CN113880608A - A superhydrophobic composite ceramic coating - Google Patents
A superhydrophobic composite ceramic coating Download PDFInfo
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- CN113880608A CN113880608A CN202111384409.4A CN202111384409A CN113880608A CN 113880608 A CN113880608 A CN 113880608A CN 202111384409 A CN202111384409 A CN 202111384409A CN 113880608 A CN113880608 A CN 113880608A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
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Abstract
The invention discloses a super-hydrophobic composite ceramic coating, which comprises a component A, a component B and a component C, wherein the component A comprises phosphoric acid, phosphate, attapulgite, natural kaolin, metakaolin, siliceous powder and the balance of water; the component B comprises metal oxide, hydroxide, wollastonite and the balance of water; the component C comprises hydrophobic nano silicon dioxide, attapulgite, polysiloxane, neutral silicone glass cement and the balance of absolute ethyl alcohol. The invention can be used for forming a hydrophobic ceramic coating on metal, makes up for the defect of hydrophilic property of an inorganic ceramic coating, and forms a hydrophobic coating with a contact angle of more than 150 degrees and excellent performance outside the ceramic coating to isolate the erosion of the ceramic coating from the external environment.
Description
Technical Field
The invention relates to the field of ceramic coatings, in particular to a super-hydrophobic composite ceramic coating.
Background
Metals such as steel and iron are widely applied to various fields of national life, but the lower corrosion resistance of the metals can bring huge loss to the economy; for most ferrous materials, corrosion protection of coatings is one of the most direct and effective ways to prevent metal corrosion.
Ceramic coatings are the most new inorganic coatings, and are of great interest for their excellent corrosion protection against metals, their excellent weatherability, their resistance to ultraviolet light, their heat and their alkali resistance. Particularly, the ceramic coating can react with the metal matrix, so that the ceramic coating has stronger bonding force with the metal matrix.
However, compared with organic coatings, ceramic coatings have strong hydrophilicity and are easily corroded by external water vapor, especially in humid environments such as oceans and lakes. After the water content of the ceramic coating is increased, the adhesive force of the ceramic coating on the metal surface is greatly reduced, so that the ceramic coating falls off from the metal matrix, the protection of the ceramic coating on the metal matrix is greatly reduced, and the metal matrix is corroded.
Disclosure of Invention
The invention aims to provide a super-hydrophobic composite ceramic coating to solve the problem that the ceramic coating for metal in the prior art is high in hydrophilicity.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the super-hydrophobic composite ceramic coating comprises a component A, a component B and a component C, wherein the weight ratio of the component A to the component B is 0.1-1: 1, and the weight ratio of the component C to the sum of the weight of the component A and the weight of the component B is 0.1-0.5: 1.
The component A comprises the following raw material components in percentage by weight: 1-10% of phosphoric acid, 1-30% of phosphate, 1-10% of attapulgite, 1-10% of natural kaolin, 1-10% of metakaolin,
1-15% of siliceous powder and 15-60% of water.
The component B comprises the following raw material components in percentage by weight: 1-30% of metal oxide, 1-40% of hydroxide, 1-15% of wollastonite and 15-70% of water.
The component C comprises the following raw material components in percentage by weight: 1-15% of hydrophobic nano silicon dioxide, 1-10% of attapulgite, 1-30% of polysiloxane, 1-6% of neutral silicone glass cement and 40-85% of absolute ethyl alcohol
The three components in the super-hydrophobic composite ceramic coating are respectively prepared separately, wherein:
the preparation process of the component A comprises the following steps:
firstly, selecting raw material components of the component A according to weight percentage, then adding phosphoric acid into water, stirring, adding attapulgite, natural kaolin, metakaolin, siliceous powder and phosphate into the water, and then continuing stirring to obtain the component A;
the preparation process of the component B comprises the following steps:
firstly, selecting raw material components of the component B according to weight percentage, then sequentially adding metal oxide, hydroxide and wollastonite into water to prepare slurry, and then grinding the stirred slurry to obtain the component B;
the preparation process of the component C comprises the following steps:
firstly, selecting raw material components of the component C according to weight percentage, then adding hydrophobic nano silicon dioxide, attapulgite, polysiloxane and neutral silicone glass cement into absolute ethyl alcohol, and then stirring to obtain the component C.
The invention also discloses a method for forming the super-hydrophobic composite ceramic coating on the metal, which comprises the steps of firstly mixing the component A and the component B, coating the mixture on a metal target position to form the ceramic base coating, then coating the component C on the ceramic base coating after the ceramic base coating is naturally cured, heating the ceramic base coating for 22 to 26 hours at the temperature of between 100 and 150 ℃, and then cooling the ceramic base coating to room temperature, thus forming the super-hydrophobic composite ceramic coating on the metal target position.
The A, B, C components of the ceramic coating of the present invention are: the component A and the component B interact to form a ceramic coating on the metal surface, and the metal-based ceramic coating is a general name of a heat-resistant inorganic protective layer and/or a surface film coated on the metal surface; it can change the appearance, structure and properties of metal matrix, so changing the new properties of material. According to the invention, the component A and the component B are uniformly mixed according to a certain proportion, so that a layer of protective film with high-temperature-resistant metal corrosion prevention effect can be formed on a metal matrix; meanwhile, in order to overcome the hydrophilicity of the inorganic coating and prevent the erosion of external moisture to the ceramic coating, a super-hydrophobic coating which can not wet the surface is compounded on the outer layer of the ceramic coating; in the coating, the linear or slightly crosslinked reticular polymer compound based on long chain methylsiloxane for the coating formed by polysiloxane in the component C has good water-repellent and waterproof performance; the modified super-hydrophobic silica in the component C has some hydrophobic groups, so that water drops are prevented from spreading at an interface.
The invention can form a ceramic coating with excellent corrosion resistance and weather resistance on the surface of metal; the defect of hydrophilic property of the inorganic ceramic coating is overcome, a hydrophobic coating with a contact angle larger than 150 degrees and excellent performance is formed outside the ceramic layer, the erosion of the ceramic coating by the external environment is isolated, and the service life of the ceramic coating is prolonged; meanwhile, the outer coating has a certain self-cleaning function due to the hydrophobicity of the outer coating.
Detailed Description
The technical solution of the embodiment of the present invention will be further described with reference to the embodiment of the present invention; it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive labor based on the embodiments of the present invention, and the embodiments belong to the protection scope of the present invention.
Example 1:
the super-hydrophobic composite ceramic coating of embodiment 1 comprises a component a, a component B, and a component C, wherein the weight ratio of the component a to the component B is 0.5:1, and the weight ratio of the component C to the sum of the weight of the component a and the component B is 0.1: 1.
The component A comprises the following raw material components in percentage by weight: 3% of phosphoric acid, 30% of phosphate, 5% of attapulgite, 5% of natural kaolin, 2% of metakaolin, 2% of siliceous powder and 53% of water.
In the component A, the phosphate is one or more of potassium dihydrogen phosphate, sodium dihydrogen phosphate and lithium dihydrogen phosphate. The siliceous powder is any one or mixture of more of silicon dioxide, quartz powder and foam glass powder in any proportion.
The component B comprises the following raw material components in percentage by weight: 7% of metal oxide, 15% of hydroxide, 5% of wollastonite and 73% of water.
In the component B, the metal oxide is any one or mixture of more of magnesium oxide, aluminum oxide, ferric oxide and ferrous oxide in any proportion. The hydroxide is any one or mixture of more of magnesium hydroxide, aluminum hydroxide, potassium hydroxide, sodium hydroxide and calcium hydroxide in any proportion.
The component C comprises the following raw material components in percentage by weight: 1.2% of hydrophobic nano silicon dioxide, 1.3% of attapulgite, 10% of polysiloxane, 1.2% of neutral silicone glass cement and 86.3% of anhydrous ethanol in balance.
In the component C, the polysiloxane is any one or mixture of a plurality of polydimethylsiloxane, cyclomethicone, aminosiloxane, polymethylphenylsiloxane and polyether polysiloxane copolymer in any proportion.
The preparation method of the super-hydrophobic composite ceramic coating in the embodiment 1 is as follows:
preparation of a component A: firstly, slowly adding 3% of phosphoric acid into water, starting stirring, then continuously adding 5% of attapulgite, 5% of natural kaolin, 2% of metakaolin, 2% of siliceous powder and 30% of phosphate, and then continuously stirring for 1 hour to obtain the component A of the coating.
B, preparation of a component: firstly adding water, then sequentially adding 7% of metal oxide, 15% of hydroxide and 5% of wollastonite, stirring for 1 hour, then pouring the obtained slurry into a sand mill, and continuously grinding for 1 hour to obtain the component B.
The component C is prepared by adding 1.2% of hydrophobic nano silicon dioxide, 1.3% of attapulgite, 10% of polysiloxane and 1.2% of neutral silicone glass cement into absolute ethyl alcohol, and then fully stirring for 12 hours to obtain the component C.
The process of the method for forming the super-hydrophobic composite ceramic coating on the metal surface in the embodiment 1 is as follows:
firstly, mixing the component A and the component B in a ratio of 0.5:1, slowly stirring, quickly, uniformly and flatly coating the mixture on an oil-derusted metal piece to form a base coating, after the base coating is completely cured, spraying or coating the component C and the component (A + B) in a weight ratio of 0.1:1 on the prepared base coating, heating at 120 ℃ for 24 hours, and cooling to room temperature, thereby forming the super-hydrophobic composite ceramic coating on the surface of the metal piece.
Example 2:
in this embodiment 2, the super-hydrophobic composite ceramic coating includes a component a, a component B, and a component C, where a weight ratio of the component a to the component B is 0.4:1, and a ratio of a weight of the component C to a sum of the weight of the component a and the weight of the component B is 0.2: 1.
The component A comprises the following raw material components in percentage by weight: 5% of phosphoric acid, 28% of phosphate, 5% of attapulgite, 7% of natural kaolin, 2% of metakaolin, 2% of siliceous powder and 51% of water.
In the component A, the phosphate is one or more of potassium dihydrogen phosphate, sodium dihydrogen phosphate and lithium dihydrogen phosphate. The siliceous powder is any one or mixture of more of silicon dioxide, quartz powder and foam glass powder in any proportion.
The component B comprises the following raw material components in percentage by weight: 10% of metal oxide, 17% of hydroxide, 3% of wollastonite and 70% of water.
In the component B, the metal oxide is any one or mixture of more of magnesium oxide, aluminum oxide, ferric oxide and ferrous oxide in any proportion. The hydroxide is any one or mixture of more of magnesium hydroxide, aluminum hydroxide, potassium hydroxide, sodium hydroxide and calcium hydroxide in any proportion.
The component C comprises the following raw material components in percentage by weight: 1.2% of hydrophobic nano silicon dioxide, 1.3% of attapulgite, 7.8% of polysiloxane, 3% of neutral silicone glass cement and 86.7% of absolute ethyl alcohol.
In the component C, the polysiloxane is any one or mixture of a plurality of polydimethylsiloxane, cyclomethicone, aminosiloxane, polymethylphenylsiloxane and polyether polysiloxane copolymer in any proportion.
The preparation method of the super-hydrophobic composite ceramic coating in the embodiment 2 is as follows:
preparation of a component A: firstly, slowly adding 5% of phosphoric acid into water, starting stirring, then continuously adding 5% of attapulgite, 7% of natural kaolin, 2% of metakaolin, 2% of siliceous powder and 28% of phosphate, and then continuously stirring for 1 hour to obtain the component A of the coating.
B, preparation of a component: firstly adding water, then sequentially adding 10% of metal oxide, 17% of hydroxide and 3% of wollastonite, stirring for 1 hour, then pouring the obtained slurry into a sand mill, and continuously grinding for 1 hour to obtain the component B.
And the component C is prepared by adding 1.2% of hydrophobic nano silicon dioxide, 1.3% of attapulgite, 7.8% of polysiloxane and 3% of neutral silicone glass cement into absolute ethyl alcohol, and then fully stirring for 12 hours to obtain the component C.
In this example 2, the process of the method for forming the super-hydrophobic composite ceramic coating on the metal surface is as follows:
firstly, mixing the component A and the component B in a ratio of 0.4:1, slowly stirring, quickly, uniformly and flatly coating the mixture on an oil-derusted metal piece to form a base coating, after the base coating is completely cured, spraying or coating the component C and the component (A + B) in a weight ratio of 0.2:1 on the prepared base coating, heating at 120 ℃ for 24 hours, and cooling to room temperature, thereby forming the super-hydrophobic composite ceramic coating on the surface of the metal piece.
Example 3:
the super-hydrophobic composite ceramic coating of the embodiment 2 comprises a component a, a component B and a component C, wherein the weight ratio of the component a to the component B is 0.3:1, and the weight ratio of the component C to the sum of the weight of the component a and the component B is 0.1: 1.
The component A comprises the following raw material components in percentage by weight: 8% of phosphoric acid, 24% of phosphate, 3% of attapulgite, 7% of natural kaolin, 3% of metakaolin, 8% of siliceous powder and 47% of water.
In the component A, the phosphate is one or more of potassium dihydrogen phosphate, sodium dihydrogen phosphate and lithium dihydrogen phosphate. The siliceous powder is any one or mixture of more of silicon dioxide, quartz powder and foam glass powder in any proportion.
The component B comprises the following raw material components in percentage by weight: 6% of metal oxide, 14% of hydroxide, 6% of wollastonite and the balance of water, wherein the balance is 74%.
In the component B, the metal oxide is any one or mixture of more of magnesium oxide, aluminum oxide, ferric oxide and ferrous oxide in any proportion. The hydroxide is any one or mixture of more of magnesium hydroxide, aluminum hydroxide, potassium hydroxide, sodium hydroxide and calcium hydroxide in any proportion.
The component C comprises the following raw material components in percentage by weight: 1.2% of hydrophobic nano silicon dioxide, 1.3% of attapulgite, 7.8% of polysiloxane, 3% of neutral silicone glass cement and the balance of 86.7% of absolute ethyl alcohol.
In the component C, the polysiloxane is any one or mixture of a plurality of polydimethylsiloxane, cyclomethicone, aminosiloxane, polymethylphenylsiloxane and polyether polysiloxane copolymer in any proportion.
The preparation method of the super-hydrophobic composite ceramic coating in the embodiment 3 is as follows:
preparation of a component A: firstly, slowly adding 8% of phosphoric acid into water, starting stirring, then continuously adding 3% of attapulgite, 7% of natural kaolin, 3% of metakaolin, 8% of siliceous powder and 24% of phosphate, and then continuously stirring for 1 hour to obtain the component A of the coating.
B, preparation of a component: firstly adding water, then sequentially adding 6% of metal oxide, 14% of hydroxide and 6% of wollastonite, stirring for 1 hour, then pouring the obtained slurry into a sand mill, and continuously grinding for 1 hour to obtain the component B.
And the component C is prepared by adding 1.2% of hydrophobic nano silicon dioxide, 1.3% of attapulgite, 7.8% of polysiloxane and 3% of neutral silicone glass cement into absolute ethyl alcohol, and then fully stirring for 12 hours to obtain the component C.
The process of the method for forming the super-hydrophobic composite ceramic coating on the metal surface in the embodiment 1 is as follows:
firstly, mixing the component A and the component B in a ratio of 0.3:1, slowly stirring, quickly, uniformly and flatly coating the mixture on an oil-derusted metal piece to form a base coating, after the base coating is completely cured, spraying or coating the component C and the component (A + B) in a weight ratio of 0.1:1 on the prepared base coating, heating at 120 ℃ for 24 hours, and cooling to room temperature, thereby forming the super-hydrophobic composite ceramic coating on the surface of the metal piece.
The performance tests of the superhydrophobic ceramic coatings provided in embodiments 1-3 of the invention are shown in the following table:
example 1 | Example 2 | Example 3 | |
Hardness of pencil | 3H | 3H | 3H |
Contact angle of water and film | 150.1° | 150.3° | 150.1° |
Salt spray test | 1080HRS | 1080HRS | 1080HRS |
Adhesion force | 10.1MPa | 9.8MPa | 9.3MPa |
Recommended thickness (A + B component) | 0.5~0.7mm | 0.5~0.7mm | 0.5~0.7mm |
Recommended thickness (C component) | 0.1~0.3 | 0.1~0.3 | 0.1~0.3 |
The embodiments of the present invention are described only for the preferred embodiments of the present invention, and not for the limitation of the concept and scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the design concept of the present invention shall fall into the protection scope of the present invention, and the technical content of the present invention which is claimed is fully set forth in the claims.
Claims (8)
1. The super-hydrophobic composite ceramic coating is characterized by comprising a component A, a component B and a component C, wherein the weight ratio of the component A to the component B is 0.1-1: 1, and the weight ratio of the component C to the sum of the weight of the component A and the weight of the component B is 0.1-0.5: 1;
the component A comprises the following raw material components in percentage by weight:
1 to 10 percent of phosphoric acid,
1 to 30 percent of phosphate,
1 to 10 percent of attapulgite,
1 to 10 percent of natural kaolin,
1 to 10 percent of metakaolin,
1 to 15 percent of siliceous powder,
15-60% of water
The component B comprises the following raw material components in percentage by weight:
1 to 30 percent of metal oxide,
1 to 40 percent of hydroxide,
1 to 15 percent of wollastonite,
15-70% of water
The component C comprises the following raw material components in percentage by weight:
1 to 15 percent of hydrophobic nano silicon dioxide,
1 to 10 percent of attapulgite,
1 to 30 percent of polysiloxane,
1 to 6 percent of neutral silicone glass cement,
40% -85% of absolute ethyl alcohol.
2. The super-hydrophobic composite ceramic coating as claimed in claim 1, wherein the phosphate in the component A is one or more of potassium dihydrogen phosphate, sodium dihydrogen phosphate and lithium dihydrogen phosphate.
3. The super-hydrophobic composite ceramic coating according to claim 1, wherein the silica powder in the component A is any one or a mixture of silica, quartz powder and foam glass powder in any proportion.
4. The super-hydrophobic composite ceramic coating according to claim 1, wherein the metal oxide in the component B is any one or a mixture of magnesium oxide, aluminum oxide, ferric oxide and ferrous oxide in any proportion.
5. The super-hydrophobic composite ceramic coating according to claim 1, wherein the hydroxide in the component B is any one or a mixture of several of magnesium hydroxide, aluminum hydroxide, potassium hydroxide, sodium hydroxide and calcium hydroxide in any proportion.
6. The super-hydrophobic composite ceramic coating as claimed in claim 1, wherein the polysiloxane in the component C is any one or more of polydimethylsiloxane, cyclomethicone, aminosiloxane, polymethylphenylsiloxane and polyether polysiloxane copolymer.
7. The preparation method of the superhydrophobic composite ceramic coating of claim 1, wherein the preparation process of the component A comprises the following steps:
firstly, selecting raw material components of the component A according to weight percentage, then adding phosphoric acid into water, stirring, adding attapulgite, natural kaolin, metakaolin, siliceous powder and phosphate into the water, and then continuing stirring to obtain the component A;
the preparation process of the component B comprises the following steps:
firstly, selecting raw material components of the component B according to weight percentage, then sequentially adding metal oxide, hydroxide and wollastonite into water, stirring to form slurry, and then grinding the stirred slurry to obtain the component B;
the preparation process of the component C comprises the following steps:
firstly, selecting raw material components of the component C according to weight percentage, then adding hydrophobic nano silicon dioxide, attapulgite, polysiloxane and neutral silicone glass cement into absolute ethyl alcohol, and then stirring to obtain the component C.
8. A method of forming the superhydrophobic composite ceramic coating of claim 1 on a metal, comprising the steps of:
(1) mixing the component A and the component B according to the weight ratio, stirring to form a mixture, then coating the mixture on a metal target position to form a base coating, and waiting for the natural curing of the base coating;
(2) and (2) after the base coating formed in the step (1) is cured, selecting a component C in a corresponding weight ratio, coating the component C on the base coating, heating at the temperature of 100-150 ℃ for 22-26 hours, and cooling to room temperature to form the super-hydrophobic composite ceramic coating at the metal target position.
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CN111116165A (en) * | 2019-11-29 | 2020-05-08 | 浙江大学 | Double-layer modified inorganic anticorrosive coating and preparation method thereof |
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CN102781871A (en) * | 2009-12-11 | 2012-11-14 | 18纬度有限公司 | Inorganic phosphate compositions and methods |
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