at high temperature, so that the problems of high energy consumption and high cost are solved, and the service life of a matrix is influenced due to damage of a matrix material caused by overhigh treatment temperature.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of an anticorrosive ceramic coating on the surface of a metal substrate, which has the advantages of simple steps, energy consumption saving, easy realization, no damage to the substrate and capability of preparing an anticorrosive coating with a transition layer.
The second purpose of the invention is to provide an anticorrosive ceramic coating on the surface of a metal substrate, which has good anticorrosive effect.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of an anticorrosive ceramic coating on the surface of a metal substrate is characterized by comprising the following steps:
(1) preparing a gel coating: polishing the surface of a metal substrate to be smooth, coating aluminum-containing sol to form a sol coating, and drying to obtain a gel coating, wherein the thickness of the gel coating is 5-150 mu m;
(2) first heat treatment: carrying out first heat treatment on the gel coating prepared in the step (1) in an inert atmosphere, and then cooling the gel coating to room temperature along with a furnace, wherein the treatment temperature is 500-600 ℃, and the treatment time is 60-360 min;
(3) and (3) second heat treatment: and (3) carrying out secondary heat treatment on the coating obtained in the step (2) in an air atmosphere, and then cooling the coating to room temperature along with a furnace to obtain a final product, wherein the treatment temperature is 900-1200 ℃, and the treatment time is 30-240 min.
After the aluminum-containing coating is coated on the surface of a metal matrix, the first heat treatment is carried out in an inert atmosphere, and a matrix-aluminum layer can be formed at a lower treatment temperature; then, the second heat treatment is carried out in the air, the treatment temperature is higher, the matrix-aluminum layer is oxidized from the surface, and the aluminum oxide layer is formed on the surface. The invention strictly controls the processing time of the second heat treatment, thereby strictly controlling the thickness of the alumina layer, so that a 'matrix-aluminum' transition layer between the matrix and the surface alumina layer can be reserved, and finally a 'matrix/matrix-aluminum/alumina' coating structure with the transition layer and the surface anti-corrosion ceramic layer is formed.
The first heat treatment temperature is low, the substrate is not damaged, the energy consumption is greatly reduced, the coating structure containing the transition layer and the ceramic anticorrosive layer can be prepared by one-time sol coating, the preparation steps are simple, and the operation is convenient and easy.
The invention also provides the metal matrix surface anticorrosive coating prepared by the preparation method, which has a good anticorrosive effect and can realize effective anticorrosion under high-temperature, high-pressure, strong-alkali/strong-acid environments.
The invention has the beneficial effects that:
1. the preparation method has simple steps, saves energy consumption, is convenient for large-area treatment, has high treatment speed, is easy to realize, does not damage a substrate, and can prepare the anticorrosive coating with the transition layer;
2. the metal matrix surface anticorrosive coating can realize effective corrosion prevention in high-temperature, high-pressure and strong alkali/strong acid environments.
Drawings
FIG. 1 is a scanning electron micrograph of a longitudinal section of sample A prepared in example 1;
FIG. 2 is a scanning electron micrograph of the back surface of sample A prepared in example 1 before testing (FIG. 2a) and after testing (FIG. 2 b);
fig. 3 is XRD patterns before and after the test of sample a prepared in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the present invention is further described with reference to specific embodiments below.
The invention provides a preparation method of an anticorrosive ceramic coating on the surface of a metal matrix, which comprises the following steps:
(1) preparing a gel coating: polishing the surface of a metal substrate to be smooth, coating aluminum-containing sol to form a sol coating, and drying to obtain a gel coating, wherein the thickness of the gel coating is 5-150 mu m;
(2) first heat treatment: carrying out first heat treatment on the gel coating prepared in the step (1) in an inert atmosphere, and then cooling the gel coating to room temperature along with a furnace, wherein the treatment temperature is 500-600 ℃, and the treatment time is 60-360 min;
(3) and (3) second heat treatment: and (3) carrying out secondary heat treatment on the coating obtained in the step (2) in an air atmosphere, and then cooling the coating to room temperature along with a furnace to obtain a final product, wherein the treatment temperature is 900-1200 ℃, and the treatment time is 30-240 min.
After the aluminum-containing coating is coated on the surface of a metal matrix, the first heat treatment is carried out in an inert atmosphere (the inert atmosphere can be a nitrogen atmosphere, a rare metal atmosphere and the like), and a matrix-aluminum layer can be formed at a lower treatment temperature; then, the second heat treatment is carried out in the air, the treatment temperature is higher, the matrix-aluminum layer is oxidized from the surface, and the aluminum oxide layer is formed on the surface. The invention strictly controls the processing time of the second heat treatment, thereby strictly controlling the thickness of the alumina layer, keeping the matrix-alumina layer transition layer between the matrix and the surface alumina layer, and finally forming the 'matrix/matrix-alumina/alumina' coating structure with the transition layer and the surface anticorrosive ceramic layer.
In the prior art, the alumina layer is prepared by heat treatment in air by adopting a sol method, and the transition layer is prepared by adopting a powder embedding method, a plasma spraying method or a thermal spraying method, wherein the temperatures of the methods acting on the surface of the matrix exceed 800 ℃, so that the method not only needs higher energy consumption and causes cost increase, but also easily causes matrix damage at higher temperature. The invention overcomes the inherent thinking of technicians in the field, creatively adopts aluminum-containing gel to process and prepare the matrix-aluminum layer in inert atmosphere through deep analysis of a sol-gel method, and then further processes the aluminum-containing gel to obtain the surface aluminum oxide layer, thereby avoiding the problems of damage to the matrix and high energy consumption caused by higher processing temperature in the prior art; in addition, the sol method is adopted, so that the surface of the matrix can be conveniently treated in a large area, and the treatment speed is high; according to the invention, the anticorrosive ceramic layer containing the transition layer can be formed only by coating the sol once, the transition layer is not required to be prepared by a powder embedding method, and then the ceramic layer is prepared by a sol-gel method, so that the preparation process is simple; the invention only needs to be processed in a high-temperature furnace, has low requirement on equipment and small equipment investment.
The final structure of the product of the invention, the thickness of the gel coat, is closely related to the time of the first and second heat treatments. The first heat treatment is required to completely convert the gel coating into a matrix-aluminum alloy layer; because the oxidation process is started from the surface, the second heat treatment needs to ensure that the surface can be oxidized to form an alumina layer with reasonable thickness, if the treatment time is too long, the surface is overoxidized, and the transition layer is completely converted into the alumina layer, and if the treatment time is too short, the thickness of the alumina layer is difficult to ensure, thereby affecting the anticorrosion effect.
Based on the above consideration, the present invention is specifically designed as follows: when the thickness of the gel coating in the step (1) is 5-30 mu m, the treatment time in the step (2) is 60-120 min, and the treatment time in the step (3) is 30-80 min; when the thickness of the gel coating in the step (1) is 30-80 mu m, the treatment time in the step (2) is 120-210 min, and the treatment time in the step (3) is 80-150 min; when the thickness of the gel coating in the step (1) is 80-150 mu m, the treatment time in the step (2) is 210-360 min, and the treatment time in the step (3) is 150-240 min.
By controlling the thickness of the coating and the time of two heat treatments, the required matrix/matrix-aluminum/aluminum oxide structure is ensured to be formed, and the optimal anti-corrosion effect is achieved.
Further preferably, the thickness of the gel coat, the time of the first heat treatment and the time of the second heat treatment may be selected as follows: the thickness of the gel coating in the step (1) is 15-25 mu m, the treatment time in the step (2) is 60-90 min, and the treatment time in the step (3) is 40-60 min; the thickness of the gel coating in the step (1) is 40-60 mu m, the treatment time in the step (2) is 150-180 min, and the treatment time in the step (3) is 100-130 min; the thickness of the gel coating in the step (1) is 130-140 mu m, the treatment time in the step (2) is 300-330 min, and the treatment time in the step (3) is 200-230 min.
In the invention, the heating rate in the step (2) is 4-6 ℃/min; the heating rate in the step (3) is 9-12 ℃/min. If the temperature rise speed of the first heat treatment is too high, the gel film is shrunk and cracked; if the temperature rise rate of the second heat treatment is too high, stress is generated in the film, and the performance of the final product is affected.
The specific steps of the step (1) in the invention are as follows: polishing the surface of a metal matrix to be smooth, dripping aluminum-containing sol on the surface of the metal matrix, spin-coating for 5-8 s at 700-750 r/min by using a spin coater, then spin-coating for 20-25 s at 1500-1600 r/min, and drying the obtained sample at 80-85 ℃ for 2-5 min; the above operations were repeated to obtain coatings of different thicknesses.
The metal matrix of the present invention is selected from a nickel alloy matrix, an iron alloy matrix, or a titanium alloy matrix. A titanium alloy matrix is preferred.
The aluminum-containing sol is prepared from aluminum isopropoxide; the specific preparation method of the aluminum-containing sol comprises the following steps: heating deionized water and aluminum isopropoxide in a water bath at 80-90 ℃ and magnetically stirring for 20-40 min, adding nitric acid, continuing to heat in the water bath at 80-90 ℃ and magnetically stirring for 8-12 h, continuing to heat in the water bath at 85-95 ℃ for 22-26 h, and filtering the obtained product to obtain transparent aluminum-containing sol; aluminum isopropoxide, deionized water and nitric acid meet the following requirements according to the molar ratio: 1: 90-100: 0.2 to 0.5, preferably 1: 90: 0.3.
the invention also provides the metal matrix surface anticorrosive ceramic coating prepared by the preparation method.
Example 1
(1) Preparing sol:
heating deionized water and aluminum isopropoxide in a 85 ℃ water bath, magnetically stirring for 30min, adding nitric acid, continuing to heat the water bath at 85 ℃ and magnetically stirring for 10h, continuing to stand in the water bath at 90 ℃ for 24h, filtering the obtained product to obtain transparent sol, wherein the molar ratio of the aluminum isopropoxide to the deionized water to the nitric acid is 1: 90: 0.3.
(2) preparing a gel coating:
and preparing a gel coating on the surface of the nickel-based alloy. Firstly, polishing the surface of a nickel-based alloy by using sand paper to be smooth, dripping sol on the surface of the nickel-based alloy, and spin-coating for 6s at 700r/min by using a spin coater, and then spin-coating for 20s at 1500 r/min; the resulting sample was dried at 80 ℃ for about 3min and the above procedure was repeated to give a gel coat thickness of 20 μm.
(3) First heat treatment:
and (3) placing the coating sample obtained in the step (2) in a tube furnace, heating to 550 ℃ at the speed of 5 ℃/min, preserving heat for 80min, cooling to room temperature along with the furnace, and introducing nitrogen in the whole process to obtain the nickel matrix/nickel-aluminum layer.
(4) And (3) second heat treatment:
and (4) placing the sample obtained in the step (3) in a tube furnace, heating to 1100 ℃ at a speed of 10 ℃/min in the air atmosphere, preserving heat for 50min, and then cooling to room temperature along with the furnace to obtain a final sample with a structure of nickel matrix/nickel-aluminum/aluminum oxide layer, wherein the final sample is marked as a sample A.
Example 2
(1) Preparing sol:
heating deionized water and aluminum isopropoxide in a 85 ℃ water bath, magnetically stirring for 30min, adding nitric acid, continuing to heat the water bath at 85 ℃ and magnetically stirring for 10h, continuing to heat the water bath at 90 ℃ for 24h, filtering the obtained product to obtain transparent sol, wherein the molar ratio of the aluminum isopropoxide to the deionized water to the nitric acid is 1: 90: 0.3.
(2) Preparing a gel coating:
and preparing a gel coating on the surface of the nickel-based alloy. Firstly, polishing the surface of a nickel-based alloy by using sand paper to be smooth, dripping sol on the surface of the nickel-based alloy, spin-coating for 6s at 700r/min by using a spin coater, and then spin-coating for 20s at 1500 r/min; the resulting sample was dried at 80 ℃ for about 3min and the above procedure was repeated to give a gel coat thickness of 50 μm.
(3) First heat treatment:
and (3) placing the coating sample obtained in the step (2) in a tube furnace, heating to 550 ℃ at the speed of 5 ℃/min, keeping the temperature for 165min, cooling to room temperature along with the furnace, and introducing nitrogen in the whole process to obtain the nickel matrix/nickel-aluminum layer.
(4) And (3) second heat treatment:
and (4) placing the sample obtained in the step (3) in a tube furnace, heating to 950 ℃ at a speed of 10 ℃/min in an air atmosphere, preserving heat for 130min, and then cooling to room temperature along with the furnace to obtain a final sample with a structure of nickel matrix/nickel-aluminum/aluminum oxide layer, wherein the final sample is marked as a sample B.
Example 3
(1) Preparing sol:
heating deionized water and aluminum isopropoxide in a 85 ℃ water bath, magnetically stirring for 30min, adding nitric acid, continuing to heat the water bath at 85 ℃ and magnetically stirring for 10h, continuing to heat the water bath at 90 ℃ for 24h, filtering the obtained product to obtain transparent sol, wherein the molar ratio of the aluminum isopropoxide to the deionized water to the nitric acid is 1: 90: 0.3.
(2) Preparing a gel coating:
and preparing a gel coating on the surface of the nickel-based alloy. Firstly, polishing the surface of a nickel-based alloy by using sand paper to be smooth, dripping sol on the surface of the nickel-based alloy, spin-coating for 6s at 700r/min by using a spin coater, and then spin-coating for 20s at 1500 r/min; the resulting sample was dried at 80 ℃ for about 3min and the above procedure was repeated to give a gel coat thickness of 135 μm.
(3) First heat treatment:
and (3) placing the coating sample obtained in the step (2) in a tube furnace, heating to 550 ℃ at the speed of 5 ℃/min, preserving heat for 310min, cooling to room temperature along with the furnace, and introducing nitrogen in the whole process to obtain the nickel matrix/nickel-aluminum layer.
(4) And (3) second heat treatment:
and (4) placing the sample obtained in the step (3) in a tube furnace, heating to 1000 ℃ at a speed of 10 ℃/min in the air atmosphere, preserving heat for 220min, and then cooling to room temperature along with the furnace to obtain a final sample with a structure of nickel matrix/nickel-aluminum/aluminum oxide layer, wherein the final sample is marked as a sample C.
Example 4
(1) Preparing sol:
heating deionized water and aluminum isopropoxide in a 85 ℃ water bath, magnetically stirring for 30min, adding nitric acid, continuing to heat the water bath at 85 ℃ and magnetically stirring for 10h, continuing to heat the water bath at 90 ℃ for 24h, filtering the obtained product to obtain transparent sol, wherein the molar ratio of the aluminum isopropoxide to the deionized water to the nitric acid is 1: 90: 0.3.
(2) Preparing a gel coating:
and preparing a gel coating on the surface of the nickel-based alloy. Firstly, polishing the surface of a nickel-based alloy by using sand paper to be smooth, dripping sol on the surface of the nickel-based alloy, spin-coating for 6s at 700r/min by using a spin coater, and then spin-coating for 20s at 1500 r/min; the resulting sample was dried at 80 ℃ for about 3min and the above procedure was repeated so that the thickness of the gel coat was 5 μm.
(3) First heat treatment:
and (3) placing the coating sample obtained in the step (2) in a tube furnace, heating to 500 ℃ at a speed of 4 ℃/min, preserving heat for 60min, cooling to room temperature along with the furnace, and introducing nitrogen in the whole process to obtain the nickel matrix/nickel-aluminum layer.
(4) And (3) second heat treatment:
and (4) placing the sample obtained in the step (3) in a tube furnace, heating to 900 ℃ at the speed of 9 ℃/min in the air atmosphere, preserving heat for 30min, and then cooling to room temperature along with the furnace to obtain a final sample with a structure of nickel matrix/nickel-aluminum/aluminum oxide layer, and marking as a sample D.
Example 5
(1) Preparing sol:
heating deionized water and aluminum isopropoxide in a 85 ℃ water bath, magnetically stirring for 30min, adding nitric acid, continuing to heat the water bath at 85 ℃ and magnetically stirring for 10h, continuing to heat the water bath at 90 ℃ for 24h, filtering the obtained product to obtain transparent sol, wherein the molar ratio of the aluminum isopropoxide to the deionized water to the nitric acid is 1: 90: 0.3.
(2) Preparing a gel coating:
and preparing a gel coating on the surface of the nickel-based alloy. Firstly, polishing the surface of a nickel-based alloy by using sand paper to be smooth, dripping sol on the surface of the nickel-based alloy, spin-coating for 6s at 700r/min by using a spin coater, and then spin-coating for 20s at 1500 r/min; the resulting sample was dried at 80 ℃ for about 3min and the above procedure was repeated to give a gel coat thickness of 150 μm.
(3) First heat treatment:
and (3) placing the coating sample obtained in the step (2) in a tube furnace, heating to 600 ℃ at the speed of 6 ℃/min, preserving heat for 360min, cooling to room temperature along with the furnace, and introducing nitrogen in the whole process to obtain the nickel matrix/nickel-aluminum layer.
(4) And (3) second heat treatment:
and (4) placing the sample obtained in the step (3) in a tube furnace, heating to 1200 ℃ at the speed of 12 ℃/min in the air atmosphere, preserving the heat for 240min, and then cooling to room temperature along with the furnace to obtain a final sample with a structure of nickel matrix/nickel-aluminum/aluminum oxide layer, and marking as a sample E.
Experimental example 1
The longitudinal section of sample a prepared in example 1 was subjected to scanning electron microscope test, and the test results are shown in fig. 1.
As can be seen from fig. 1, the longitudinal section of sample a is sequentially divided into three different structural layers, namely, a nickel-based layer/a nickel-aluminum layer/an aluminum oxide layer, from bottom to top. The preparation method can be used for preparing the anticorrosive ceramic coating with the structure of nickel base layer/nickel-aluminum layer/aluminum oxide layer.
Experimental example 2
Supercritical corrosion test
A supercritical corrosion test was carried out using sample A prepared in example 1 under test conditions of 500 ℃ at 25MPa for 72 hours. And (3) putting the sample into a supercritical reaction device, heating to a test temperature, and carrying out heat preservation and pressure maintaining for experimental treatment.
(1) And (b) performing scanning electron microscope test on the sample surface before and after the test, wherein the test result is shown in the attached drawing 2, wherein (a) in the attached drawing 2 is a surface scanning electron microscope image of the sample before the test, and (b) in the attached drawing 2 is a surface scanning electron microscope image of the sample after the test.
As can be seen from the attached figure 2, the tested sample has compact surface, no open pore, no crack, no shedding and other phenomena, and the surface coating is not corroded under the test condition, so that the corrosion-resistant effect is good.
(2) XRD tests were performed on the coating samples before and after the test, and the test results are shown in FIG. 2.
As can be seen from fig. 3, the XRD phase of the coating sample did not change substantially before and after the test, indicating that the coating remained stable under the test conditions.
In conclusion, the method provided by the invention has the advantages of simple steps, energy consumption saving, convenience for large-area treatment, high treatment speed, easiness in realization and no damage to the substrate, and the metal substrate anticorrosive coating prepared by the method provided by the invention has a good anticorrosive effect and can be kept stable for a long time under the corrosion and oxidation conditions of the supercritical condition.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of an anticorrosive ceramic coating on the surface of a metal substrate is characterized by comprising the following steps:
(1) preparing a gel coating: polishing the surface of a metal substrate to be smooth, coating aluminum-containing sol to form a sol coating, and drying to obtain a gel coating, wherein the thickness of the gel coating is 5-150 mu m;
(2) first heat treatment: carrying out first heat treatment on the gel coating prepared in the step (1) in an inert atmosphere, and then cooling the gel coating to room temperature along with a furnace to prepare a matrix-aluminum layer, wherein the treatment temperature is 500-600 ℃, and the treatment time is 60-360 min;
(3) and (3) second heat treatment: carrying out secondary heat treatment on the coating obtained in the step (2) in an air atmosphere, and then cooling the coating to room temperature along with a furnace to obtain a final product, wherein the treatment temperature is 900-1200 ℃, and the treatment time is 30-240 min;
when the thickness of the gel coating in the step (1) is 5-30 micrometers, the treatment time in the step (2) is 60-120 min, and the treatment time in the step (3) is 30-80 min;
when the thickness of the gel coating in the step (1) is 30-80 μm, the treatment time in the step (2) is 120-210 min, and the treatment time in the step (3) is 80-150 min;
when the thickness of the gel coating in the step (1) is 80-150 mu m, the treatment time in the step (2) is 210-360 min, and the treatment time in the step (3) is 150-240 min.
2. The method for preparing the anticorrosive ceramic coating on the surface of the metal substrate according to claim 1, wherein the thickness of the gel coating in the step (1) is 15-25 μm, the treatment time in the step (2) is 60-90 min, and the treatment time in the step (3) is 40-60 min.
3. The method for preparing the anticorrosive ceramic coating on the surface of the metal substrate according to claim 1, wherein the thickness of the gel coating in the step (1) is 40-60 μm, the treatment time in the step (2) is 150-180 min, and the treatment time in the step (3) is 100-130 min.
4. The method for preparing the anti-corrosion ceramic coating on the surface of the metal substrate according to claim 1, wherein the thickness of the gel coating in the step (1) is 130-140 μm, the treatment time in the step (2) is 300-330 min, and the treatment time in the step (3) is 200-230 min.
5. The preparation method of the metal substrate surface anti-corrosion ceramic coating according to claim 1, wherein the temperature rise rate in the step (2) is 4-6 ℃/min; and (4) the heating rate in the step (3) is 9-12 ℃/min.
6. The preparation method of the anti-corrosion ceramic coating on the surface of the metal substrate according to claim 1, wherein the step (1) comprises the following specific steps:
polishing the surface of a metal matrix to be smooth, dripping aluminum-containing sol on the surface of the metal matrix, spin-coating for 5-8 s at 700-750 r/min by using a spin coater, then spin-coating for 20-25 s at 1500-1600 r/min, and drying the obtained sample at 80-85 ℃ for 2-5 min; the above operations were repeated to obtain coatings of different thicknesses.
7. The method for preparing the anti-corrosion ceramic coating on the surface of the metal substrate according to any one of claims 1 to 6, wherein the metal substrate is selected from a nickel alloy substrate, an iron alloy substrate or a titanium alloy substrate.
8. The method for preparing the anti-corrosion ceramic coating on the surface of the metal matrix according to claim 7, wherein the aluminum-containing sol is prepared from aluminum isopropoxide; the specific preparation method of the aluminum-containing sol comprises the following steps:
heating deionized water and aluminum isopropoxide in a water bath at 80-90 ℃ and magnetically stirring for 20-40 min, adding nitric acid, continuing to heat the water bath at 80-90 ℃ and magnetically stirring for 8-12 h, continuing to stand in the water bath at 85-95 ℃ for 22-26 h, and filtering the obtained product to obtain transparent aluminum-containing sol;
the molar ratio of the aluminum isopropoxide to the deionized water to the nitric acid satisfies the following conditions: 1: 90-100: 0.2 to 0.5.
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