CN113548907A - Hydrophobic antifouling rock plate imitating banana leaf and preparation method thereof - Google Patents
Hydrophobic antifouling rock plate imitating banana leaf and preparation method thereof Download PDFInfo
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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
- C04B41/5346—Dry etching
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- 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
- C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
- C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
- C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
- C04B41/4922—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
- C04B41/4933—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane containing halogens, i.e. organohalogen silanes
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- 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
- C04B41/5315—Cleaning compositions, e.g. for removing hardened cement from ceramic tiles
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- 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
- C04B41/82—Coating or impregnation with organic materials
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- 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
Abstract
The invention discloses a banana leaf-imitated hydrophobic antifouling rock plate and a preparation method thereof. The preparation method comprises the following steps: etching the surface of the ceramic rock plate by ultraviolet laser to form a micro-nano secondary composite structure; the micro-nano secondary composite structure comprises a micro-scale groove and nano-scale particles attached to the micro-scale groove; cleaning and drying the rock plate with the micro-nano secondary composite structure formed on the surface; soaking the dried rock plate in an ethanol solution containing fluorine silane to enable fluorosilane molecules to be connected to the surface of the rock plate in a covalent bond mode; and taking out the soaked rock plate and drying again to obtain the hydrophobic antifouling rock plate imitating the banana leaf. According to the preparation method, the micro-nano structure of the banana leaf is introduced to the surface of the rock plate through ultraviolet laser etching, and the micro-nano structure is in modified coupling with fluorosilane, so that the hydrophobic antifouling functionalization of the rock plate is promoted while the decorative property of the rock plate is considered.
Description
Technical Field
The invention relates to the field of functional ceramics, in particular to a banana leaf-imitated hydrophobic antifouling rock plate and a preparation method thereof.
Background
The ceramic rock plate is a novel ceramic material which is prepared by pressing and molding a ceramic raw material by a press and sintering the ceramic raw material at a high temperature of more than 1200 ℃, and can be reprocessed by cutting, drilling, polishing and other processes. The ceramic rock plate is mainly used in the field of household and kitchen plate decoration at present, and the hydrophobic and antifouling performance of the rock plate is required to be high.
The prior art mainly improves the hydrophobic property of the rock plate by adjusting the formula of a ceramic material or preparing a coating on the surface of the rock plate. Chinese patent CN 211666134U discloses a preparation method of a self-cleaning ceramic tile, wherein a layer of epoxy resin is sprayed on the surface of the ceramic tile, and fumed silica is sprayed on the epoxy resin layer to form a micro-nano mastoid structure. When the surface of the ceramic tile obtained by the method is contacted with water, the micro-nano structure on the surface of the ceramic tile can capture air, and the contact area between the water and the ceramic tile is reduced, so that the hydrophobic and antifouling effects are realized. But the bonding force between the epoxy resin layer and the ceramic tile is weak, which causes poor hydrophobic durability of the ceramic tile, and the epoxy resin can be affected by factors such as light, time and the like, and can be yellowed, thereby affecting the decoration of the ceramic tile.
Disclosure of Invention
Aiming at the problems, the invention provides a banana leaf-imitated hydrophobic antifouling rock plate and a preparation method thereof. According to the preparation method, the micro-nano structure of the banana leaf is introduced to the surface of the rock plate through ultraviolet laser etching, and the micro-nano structure is in modified coupling with fluorosilane, so that the hydrophobic antifouling functionalization of the rock plate is promoted while the decorative property of the rock plate is considered.
In a first aspect, the invention provides a preparation method of a banana leaf imitated hydrophobic antifouling rock plate. The preparation method comprises the following steps:
etching the surface of the ceramic rock plate by ultraviolet laser to form a micro-nano secondary composite structure; the micro-nano secondary composite structure comprises a micro-scale groove and nano-scale particles attached to the micro-scale groove;
cleaning and drying the rock plate with the micro-nano secondary composite structure formed on the surface;
soaking the dried rock plate in an ethanol solution containing fluorine silane to enable fluorosilane molecules to be connected to the surface of the rock plate in a covalent bond mode;
and taking out the soaked rock plate and drying again to obtain the hydrophobic antifouling rock plate imitating the banana leaf.
According to the preparation method, the ultraviolet laser processing microstructure is combined with the fluorosilane modification mode to prepare the ceramic rock plate with the banana leaf imitated micro-nano composite structure (the banana leaf imitated micro-nano composite structure is in the shape of the groove-shaped distributed micron-scale stripes, and a large number of nano-scale particles are attached to the bottom of the groove) on the surface, water drops, ink, soy sauce and other stains are spherical on the surface of the rock plate with the structure instead of being spread, and the ceramic rock plate quickly rolls off the surface along with the inclination of the rock plate, so that the ceramic rock plate has an excellent hydrophobic and antifouling effect.
Preferably, the width of the micron-sized trenches is 20-60 μm, and the distance between adjacent micron-sized trenches is 100-250 μm.
Preferably, the particle size of the nano-scale particles is 100-400 nm.
Preferably, the processing parameters of the ultraviolet laser etching are as follows: the scanning speed is 100-250mm/s, the processing times are 2-8, the laser repetition frequency is 10-25kHz, and the power is 1-3W.
Preferably, the volume ratio of the fluorosilane to the ethanol is 1:100-1: 50.
Preferably, the soaking time of the dried rock plate in the ethanol solution containing the fluorine silane is 3-4 h.
Preferably, the fluorosilane is 1H,1H,2H, 2H-perfluorodecyl triethoxysilane.
In a second aspect, the invention provides a hydrophobic antifouling rock plate imitating plantain leaves obtained by the preparation method of any one of the above. The hydrophobic antifouling rock plate imitating the banana leaf takes water as a medium, the static contact angle is 146-160 degrees, and the rolling angle is 6-20 degrees.
Preferably, the specifications of the hydrophobic antifouling rock plate imitating the plantain leaves are 900mm long, 900mm wide and 3-6mm high.
Drawings
FIG. 1 is (A) SEM image of surface of hydrophobic anti-fouling rock plate imitating banana leaf, (B) SEM image of local micro-scale grooves; (C) is SEM image of local nano-scale particles with the ruler of 100 μm, and (D) is the contact angle of the hydrophobic antifouling rock plate imitating the banana leaf and water;
FIG. 2 is a graph of the anti-soil assay of the hydrophobic anti-fouling slate of the simulated Japanese banana leaf of example 1.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative of, and not restrictive on, the present invention. Unless otherwise specified, each percentage means a mass percentage.
The following is an exemplary illustration of the preparation method of the hydrophobic anti-fouling rock plate imitating banana leaf according to the present invention.
And etching the surface of the ceramic rock plate by ultraviolet laser to form a micro-nano secondary composite structure. The ceramic rock plate may be a finished ceramic rock plate. The finished ceramic rock plate (after sintering) belongs to a brittle material, has poor plasticity, and is difficult to directly press and form through a die to obtain a special micro-nano secondary composite structure. The advantage of carrying out ceramic rock plate surface sculpture through ultraviolet laser is that ultraviolet laser beam is of high quality, and the focus facula is minimum, and it is minimum to carry out the heat affected zone when hyperfine micro-nano structure processing to ceramic rock plate, can not produce the heat effect, can not produce the scorch.
The micro-nano secondary composite structure comprises a micron-sized groove and nano-scale particles attached to the micron-sized groove. The reason why the micro-groove-shaped and nano-particle structures can be generated on the surface of the ceramic rock plate simultaneously through ultraviolet laser etching is that: the effects of laser light on ceramic materials include photothermal and photochemical effects. The photothermal effect is that the temperature of the material is increased after the laser energy is absorbed by the ceramic material, and the separation of the material is realized through physical processes such as melting, vaporization and the like. Photochemical interactions are characterized by the fact that the laser energy density is greater than the chemical binding energy of the material being processed, causing the laser photons to directly break the chemical bonds of the material and thereby dissociate the material. If the etching is carried out by adopting the fiber laser with the wavelength of 1064nm, the absorption of the fiber laser from near infrared to far infrared wave bands by the ceramic material belongs to typical heat absorption, the fiber laser is quickly converted into heat energy after being absorbed to melt the surface of the material, and the heat influence on the peripheral area of the material is larger while the material is removed, so that the whole structure is in a molten state, and no obvious microstructure is generated on the surface of the material after cooling. The processing of ceramic materials by ultraviolet laser with the wave band of 355nm mainly belongs to photochemical action, so that the breaking speed of chemical bonds of the materials is greater than the binding speed, the local air pressure of the processed area of the materials is increased, the materials after dissociation are rapidly expanded, and finally the materials are separated from a matrix in an explosion mode and residual heat is taken away. The heat affected zone of the ultraviolet laser processing on the peripheral materials is very small, the obtained laser processing precision and surface quality are high, and a fine micro-nano secondary structure with a micro-groove shape and nano-particles compounded can be obtained. The micron groove-shaped structure is a design pattern, and the nano particle structure attached to the groove (edge) is formed by re-solidifying and stacking ceramic materials after micro melting and splashing.
The processing parameters of the ultraviolet laser etching can be as follows: the scanning speed is 100-250mm/s, the processing times are 2-8, the laser repetition frequency is 10-25kHz, and the power is 1-3W. The processing parameters of the ultraviolet laser etching mainly affect the dimension of the micro-nano secondary composite structure, thereby affecting the wettability and the hydrophobic effect. The micro-nano secondary composite structure can be formed on the surface of the rock plate by utilizing an ultraviolet laser. For example, ultraviolet laser with the wavelength of 355nm is used for etching the surface of the rock plate to form a micro-nano secondary composite structure.
The micron-sized grooves may have a width of 20-60 μm. The micron-sized grooves are determined by the spot diameter of the ultraviolet laser. The spacing between adjacent micron-sized trenches is 100-. The spacing between adjacent micron-scale grooves is determined by the design pattern. In some embodiments, the nanoscale particles have a particle size of 100-400 nm. The width of the micron-sized groove, the distance between the adjacent micron-sized grooves and the particle size of the nano-scale particles are limited in the above range, so that the phenomenon that the processing time is longer under the condition of the same processing area due to the over-small dimension of the microstructure is avoided, and the production efficiency of large-scale manufacturing of the ceramic rock plate is influenced; the influence of overlarge microstructure dimension on the decoration of the ceramic rock plate can be avoided, and meanwhile, the hydrophobic effect is reduced.
The chemical composition of the ceramic rock plate is not limited, and the ceramic rock plate formula commonly used in the field can be adopted. For example, the chemical composition of the ceramic rock plate includes: by mass percent, SiO2 60-70％、Al2O3 20-30％、K2O 0-10％、Na2O0-10%, CaO 1-3%, and MgO 1-3%. Likewise, the specifications of the ceramic rock plate are not limited. For example, the ceramic rock plate can have a length of 300-.
And cleaning and drying the rock plate with the micro-nano secondary composite structure formed on the surface. The cleaning is to remove the residual slag dirt after the laser processing of the ceramic rock plate. For example, the rock plate with the micro-nano secondary composite structure formed on the surface is ultrasonically cleaned in deionized water for 10-15min and then dried. The drying temperature can be 80-110 deg.C, and the drying time can be 15-40 min.
The dried rock plate was soaked in a solution of the fluorosilane in ethanol to reduce the surface energy of the rock plate, but this did not form a low surface energy coating on the surface of the rock plate. This is because fluorosilane is mainly covalently bonded to the dense rock surface and thus it is difficult to form a continuous coating). The fluorosilane may be 1H,1H,2H, 2H-perfluorodecyltriethoxysilane.
The volume ratio of the fluorosilane to the ethanol is 1:100-1: 50. Thus, excellent hydrophobic properties can be obtained while controlling costs.
And soaking the dried rock plate in an ethanol solution containing fluorine silane for 3-4 h. The soaking time is controlled within the range, so that a good hydrophobic effect can be obtained, and the time cost is effectively controlled.
And taking out the soaked rock plate and drying again to obtain the hydrophobic antifouling rock plate imitating the banana leaf. The drying temperature is 90-120 deg.C, and the drying time is 20-40 min.
The preparation method of the banana leaf-imitated hydrophobic antifouling rock plate disclosed by the invention applies a bionics principle, takes the banana leaf as a bionic object, constructs a groove array microstructure on the surface of the rock plate, and modifies the groove array microstructure by fluorosilane, so that the obtained rock plate surface is in a hydrophobic state and has an antifouling function.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
The preparation method of the banana leaf-imitated hydrophobic antifouling rock plate comprises the following steps:
step (1): etching and processing the surface of the rock plate by using ultraviolet nanosecond laser to form a micro-nano secondary composite structure; the distance between the micron-sized grooves of the micro-nano secondary composite structure is 100 micrometers; the ultraviolet nanosecond laser processing parameters are as follows: the laser scanning speed is 150mm/s, the processing times are 4 times, and the power is 1W;
step (2): ultrasonically cleaning the rock plate subjected to laser etching for 10min by using deionized water, and then drying; drying at 80 deg.C for 15 min;
and (3): immersing the dried rock plate bubble into an ethanol solution containing 1H,1H,2H, 2H-perfluorodecyl triethoxysilane for 3H, wherein the volume ratio of the 1H,1H,2H, 2H-perfluorodecyl triethoxysilane to ethanol is 1:100, respectively;
and (4): and taking out the rock plate and drying at the drying temperature of 90 ℃ for 20min to obtain the hydrophobic antifouling rock plate imitating the banana leaf.
The static contact angle was measured by a contact angle measuring instrument of type C2000D1 in shanghai and morning, and the rolling angle was measured by a tilted plate method. The test drop volume was 6 microliters. Six measurements were taken at randomly selected areas of the surface of each rock sample and averaged as a test result to reduce error. The hydrophobic antifouling rock plate of the banana leaf takes water as a medium, the static contact angle is 146.5 degrees, and the rolling angle is 19 degrees. As shown in figure 2, the hydrophobic antifouling rock plate is inclined, dark soy sauce, light soy sauce, oil consumption and the like are dropped on the surface of the ceramic tile, and the dark soy sauce, the light soy sauce and the oil consumption roll down from the surface of the rock plate, so that basically no residue is left.
Example 2
The preparation method of the banana leaf-imitated hydrophobic antifouling rock plate comprises the following steps:
step (1): etching and processing the surface of the rock plate by using ultraviolet nanosecond laser to form a micro-nano secondary composite structure; the distance between the micron-sized grooves of the micro-nano secondary composite structure is 150 micrometers; the ultraviolet nanosecond laser processing parameters are as follows: the laser scanning speed is 100mm/s, the processing times are 4 times, and the power is 2W;
step (2): ultrasonically cleaning the rock plate subjected to laser etching for 10min by using deionized water, and then drying; drying at 80 deg.C for 15 min;
and (3): immersing the dried rock vacuole into an ethanol solution containing 1H,1H,2H, 2H-perfluorodecyl triethoxysilane for 3.5H, wherein the volume ratio of the 1H,1H,2H, 2H-perfluorodecyl triethoxysilane to the ethanol is 1: 80;
and (4): and taking out the rock plate and drying at the drying temperature of 100 ℃ for 30min to obtain the hydrophobic antifouling rock plate imitating the banana leaf.
The hydrophobic antifouling rock plate imitating the banana leaf takes water as a medium, the static contact angle is 152 degrees, and the rolling angle is 12 degrees. The hydrophobic antifouling rock plate is inclined, dark soy sauce, light soy sauce, oil consumption and the like are dropped on the surface of the ceramic tile, and the dark soy sauce, the light soy sauce and the oil consumption roll down from the surface of the rock plate basically without residues.
Example 3
The preparation method of the banana leaf-imitated hydrophobic antifouling rock plate comprises the following steps:
step (1): etching and processing the surface of the rock plate by using ultraviolet nanosecond laser to form a micro-nano secondary composite structure; the distance between the micron-sized grooves of the micro-nano secondary composite structure is 150 micrometers; the ultraviolet nanosecond laser processing parameters are as follows: the laser scanning speed is 150mm/s, the processing times are 8 times, and the power is 3W;
step (2): ultrasonically cleaning the rock plate subjected to laser etching for 10min by using deionized water, and then drying; drying at 80 deg.C for 15 min;
and (3): immersing the dried rock plate bubble into ethanol solution containing 1H,1H,2H, 2H-perfluorodecyl triethoxysilane for 4H, wherein the volume ratio of 1H,1H,2H, 2H-perfluorodecyl triethoxysilane to ethanol is 1: 60, adding a solvent to the mixture;
and (4): and taking out the rock plate and drying at the drying temperature of 120 ℃ for 40min to obtain the hydrophobic antifouling rock plate imitating the banana leaf.
The hydrophobic antifouling rock plate imitating the banana leaf takes water as a medium, the static contact angle is 158 degrees, and the rolling angle is 10 degrees. The hydrophobic antifouling rock plate is inclined, dark soy sauce, light soy sauce, oil consumption and the like are dropped on the surface of the ceramic tile, and the dark soy sauce, the light soy sauce and the oil consumption roll down from the surface of the rock plate basically without residues.
Comparative example 1
The preparation method of the hydrophobic rock plate comprises the following steps:
step (1): etching the surface of the rock plate by using optical fiber nanosecond laser; the nanosecond laser processing parameters of the optical fiber are as follows: the laser scanning speed is 150mm/s, the processing times are 8 times, and the power is 3W;
step (2): ultrasonically cleaning the rock plate subjected to laser etching for 10min by using deionized water, and then drying; drying at 80 deg.C for 15 min;
and (3): immersing the dried rock plate bubble into ethanol solution containing 1H,1H,2H, 2H-perfluorodecyl triethoxysilane for 4H, wherein the volume ratio of 1H,1H,2H, 2H-perfluorodecyl triethoxysilane to ethanol is 1: 60, adding a solvent to the mixture;
and (4): and taking out the rock plate and drying at 100 ℃ for 20min to obtain the hydrophobic rock plate.
The static contact angle of the hydrophobic rock plate with water as a medium is 110 degrees, and water drops do not roll on the hydrophobic rock plate. The reason is that when the fiber laser with the wavelength of 1064nm is adopted for etching, the absorption of the ceramic material to the laser in the near-infrared to far-infrared wave band belongs to typical heat absorption, the laser is quickly converted into heat energy after being absorbed, so that the surface is melted, the heat influence on the peripheral area of the material is large while the material is removed, and the whole structure is in a molten state, so that no obviously regular micro-nano structure appears on the surface of the rock plate after etching, and only the effect of improving the surface roughness of the rock plate is achieved, and the rock plate cannot be endowed with good super-hydrophobic performance.
Comparative example 2
The preparation method of the hydrophobic rock plate comprises the following steps:
step (1): etching and processing the surface of the rock plate by using ultraviolet nanosecond laser to form a micro-nano secondary composite structure of the banana leaves; the distance between the micron-sized grooves of the micro-nano secondary composite structure is 400 mu m; the ultraviolet nanosecond laser processing parameters are as follows: the laser scanning speed is 300mm/s, the processing times are 1 time, and the power is 3W;
step (2): ultrasonically cleaning the rock plate subjected to laser etching for 10min by using deionized water, and then drying; drying at 80 deg.C for 15 min;
and (3): immersing the dried rock plate bubble into ethanol solution containing 1H,1H,2H, 2H-perfluorodecyl triethoxysilane for 4H, wherein the volume ratio of 1H,1H,2H, 2H-perfluorodecyl triethoxysilane to ethanol is 1: 60, adding a solvent to the mixture;
and (4): and taking out the rock plate and drying at the drying temperature of 120 ℃ for 40min to obtain the hydrophobic rock plate.
The static contact angle of the hydrophobic rock plate with water as a medium is 123 degrees, and water drops cannot roll on the surface. The reason is that the interval of the groove-shaped structures is too large, the laser scanning speed is high, the processing times are few, and a densely distributed micro-nano secondary composite structure cannot be formed on the surface of the rock plate, so that the rock plate cannot reach a super-hydrophobic state, and does not have a corresponding antifouling effect.
Comparative example 3
The preparation method of the hydrophobic rock plate comprises the following steps:
step (1): etching and processing the surface of the rock plate by using ultraviolet nanosecond laser to form a micro-nano secondary composite structure of the banana leaves; the distance between the micron-sized grooves of the micro-nano secondary composite structure is 150 micrometers; the laser processing parameters are that the laser scanning rate is 150mm/s, the processing times are 8 times, and the power is 3W;
step (2): ultrasonically cleaning the rock plate subjected to laser etching for 10min by using deionized water, and then drying; drying at 80 deg.C for 15 min;
and (3): air on the surface of the dried rock plateSpraying polytetrafluoroethylene coating, wherein the spraying amount of the polytetrafluoroethylene is 100g/m2；
And (4): and drying the rock plate sprayed with the polytetrafluoroethylene coating at the drying temperature of 120 ℃ for 20min to obtain the hydrophobic rock plate.
The static contact angle of the hydrophobic rock plate with water as a medium is 118 degrees, and water drops cannot roll on the surface. Adopt the mode of spraying polytetrafluoroethylene coating when reducing the rock plate surface energy, polytetrafluoroethylene can form the film on the rock plate surface, and the imitative banana leaf that film cover rock plate surface laser beam machining goes out receives the composite construction a little, loses the coupling of imitative banana leaf receives the composite construction a little with low surface energy material, leads to the rock plate can't reach super hydrophobic state, does not possess corresponding antifouling effect yet. According to the invention, a micro-nano secondary composite structure is formed on the surface of a compact rock plate, and silicon hydroxyl in fluorosilane molecules and hydroxyl on the surface of the rock plate are subjected to dehydration reaction, so that fluorosilane molecules are connected to the surface of the rock plate in a covalent bond mode, the surface free energy is further remarkably reduced, and the surface with super-hydrophobic characteristics can be obtained.
Claims (9)
1. The preparation method of the banana leaf-imitated hydrophobic antifouling rock plate is characterized by comprising the following steps of:
etching the surface of the ceramic rock plate by ultraviolet laser to form a micro-nano secondary composite structure; the micro-nano secondary composite structure comprises a micro-scale groove and nano-scale particles attached to the micro-scale groove;
cleaning and drying the rock plate with the micro-nano secondary composite structure formed on the surface;
soaking the dried rock plate in an ethanol solution containing fluorine silane to enable fluorosilane molecules to be connected to the surface of the rock plate in a covalent bond mode;
and taking out the soaked rock plate and drying again to obtain the hydrophobic antifouling rock plate imitating the banana leaf.
2. The method as claimed in claim 1, wherein the width of the micron-sized trenches is 20-60 μm, and the distance between adjacent micron-sized trenches is 100-250 μm.
3. The method according to claim 1 or 2, wherein the nano-sized particles have a particle size of 100-400 nm.
4. The production method according to any one of claims 1 to 3, wherein the processing parameters of the ultraviolet laser etching are as follows: the scanning speed is 100-250mm/s, the processing times are 2-8, the laser repetition frequency is 10-25kHz, and the power is 1-3W.
5. The production method according to any one of claims 1 to 4, characterized in that the volume ratio of fluorosilane and ethanol is 1:100 to 1: 50.
6. The method according to any one of claims 1 to 5, wherein the soaking time of the dried rock plate in the ethanol solution containing the fluorosilane is 3-4 h.
7. The production method according to any one of claims 1 to 6, wherein the fluorosilane is 1H,1H,2H, 2H-perfluorodecyltriethoxysilane.
8. The hydrophobic antifouling slate of artificial banana leaf obtained by the preparation method according to any one of claims 1 to 7, wherein the hydrophobic antifouling slate of artificial banana leaf has a static contact angle of 146-160 degrees and a rolling angle of 6-20 degrees with water as a medium.
9. The hydrophobic antifouling slate of artificial banana leaf according to claim 8, wherein the specification of the hydrophobic antifouling slate of artificial banana leaf is 300-900mm long x 300-900mm wide x 3-6mm high.
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