CN114085099B - Surface hydrophobic ceramic and processing method thereof - Google Patents
Surface hydrophobic ceramic and processing method thereof Download PDFInfo
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- CN114085099B CN114085099B CN202111446124.9A CN202111446124A CN114085099B CN 114085099 B CN114085099 B CN 114085099B CN 202111446124 A CN202111446124 A CN 202111446124A CN 114085099 B CN114085099 B CN 114085099B
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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
- C04B41/91—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics involving the removal of part of the materials of the treated articles, e.g. etching
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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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- 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
- C04B41/53—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone involving the removal of at least part of the materials of the treated article, e.g. etching, drying of hardened concrete
- C04B41/5338—Etching
- C04B41/5353—Wet etching, e.g. with etchants dissolved in organic solvents
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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
Abstract
The invention belongs to the technical field of ceramic surface treatment, and particularly discloses a surface hydrophobic ceramic and a treatment method thereof. The surface hydrophobic ceramic comprises a ceramic substrate and a hydrophobic layer, wherein the inner surface of the ceramic substrate is provided with a first micropore and a second micropore, and the hydrophobic layer covers the outer surface of the ceramic substrate; the first micropores are filled with silane coupling agent, the second micropores contain filler, and the filler and the hydrophobic layer are all hydrophobic materials. The processing method adopts an etching method to construct a micropore structure on the surface of a ceramic matrix, and comprises the following steps: etching the surface of the ceramic substrate by using an etchant for one time to form first micropores; coating a silane coupling agent on the surface of the ceramic substrate; polishing and grinding the surface of the ceramic substrate, and then performing secondary etching by using an etching agent to form second micropores; the hydrophobic material is coated on the surface of the ceramic matrix, so that the hydrophobic property of the ceramic surface is improved, the contact angle of the ceramic surface is 118.7-123.5 degrees, and the adhesion property of the hydrophobic material and the ceramic matrix is good.
Description
Technical Field
The invention belongs to the technical field of ceramic surface treatment, and particularly relates to surface hydrophobic ceramic and a treatment method thereof.
Background
With the continuous improvement of living standard and sanitary condition of people, people spend a lot of time on cleaning stains on the surfaces of building decoration materials such as home and office environments, and simultaneously waste a lot of water resources.
The building ceramic tile is a building material widely adopted in home and office environments, and a certain hydrophobic property is given to the surface of the ceramic tile through a surface treatment technology, so that the attachment of stains on the surface of the ceramic tile can be effectively reduced, and in addition, the ceramic tile with the stains attached is easier to clean through a simple wiping means, so that the cleaning time and the resource consumption are greatly reduced.
The surface of the ceramic product has certain roughness, a certain number of micropores are formed in the surface of the ceramic product, the flatness is lower than that of glass and metal materials, and the adhesion of hydrophobic materials is not facilitated, and the surfaces of materials such as glass, metal and the like are relatively more flat, so that after surface treatment, some hydrophobic functional agents can reach contact angles of more than 140 degrees on the surface of the glass, but the hydrophobic functional agents are difficult to apply to the surface of the ceramic, or the hydrophobic effect after the hydrophobic functional agents are applied is far worse than that on the surface of the glass. From the research perspective, at present, a method for constructing a hydrophobic structure on the surface of functional ceramics or structural ceramics by a Physical Vapor Deposition (PVD) mode exists, and the contact angle can reach 150 degrees at most, but the method has no practical application prospect in the building ceramic industry.
Therefore, a surface treatment method which can be adapted to the production process of architectural ceramics, has simple process and can improve the hydrophobic property of the ceramic surface is needed to be found.
Disclosure of Invention
The invention provides a surface hydrophobic ceramic and a processing method thereof, which are used for solving one or more technical problems in the prior art and providing at least one beneficial selection or creation condition.
In order to overcome the technical problems, the invention provides a ceramic with a hydrophobic surface in a first technical scheme.
The surface hydrophobic ceramic comprises a ceramic substrate and a hydrophobic layer, wherein the inner surface of the ceramic substrate is provided with a first micropore and a second micropore, and the hydrophobic layer covers the outer surface of the ceramic substrate; the first micropores are filled with silane coupling agents, the second micropores contain fillers, and the fillers and the hydrophobic layer are both hydrophobic materials.
According to the invention, a first micropore and a second micropore are formed on the surface of a ceramic substrate, a silane coupling agent is filled in the first micropore, a layer of polymer resin film is formed by utilizing the interface chemical reaction of the silane coupling agent and the surface of the ceramic substrate, and the silane coupling agent filled in the first micropore forms individual anchoring points; meanwhile, the second micropores contain hydrophobic materials, and the hydrophobic materials and the anchoring points formed by the silane coupling agent act together to improve the spreading and the cohesiveness of the hydrophobic layer on the surface of the ceramic matrix, so that the adhesive force of the hydrophobic layer and the ceramic matrix is improved, and the hydrophobic performance of the surface of the ceramic is improved.
As a further improvement of the scheme, the silane coupling agent is selected from gamma-aminopropyltriethoxysilane or gamma-methacryloxypropyltrimethoxysilane, and the two silane coupling agents can perform interfacial reaction with the ceramic matrix to form a polymer resin film which can be well adhered to the surface of the ceramic matrix.
The hydrophobic material is further improved to comprise nano organic silicon resin, the nano organic silicon resin has lower surface free energy and is difficult to fully spread on the surface of inorganic ceramic, and if the nano organic silicon resin is directly coated on the surface of a ceramic matrix, a good hydrophobic effect cannot be achieved; according to the invention, the micropore structure is constructed on the surface of the ceramic matrix, and the silane coupling agent and the hydrophobic material are filled in the micropores, so that the adhesion of the nano organic silicon resin on the ceramic matrix is improved, and the hydrophobic property of the nano organic silicon resin is fully exerted.
Preferably, the thickness of the hydrophobic layer is 5-25 μm.
Further, the ceramic matrix can be glazed ceramic or unglazed ceramic.
The second technical scheme of the invention is to provide a method for processing surface hydrophobic ceramics.
Specifically, the method for processing the surface hydrophobic ceramic adopts an etching method to construct a microporous structure on the surface of a ceramic matrix and comprises the following steps:
(1) Etching the surface of the ceramic substrate by using an etchant for one time to form first micropores;
(2) Coating a silane coupling agent on the surface of the ceramic substrate;
(3) Polishing and grinding the surface of the ceramic substrate, and then carrying out secondary etching by using an etching agent to form second micropores;
(4) And coating a hydrophobic material on the surface of the ceramic substrate to obtain the surface hydrophobic ceramic.
The invention constructs micropores on the surface of a ceramic matrix by a process of combining secondary etching, wherein: etching for the first time to form first micropores on the surface of the ceramic matrix, coating a silane coupling agent on the surface of the ceramic matrix to form a layer of polymer resin film, and filling a part of the silane coupling agent in the first micropores; polishing and grinding the surface of the ceramic matrix, removing the silane coupling agent on the surface of the ceramic matrix, and only leaving the silane coupling agent in the micropores to form anchoring points one by one; the anchoring points do not react with the etchant in the second etching, the surface of the ceramic matrix which is not covered by the silicon coupling agent is polished, the ceramic matrix reacts with the etchant to form second micropores in the second etching, the hydrophobic material is coated on the surface of the ceramic matrix, the hydrophobic material fills the second micropores while forming a hydrophobic layer, the hydrophobic material is combined with the anchoring points, the proportion of the hydrophobic material filling the micropores is improved, and the hydrophobic effect of the ceramic surface is improved.
As a further improvement of the scheme, the etching agent is hydrofluoric acid, and the mass concentration of the hydrofluoric acid is 2-8 per mill; the etching time is 2-10 minutes.
Specifically, hydrofluoric acid as an etchant reacts with silicon dioxide in the ceramic substrate to generate silicon tetrafluoride gas, thereby forming a microporous structure on the surface of the ceramic substrate.
As a further improvement of the above aspect, the method further comprises a step of cleaning the surface of the ceramic substrate before the step (1) to clean the surface of the ceramic substrate.
Preferably, the cleaning detergent comprises 15 wt% of sodium dodecyl sulfate, 7 wt% of fatty alcohol-polyoxyethylene ether AEO-9,1.2 wt% of dispersant Alcosperse 747,0.5 wt% of disodium ethylene diamine tetraacetate, and the balance deionized water.
As a further improvement of the scheme, the coating thickness of the silane coupling agent is 0.01-0.03mm, and the proper coating thickness can ensure that the first micropores are filled.
As a further improvement of the above scheme, in the step (2) and the step (4), the coating mode is spray coating or roll coating.
Preferably, the method for processing the surface hydrophobic ceramic comprises the following steps:
(1) Preparing a detergent, putting the ceramic substrate into an ultrasonic instrument, adding a certain amount of the detergent, setting the ultrasonic power to be 180-220W, the temperature to be 60-80 ℃, and the ultrasonic time to be 10-20 minutes; after the ultrasonic cleaning is finished, fully cleaning the surface of the ceramic substrate by using deionized water until no bubbles are generated, and drying in an oven at 120-200 ℃;
(2) Hydrofluoric acid solution with the concentration of 2-8 per mill is used as an etchant, the surface of the ceramic substrate is fully covered in a rolling coating mode, and all the etchant is washed away by water after etching for 2-10 minutes; then, cleaning the surface of the ceramic substrate by using a sodium hydroxide solution; washing with deionized water, and drying in an oven at 120-200 deg.C;
(3) Covering the silane coupling agent on the surface of the ceramic substrate in a spraying or rolling way, wherein the coating thickness is 0.1-0.3mm; then transferring the mixture into an infrared drying oven for leveling reaction to form a film;
(4) Polishing the surface of the ceramic matrix by using a soft polishing and grinding sheet, blowing high-pressure air on the surface of the ceramic matrix after polishing, performing secondary etching on the surface of the ceramic by using an etchant with the concentration of 2-8 per mill for 2-10 minutes, and washing off all the etchant by using water after polishing; then, cleaning the surface of the ceramic matrix by using a sodium hydroxide solution; washing with deionized water, and drying in an oven at 120-200 deg.C;
(5) And spraying the nano organic silicon resin on the surface of the ceramic matrix, and controlling the spraying thickness to be 5-25 mu m to obtain the surface hydrophobic ceramic.
Preferably, when the applicable environmental humidity of the treatment method is less than 75% and the environmental humidity is higher than 75%, a layer of water vapor film is easily formed on the surface of the ceramic substrate, so that the hydrophobic layer material is difficult to adhere to the surface of the ceramic substrate, thereby affecting the adhesion performance.
The technical scheme provided by the embodiment of the application at least has the following technical effects or advantages:
according to the invention, a first micropore and a second micropore are formed on the surface of a ceramic substrate, a silane coupling agent is filled in the first micropore, and the silane coupling agent filled in the first micropore forms individual anchoring points; and meanwhile, a hydrophobic material is filled in the second micropores, and the hydrophobic material and an anchoring point formed by a silane coupling agent act together to improve the adhesive force of the hydrophobic layer and the ceramic substrate and realize the improvement of the hydrophobic property of the ceramic surface.
The invention constructs micropores on the surface of a ceramic matrix by a process of combining secondary etching, wherein: etching for the first time to form first micropores on the surface of the ceramic substrate, and filling a silane coupling agent into the first micropores to form anchoring points; the second etching forms second micropores on the surface of the ceramic matrix, the hydrophobic material is filled in the second micropores, the hydrophobic material is coated on the outer surface of the ceramic matrix and is combined with the anchoring points, the proportion of the hydrophobic material for filling the micropores is improved, the hydrophobic effect of the surface of the ceramic is improved, the contact angle of the prepared surface hydrophobic ceramic is 118.7-123.5 degrees, and the adhesion performance of the hydrophobic material and the ceramic matrix is good.
Drawings
FIG. 1 is a schematic structural diagram of the surface hydrophobic ceramic of the present invention.
In the figure: 100 represents a ceramic matrix; 200 denotes a first micropore; 300 denotes a second microwell; 400 denotes a hydrophobic layer.
Detailed Description
The present invention is described in detail by the following examples to facilitate the understanding of the present invention by those skilled in the art, and it is necessary to point out that the examples are only used for further illustration of the present invention and should not be construed as limiting the scope of the present invention, and that the non-essential modifications and adjustments of the present invention by those skilled in the art should still fall within the scope of the present invention, and that the raw materials mentioned below are not specified in detail and are all commercially available products, and that the process steps or preparation methods not mentioned in detail are all known to those skilled in the art.
As shown in fig. 1, the surface hydrophobic ceramic of the present invention includes a ceramic substrate 100 and a hydrophobic layer 400, wherein the ceramic substrate 100 has first micropores 200 and second micropores 300 on an inner surface thereof, and the hydrophobic layer 400 covers an outer surface of the ceramic substrate 100; the first micro-holes 200 are filled with a silane coupling agent, the second micro-holes 300 contain a filler, and the filler and the hydrophobic layer 400 are both hydrophobic materials.
The ceramic substrates 100 of the following examples and comparative examples were each selected from polished tiles having dimensions of 200X 200 mm; the relative humidity of the environment in the surface treatment process is 65 percent; the nano-silicone resin is selected from QY-60 nano-silicone resin.
Example 1
The surface hydrophobic ceramic comprises a ceramic substrate and a hydrophobic layer, wherein the inner surface of the ceramic substrate is provided with a first micropore and a second micropore, and the hydrophobic layer covers the outer surface of the ceramic substrate; the first micropores are filled with silane coupling agent gamma-aminopropyltriethoxysilane, the second micropores contain fillers, and the fillers and the hydrophobic layer are hydrophobic material nano organic silicon resin; the thickness of the hydrophobic layer was 15 μm.
A method for processing surface hydrophobic ceramics comprises the following steps:
(1) Preparing a detergent according to the weight percentage of 15% of sodium dodecyl sulfate, 7% of AEO-9,1.2% of Alcosperse 747,0.5% of disodium ethylene diamine tetraacetate and the balance of deionized water, putting the polished ceramic tile into an ultrasonic instrument, adding a certain amount of the prepared detergent, setting the ultrasonic power at 200W, the temperature at 70 ℃ and the ultrasonic time at 15 minutes; after the ultrasonic cleaning is finished, fully cleaning the surface of the ceramic substrate by using deionized water until no bubbles are generated, and drying the ceramic substrate in a drying oven at the temperature of 120 ℃;
(2) Hydrofluoric acid solution with the concentration of 2 per mill is used as an etching agent, the surface of the polished ceramic tile is fully covered in a rolling coating mode, and all the etching agent is washed away by water after etching for 10 minutes; then cleaning and polishing the surface of the ceramic tile by using a sodium hydroxide solution; washing with deionized water, and drying in a 120 deg.C oven;
(3) Covering the gamma-aminopropyltriethoxysilane on the surface of the ceramic substrate in a spraying manner, wherein the coating thickness is 0.1mm; then transferring the mixture into an infrared drying oven for leveling reaction to form a film;
(4) Polishing the surface of the ceramic substrate by using a soft polishing and grinding sheet, blowing high-pressure air to polish the surface of the ceramic tile after polishing, performing secondary etching on the surface of the ceramic by using an etching agent with the concentration of 2 per mill for 8 minutes, and washing away all the etching agent by using water after polishing; then, cleaning the surface of the ceramic substrate by using a sodium hydroxide solution; washing with deionized water, and drying in a 120 deg.C oven;
(5) The nano organic silicon resin is sprayed on the surface of the polished ceramic tile, and the spraying thickness is controlled to be 15 mu m, so that the polished ceramic tile with the hydrophobic surface is prepared.
Example 2
The surface hydrophobic ceramic comprises a ceramic matrix and a hydrophobic layer, wherein the inner surface of the ceramic matrix is provided with a first micropore and a second micropore, and the hydrophobic layer covers the outer surface of the ceramic matrix; the first micropores are filled with silane coupling agent gamma-methacryloxypropyl trimethoxy silane, the second micropores contain fillers, and the fillers and the hydrophobic layer are hydrophobic material nano organic silicon resin; the thickness of the hydrophobic layer was 25 μm.
A method for processing surface hydrophobic ceramics comprises the following steps:
(1) Preparing a detergent according to the weight percentage of 15% of sodium dodecyl sulfate, 7% of AEO-9,1.2% of Alcosperse 747,0.5% of disodium ethylene diamine tetraacetate and the balance of deionized water, putting the polished tile into an ultrasonic instrument, adding a certain amount of the prepared detergent, setting the ultrasonic power at 200W, the temperature at 70 ℃ and the ultrasonic time at 15 minutes; after the ultrasonic cleaning is finished, the surface of the ceramic substrate is fully cleaned by deionized water until no bubbles are generated, and the ceramic substrate is placed into a drying oven at 120 ℃ for drying;
(2) Taking hydrofluoric acid solution with the concentration of 8 per mill as an etching agent, fully covering the surface of the polished ceramic tile in a rolling coating mode, and cleaning away all the etching agent by water after etching for 10 minutes; then cleaning and polishing the surface of the ceramic tile by using a sodium hydroxide solution; washing with deionized water, and drying in a 120 deg.C oven;
(3) Covering gamma-methacryloxypropyltrimethoxysilane on the surface of a ceramic matrix in a spraying manner, wherein the coating thickness is 0.2mm; then transferring the film into an infrared drying oven to carry out leveling reaction to form a film;
(4) Polishing the surface of the ceramic substrate by using a soft polishing and grinding sheet, blowing and polishing the surface of the ceramic tile by using high-pressure air after polishing, performing secondary etching on the surface of the ceramic by using an etching agent with the concentration of 2 per mill for 8 minutes, and washing off all the etching agent by using water after polishing; then, cleaning the surface of the ceramic substrate by using a sodium hydroxide solution; washing with deionized water, and drying in a 120 deg.C oven;
(5) The nano organic silicon resin is sprayed on the surface of the polished ceramic tile, and the spraying thickness is controlled to be 25 μm, so that the polished ceramic tile with the hydrophobic surface is prepared.
Example 3
The surface hydrophobic ceramic comprises a ceramic matrix and a hydrophobic layer, wherein the inner surface of the ceramic matrix is provided with a first micropore and a second micropore, and the hydrophobic layer covers the outer surface of the ceramic matrix; the first micropores are filled with silane coupling agent gamma-aminopropyl triethoxysilane, the second micropores are filled with fillers, and the fillers and the hydrophobic layer are hydrophobic material nano organic silicon resin; the thickness of the hydrophobic layer was 5 μm.
A method for processing surface hydrophobic ceramics comprises the following steps:
(1) Preparing a detergent according to the weight percentage of 15% of sodium dodecyl sulfate, 7% of AEO-9,1.2% of Alcosperse 747,0.5% of disodium ethylene diamine tetraacetate and the balance of deionized water, putting the polished ceramic tile into an ultrasonic instrument, adding a certain amount of the prepared detergent, setting the ultrasonic power at 200W, the temperature at 70 ℃ and the ultrasonic time at 15 minutes; after the ultrasonic cleaning is finished, fully cleaning the surface of the ceramic substrate by using deionized water until no bubbles are generated, and drying the ceramic substrate in a drying oven at the temperature of 120 ℃;
(2) Hydrofluoric acid solution with the concentration of 2 per mill is used as an etching agent, the surface of the polished ceramic tile is fully covered in a rolling coating mode, and all the etching agent is washed away by water after etching for 2 minutes; then cleaning and polishing the surface of the ceramic tile by using a sodium hydroxide solution; washing with deionized water, and drying in a 120 deg.C oven;
(3) Covering the gamma-aminopropyltriethoxysilane on the surface of the ceramic matrix in a spraying manner, wherein the coating thickness is 0.1mm; then transferring the mixture into an infrared drying oven for leveling reaction to form a film;
(4) Polishing the surface of the ceramic substrate by using a soft polishing and grinding sheet, blowing and polishing the surface of the ceramic tile by using high-pressure air after polishing, performing secondary etching on the surface of the ceramic by using an etching agent with the concentration of 2 per mill for 8 minutes, and washing off all the etching agent by using water after polishing; then, cleaning the surface of the ceramic substrate by using a sodium hydroxide solution; washing with deionized water, and drying in a 120 deg.C oven;
(5) The nano organic silicon resin is sprayed on the surface of the polished tile, and the spraying thickness is controlled to be 5 mu m, so that the polished tile with the hydrophobic surface is prepared.
Example 4
The surface hydrophobic ceramic comprises a ceramic substrate and a hydrophobic layer, wherein the inner surface of the ceramic substrate is provided with a first micropore and a second micropore, and the hydrophobic layer covers the outer surface of the ceramic substrate; the first micropores are filled with silane coupling agent gamma-methacryloxypropyl trimethoxy silane, the second micropores contain fillers, and the fillers and the hydrophobic layer are hydrophobic material nano organic silicon resin; the thickness of the hydrophobic layer was 15 μm.
A method for processing surface hydrophobic ceramics comprises the following steps:
(1) Preparing a detergent according to the weight percentage of 15% of sodium dodecyl sulfate, 7% of AEO-9,1.2% of Alcosperse 747,0.5% of disodium ethylene diamine tetraacetate and the balance of deionized water, putting the polished tile into an ultrasonic instrument, adding a certain amount of the prepared detergent, setting the ultrasonic power at 200W, the temperature at 70 ℃ and the ultrasonic time at 15 minutes; after the ultrasonic cleaning is finished, fully cleaning the surface of the ceramic substrate by using deionized water until no bubbles are generated, and drying the ceramic substrate in a drying oven at the temperature of 120 ℃;
(2) Taking hydrofluoric acid solution with the concentration of 6 per mill as an etching agent, fully covering the surface of the polished ceramic tile in a rolling coating mode, and cleaning away all the etching agent by water after etching for 4 minutes; then cleaning and polishing the surface of the ceramic tile by using a sodium hydroxide solution; washing with deionized water, and drying in a 120 deg.C oven;
(3) Covering the gamma-methacryloxypropyl trimethoxy silane on the surface of a ceramic substrate in a spraying manner, wherein the coating thickness is 0.3mm; then transferring the mixture into an infrared drying oven for leveling reaction to form a film;
(4) Polishing the surface of the ceramic substrate by using a soft polishing and grinding sheet, blowing high-pressure air to polish the surface of the ceramic tile after polishing, performing secondary etching on the surface of the ceramic by using an etching agent with the concentration of 2 per mill for 8 minutes, and washing away all the etching agent by using water after polishing; then, cleaning the surface of the ceramic substrate by using a sodium hydroxide solution; washing with deionized water, and drying in a 120 deg.C oven;
(5) The nano organic silicon resin is sprayed on the surface of the polished ceramic tile, and the spraying thickness is controlled to be 15 mu m, so that the polished ceramic tile with the hydrophobic surface is prepared.
Comparative example 1
A polished tile having a size of 200X 200mm without any surface treatment was used as comparative example 1.
Comparative example 2
A surface hydrophobic ceramic comprising a ceramic substrate and a hydrophobic layer, the hydrophobic layer having a thickness of 15 μm.
A method for processing surface hydrophobic ceramics comprises the following steps:
(1) Preparing a detergent according to the weight percentage of 15% of sodium dodecyl sulfate, 7% of AEO-9,1.2% of Alcosperse 747,0.5% of disodium ethylene diamine tetraacetate and the balance of deionized water, putting the polished tile into an ultrasonic instrument, adding a certain amount of the prepared detergent, setting the ultrasonic power at 200W, the temperature at 70 ℃ and the ultrasonic time at 15 minutes; after the ultrasonic cleaning is finished, fully cleaning the surface of the ceramic substrate by using deionized water until no bubbles are generated, and drying the ceramic substrate in a drying oven at the temperature of 120 ℃;
(2) And spraying the nano organic silicon resin on the surface of the ceramic matrix, and controlling the spraying thickness to be 15 mu m to obtain the surface hydrophobic polished ceramic tile of the comparative example.
Comparative example 3
The surface hydrophobic ceramic comprises a ceramic matrix and a hydrophobic layer, wherein micropores are formed in the inner surface of the ceramic matrix, and the hydrophobic layer covers the outer surface of the ceramic matrix; the micropores are filled with hydrophobic material nano organic silicon resin; the thickness of the hydrophobic layer was 15 μm.
A method for processing surface hydrophobic ceramics comprises the following steps:
(1) Preparing a detergent according to the weight percentage of 15% of sodium dodecyl sulfate, 7% of AEO-9,1.2% of Alcosperse 747,0.5% of disodium ethylene diamine tetraacetate and the balance of deionized water, putting the polished tile into an ultrasonic instrument, adding a certain amount of the prepared detergent, setting the ultrasonic power at 200W, the temperature at 70 ℃ and the ultrasonic time at 15 minutes; after the ultrasonic cleaning is finished, fully cleaning the surface of the ceramic substrate by using deionized water until no bubbles are generated, and drying the ceramic substrate in a drying oven at the temperature of 120 ℃;
(2) Hydrofluoric acid solution with the concentration of 2 per mill is used as an etching agent, the surface of the polished ceramic tile is fully covered in a rolling coating mode, and all the etching agent is washed away by water after etching for 10 minutes; then cleaning and polishing the surface of the ceramic tile by using a sodium hydroxide solution; washing with deionized water, and drying in a 120 deg.C oven;
(3) And spraying the nano organic silicon resin on the surface of the polished ceramic tile, and controlling the spraying thickness to be 15 mu m to prepare the surface hydrophobic polished ceramic tile of the comparative example.
Comparative example 4
The surface hydrophobic ceramic comprises a ceramic matrix and a hydrophobic layer, wherein micropores are formed in the inner surface of the ceramic matrix, and the hydrophobic layer covers the outer surface of the ceramic matrix; the micropores are filled with organosilane coupling agent gamma-aminopropyl triethoxysilane; the thickness of the hydrophobic layer was 15 μm.
A method for processing surface hydrophobic ceramics comprises the following steps:
(1) Preparing a detergent according to the weight percentage of 15% of sodium dodecyl sulfate, 7% of AEO-9,1.2% of Alcosperse 747,0.5% of disodium ethylene diamine tetraacetate and the balance of deionized water, putting the polished tile into an ultrasonic instrument, adding a certain amount of the prepared detergent, setting the ultrasonic power at 200W, the temperature at 70 ℃ and the ultrasonic time at 15 minutes; after the ultrasonic cleaning is finished, fully cleaning the surface of the ceramic substrate by using deionized water until no bubbles are generated, and drying the ceramic substrate in a drying oven at the temperature of 120 ℃;
(2) Using hydrofluoric acid solution with the concentration of 2 per mill as an etching agent, fully covering the surface of the polished ceramic tile in a rolling coating mode, and cleaning away all the etching agent by water after etching for 10 minutes; then cleaning and polishing the surface of the ceramic tile by using a sodium hydroxide solution; washing with deionized water, and drying in a 120 deg.C oven;
(3) Covering the gamma-aminopropyltriethoxysilane on the surface of the ceramic substrate in a spraying manner, wherein the coating thickness is 0.1mm; then transferring the film into an infrared drying oven to carry out leveling reaction to form a film;
(4) The nano organic silicon resin is sprayed on the surface of the polished ceramic tile, and the spraying thickness is controlled to be 15 mu m, so that the polished ceramic tile with the hydrophobic surface is prepared.
Performance test
1. Hydrophobic properties
The contact angles of the hydrophobic surfaces of the polished tiles obtained in each of the examples and the comparative examples were measured by a contact angle meter model LAUDA LSA60, and the results are shown in Table 1.
The test conditions were: at random 25 points on the hydrophobic surface of each polished tile were tested and averaged to give an ambient temperature of 26 c.
Table 1: contact angle of hydrophobic surface of polished tiles obtained in each of examples and comparative examples
As can be seen from Table 1, the contact angles of the hydrophobic surfaces of the polished tiles obtained in examples 1 to 4 were all larger than those of comparative examples 1 to 4, in which: comparative example 1 in which no surface treatment was performed and comparative example 2 in which a nano silicone resin was directly sprayed on the surface of the polished tile, both had poor hydrophobic properties; in contrast, comparative example 3 in which only the nano-silicone resin was filled in the microporous layer by performing the primary etching and comparative example 4 in which only the organic silane coupling agent was filled in the microporous layer, both of which were not as hydrophobic as those of examples 1 to 4 in which the nano-silicone resin and the organic silane coupling agent were simultaneously filled in the microporous layer, were not subjected to the secondary etching according to the present invention.
2. Adhesion Properties
The adhesion of the hydrophobic surface of the polished tile prepared in each example was tested by the following method: firstly, adopting a steel wool friction experiment, wherein the experimental conditions are as follows: a500-gram weight was placed on 0# steel wool and continuously rubbed 500 times with a rubbing area of 2X 2cm, and then the hydrophobic property test was performed by the above method, and the test results are shown in Table 2.
Table 2: contact Angle of the hydrophobic surface of the polished tiles obtained in the examples after rubbing
| Sample(s) | Example 1 | Example 2 | Example 3 | Example 4 |
| Contact angle (average) | 113.8° | 112.9° | 110.2° | 113.1° |
As can be seen from Table 2: after the rubbing treatment, the decrease of the contact angle of the hydrophobic surface of the polished tile is only between 8 and 9 degrees, which indicates that the polished tile has good adhesion performance.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are intended to be within the scope of the invention.
Claims (7)
1. The surface hydrophobic ceramic is characterized by comprising a ceramic substrate and a hydrophobic layer, wherein a first micropore and a second micropore are formed in the inner surface of the ceramic substrate, and the hydrophobic layer covers the outer surface of the ceramic substrate; the first micropores are filled with silane coupling agents, the second micropores contain fillers, and the fillers and the hydrophobic layer are both hydrophobic materials;
the silane coupling agent is selected from gamma-aminopropyltriethoxysilane or gamma-methacryloxypropyltrimethoxysilane;
the hydrophobic material is nano organic silicon resin;
the surface hydrophobic ceramic adopts an etching method to construct a microporous structure on the surface of a ceramic matrix and is prepared by a treatment method comprising the following steps:
(1) Etching the surface of the ceramic substrate by using an etchant for one time to form first micropores;
(2) Coating a silane coupling agent on the surface of the ceramic substrate;
(3) Polishing and grinding the surface of the ceramic substrate, and then performing secondary etching by using an etching agent to form second micropores;
(4) And coating a hydrophobic material on the surface of the ceramic matrix to obtain the surface hydrophobic ceramic.
2. The surface hydrophobic ceramic of claim 1, wherein the hydrophobic layer has a thickness of 5-25 μ ι η.
3. The surface hydrophobic ceramic of claim 1, wherein the etchant is hydrofluoric acid, and the mass concentration of the hydrofluoric acid is 2-8 ‰; the etching time is 2-10 minutes.
4. The surface hydrophobic ceramic of claim 1, further comprising a step of cleaning the ceramic surface prior to step (1).
5. The surface hydrophobic ceramic of claim 1, wherein the silane coupling agent is applied at a thickness of 0.01 to 0.03mm.
6. The surface hydrophobic ceramic of claim 1, wherein in step (2) and step (4), the coating is by spraying or rolling.
7. The surface hydrophobic ceramic of claim 1, wherein the process is applied at an ambient humidity of less than 75%.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9127171D0 (en) * | 1991-12-20 | 1992-02-19 | Courtaulds Coatings Holdings | Coating compositions |
| FR2910315A1 (en) * | 2006-12-20 | 2008-06-27 | Oreal | Cosmetic kit, containing different compositions packaged separately, comprises hydrophobic solid particles, silicone particles capable of reacting with one another by hydrosilylation or condensation reaction; and optionally catalyst |
| CN101250376A (en) * | 2008-03-19 | 2008-08-27 | 汕头经济特区龙湖科技有限公司 | Silicone exterior wall paint and preparation method thereof |
| CN102108256A (en) * | 2010-12-31 | 2011-06-29 | 哈尔滨工业大学深圳研究生院 | Inorganic-organic superhydrophobic nanocomposite for stone historical relics and preparation method thereof |
| CN110790935A (en) * | 2019-08-28 | 2020-02-14 | 中国科学院兰州化学物理研究所 | Fluorine-free hydrophobic treatment agent, preparation method and application thereof, and self-cleaning glass |
| CN114891403A (en) * | 2022-05-27 | 2022-08-12 | 中德新亚建筑材料有限公司 | Permeable composite fluorocarbon protective water-based paint |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1121186A (en) * | 1997-07-02 | 1999-01-26 | Inax Corp | Water repellent treatment of ceramic article |
| JP2007536387A (en) * | 2003-07-14 | 2007-12-13 | スーパーシール リミテッド | Hydrophobic composition and fine particles, and uses thereof |
| WO2005065199A2 (en) * | 2003-12-31 | 2005-07-21 | Corning Incorporated | Ceramic structures having hydrophobic coatings |
| CN105347690B (en) * | 2015-12-28 | 2017-12-22 | 中国科学院兰州化学物理研究所 | Recoverable coating material of a kind of transparent and ultra-hydrophobicity and preparation method thereof |
| CN107555963A (en) * | 2016-06-30 | 2018-01-09 | 南京理工大学 | A kind of super-hydrophobic ceramic preparation method |
| CN109481989B (en) * | 2018-09-10 | 2021-02-26 | 景应政 | High-temperature-resistant dehumidifying ceramic filter element and preparation method thereof |
| CN110143809A (en) * | 2019-04-18 | 2019-08-20 | 浙江金海环境技术股份有限公司 | Ceramic foam filter of hydrophobic oleophobic and preparation method thereof |
| CN111635258B (en) * | 2020-05-08 | 2022-05-03 | 北京林业大学 | TiO based on ceramic membrane2Super-hydrophobic modification method |
| CN113292898B (en) * | 2021-05-20 | 2022-03-04 | 东莞理工学院 | Wear-resistant high-adhesion super-hydrophobic coating and preparation method thereof |
| CN114300270A (en) * | 2022-01-25 | 2022-04-08 | 天津大学 | Preparation method of multilayer ceramic capacitor structure with waterproof and breakdown-resistant characteristics |
-
2021
- 2021-11-29 CN CN202111446124.9A patent/CN114085099B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9127171D0 (en) * | 1991-12-20 | 1992-02-19 | Courtaulds Coatings Holdings | Coating compositions |
| FR2910315A1 (en) * | 2006-12-20 | 2008-06-27 | Oreal | Cosmetic kit, containing different compositions packaged separately, comprises hydrophobic solid particles, silicone particles capable of reacting with one another by hydrosilylation or condensation reaction; and optionally catalyst |
| CN101250376A (en) * | 2008-03-19 | 2008-08-27 | 汕头经济特区龙湖科技有限公司 | Silicone exterior wall paint and preparation method thereof |
| CN102108256A (en) * | 2010-12-31 | 2011-06-29 | 哈尔滨工业大学深圳研究生院 | Inorganic-organic superhydrophobic nanocomposite for stone historical relics and preparation method thereof |
| CN110790935A (en) * | 2019-08-28 | 2020-02-14 | 中国科学院兰州化学物理研究所 | Fluorine-free hydrophobic treatment agent, preparation method and application thereof, and self-cleaning glass |
| CN114891403A (en) * | 2022-05-27 | 2022-08-12 | 中德新亚建筑材料有限公司 | Permeable composite fluorocarbon protective water-based paint |
Non-Patent Citations (3)
| Title |
|---|
| 有机-无机复合疏水型二氧化硅涂层制备及性能;杨隽永等;《文物保护与考古科学》;20180415(第02期);全文 * |
| 疏水性多孔材料的合成及其吸附性能的研究;禹如荫;《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》;20220115;全文 * |
| 超疏水有机硅涂层的制备与性质研究;李恒等;《功能材料》;20141230;全文 * |
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