Super wear-resistant coating, preparation method thereof and glass applying coating

Abstract

The invention belongs to the technical field of glass coatings, and particularly relates to a super wear-resistant coating, a preparation method thereof and glass applying the coating. The super-wear-resistant coating comprises photosensitive glue and double-super-hydrophobic powder, the double-super-hydrophobic powder is composed of fluorinated octagonal prismatic silicon dioxide, octagonal prismatic linear silicon dioxide is obtained from the fluorinated octagonal prismatic silicon dioxide in the presence of hydrochloric acid by using dodecyl ammonium chloride as a template, tetraethoxysilane as a silicon source and deionized water as a solvent, and the double-super-hydrophobic powder is prepared from the photosensitive glue and the double-super-hydrophobic powder. And after sintering, dipping in a perfluorosilane solution to prepare the composite material. The preparation method comprises the following steps: preparing fluorinated octagonal prismatic silicon dioxide, bonding, pressing and curing the fluorinated octagonal prismatic silicon dioxide through a photosensitive adhesive to obtain the friction-resistant coating with an uneven double-super-hydrophobic function, and the obtained coating has super-strong friction resistance and still has a super-hydrophobic function after being rubbed for 1000 times.

Description

Technical Field

[0001] The present invention belongs to the technical field of glass coatings, and particularly relates to an ultra-wear-resistant coating, a preparation method thereof, and glass applying the coating. Background Art

[0002] A superhydrophobic surface refers to a surface with a contact angle with water greater than 150° and a rolling angle less than 10°. Such a surface has extremely strong hydrophobicity, making water almost spherical on its surface and capable of easily rolling and slipping. Superhydrophobic and dual-superhydrophobic surfaces are essentially the same, but the dual-superhydrophobic surface is an improvement in the coating performance of the superhydrophobic surface. A superhydrophobic surface can be superhydrophobic to liquid water with a surface tension of 72.1 mN / m. A dual-superhydrophobic surface can not only be superhydrophobic but also be superhydrophobic to other liquids with a surface tension lower than 72.1 mN / m, such as various oil droplets with a surface tension of 20 - 40 mN / m. If the solid surface is treated with the same low-surface-energy fluorine-containing material, then the microscopic structure and morphology of the solid surface can determine the superhydrophobic performance of the coating surface. Different microscopic structures result in different superhydrophobic surface properties.

[0003] Glass with dual-superhydrophobic properties has various uses: Dual-superhydrophobic glass installed on the exterior wall of a building can effectively prevent the attachment of rainwater, dust, and oil stains, keeping the curtain wall always clean. This not only improves the aesthetic appearance of the building but also reduces the labor and cost of cleaning the curtain wall. Windows in homes and offices using dual-superhydrophobic glass can better resist the erosion of pollutants on the glass and extend the service life of the window glass in areas with frequent acid rain weather. After the windshield of a car adopts the dual-superhydrophobic technology, rainwater will form water droplets on the glass surface and quickly slide off, reducing the frequency of using the windshield wiper and improving driving safety. When dual-superhydrophobic glass covers the surface of a solar panel, it can avoid the accumulation of pollutants such as dust and bird droppings, keep the surface of the panel clean, improve its absorption rate of sunlight, and thus enhance the photoelectric conversion efficiency.

[0004] However, currently, dual-superhydrophobic glass usually directly constructs micro-nano structures on the glass by methods such as the sol-gel method and chemical vapor deposition method to form dual-superhydrophobic properties. However, such micro-nano structures usually have a relatively high specific surface area and small size, and are relatively fragile. When subjected to external forces such as friction and scratching, the micro-nano structures on the surface are easily damaged, resulting in a decline in dual-superhydrophobic properties. Secondly, in order to achieve dual-superhydrophobic properties, the coatings on the glass surface are mostly coatings containing low-surface-energy substances. However, the bonding force between these coatings and the glass substrate is often limited. During long-term friction, due to the action of friction force, the coating may gradually separate from the glass substrate, thus exposing the glass surface and reducing the dual-superhydrophobic and wear-resistant properties of the glass. Summary of the Invention

[0005] In view of the above problems, the present invention provides a super wear-resistant coating, a preparation method thereof, and glass using the coating, which effectively solve the wear resistance problem of double super-hydrophobic and super-oleophobic glass.

[0006] To achieve the above object, the technical solution adopted by the present invention is as follows: a super wear-resistant coating, a preparation method thereof, and glass using the coating.

[0007] In the first aspect, the present invention provides a super wear-resistant coating: A super wear-resistant coating includes a photosensitive adhesive and double super-hydrophobic and super-oleophobic powder, and the double super-hydrophobic and super-oleophobic powder is composed of fluorinated octagonal silica.

[0008] Furthermore, the preparation method of the fluorinated octagonal silica is as follows: S1, Dissolve dodecyl ammonium chloride in a mixed solution of deionized water and hydrochloric acid, and stir and mix evenly under an ice bath to obtain a mixed solution I; S2, Dropwise add tetraethyl orthosilicate to the mixed solution I, react for 30 - 40 min under an ice bath, stir and react at room temperature for 10 - 12 h. After the reaction is complete, centrifuge and wash the precipitate in the reaction solution with deionized water, and dry the precipitate at 75 - 80 °C to obtain octagonal silica powder; S3, Calcinate the octagonal silica powder at 500 - 550 °C for 5 - 8 h, then put it into a perfluorosilane solution, and after natural drying, dry it to obtain fluorinated octagonal silica.

[0009] Furthermore, in S1, the dosage ratio of dodecyl ammonium chloride, deionized water, and hydrochloric acid is (1.5 - 1.8) g : (120 - 140) mL : (60 - 75) mL; the concentration of hydrochloric acid is 8 - 9 mol / L.

[0010] Furthermore, in S2, the dosage ratio of tetraethyl orthosilicate to dodecyl ammonium chloride is (2.7 - 3.1) mL : (1.5 - 1.8) g.

[0011] Furthermore, in S3, the dosage ratio of octagonal silica powder to perfluorosilane solution is (3 - 5) g : (5 - 8) mL.

[0012] Furthermore, the perfluorosilane solution in S3 is a cyclohexane solution containing one or more of 1H,1H,2H,2H-perfluorooctyltrichlorosilane, 1H,1H,2H,2H-perfluorodecyltrichlorosilane, 1H,1H,2H,2H-perfluorooctyltriethoxysilane, and 1H,1H,2H,2H-perfluorododecyltrimethoxysilane.

[0013] Furthermore, the concentration of the perfluorosilane solution in S3 is 1.2 - 1.5 wt%.

[0014] Further, the photosensitive adhesive is an acrylate adhesive or an epoxy resin adhesive.

[0015] In a second aspect, the present invention provides a method for preparing a super wear-resistant coating: A method for preparing a super wear-resistant coating includes the following steps: uniformly coating a photosensitive adhesive on the surface of a glass substrate, then covering the photosensitive adhesive bonding layer on the glass substrate with a large amount of the above-mentioned fluorinated octagonal silica, pressing the powder tightly, putting the pressed glass under an ultraviolet lamp for irradiation curing, removing the excess powder on the surface, and the coating on the obtained glass surface is the super wear-resistant coating.

[0016] In a third aspect, the present invention provides a glass with a super wear-resistant coating: A glass with a super wear-resistant coating is prepared by the following method: uniformly coating a photosensitive adhesive on the surface of a glass substrate, then covering the photosensitive adhesive bonding layer on the glass substrate with a large amount of fluorinated octagonal silica, pressing the powder tightly, putting the pressed glass under an ultraviolet lamp for irradiation curing, removing the excess powder on the surface, and obtaining a super wear-resistant coating glass.

[0017] Compared with the prior art, the present invention has the following beneficial effects: By preparing a special-shaped silica material and bonding it to a glass substrate using a photosensitive adhesive binder, the present invention obtains a glass material with dual superhydrophobic functions. Compared with the dual superhydrophobic glass material obtained by the traditional sol-gel method, it has stronger friction resistance.

[0018] This application preferentially uses dodecylammonium chloride as a template, tetraethyl orthosilicate as a silicon source, deionized water as a solvent, obtains octagonal linear silica under the condition of hydrochloric acid, sinters it, impregnates it with a perfluorosilane solution to obtain fluorinated octagonal silica, and obtains a dual superhydrophobic coating with unevenness through bonding, pressing and curing. An inner concave structure is formed by the fluorinated octagonal silica, and finally it has extremely strong friction resistance and still has a superhydrophobic function after 1000 times of friction. Description of the Drawings

[0019] Figure 1 SEM and TEM diagrams of the glass coating prepared by the spraying method, where a is the TEM of Comparative Example 1; b is the TEM of Comparative Example 2; c is the TEM of Comparative Example 3; d is the TEM of Example 2; the following are their corresponding SEMs respectively; Figure 2 Liquid contact angle of the fluorinated glass coating prepared by the spraying method; Figure 3 Schematic diagram of superoleophobicity of the octagonal coating glass; Figure 4 Wear resistance test of the super wear-resistant coating glass of Example 2; Figure 5 SEM image of the super wear-resistant coating glass of Example 2 after friction. Detailed implementation manners

[0020] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0021] Example 1 A super wear-resistant coating, characterized in that: it includes a photosensitive adhesive and a double super-hydrophobic powder, and the double super-hydrophobic powder is composed of fluorinated octagonal silica.

[0022] The preparation method of the fluorinated octagonal silica is as follows: S1, 1.5 g of dodecylammonium chloride is dissolved in a mixed solution of 120 mL of deionized water and 60 mL of 8 mol / L hydrochloric acid, and stirred and mixed evenly under an ice bath to obtain a mixed solution I; S2, 2.7 mL of tetraethyl orthosilicate is added dropwise to the mixed solution I, reacted for 30 min under an ice bath, stirred and reacted at room temperature for 10 h. After the reaction is complete, the precipitate in the reaction solution is centrifuged and washed with deionized water, and the precipitate is dried at 75 °C to obtain octagonal silica powder; S3, 3 g of the octagonal silica powder is calcined at 500 °C for 5 h, then put into 5 mL of a 1.2 wt% perfluorosilane solution, naturally dried, and then dried at 100 °C for 1 h to obtain fluorinated octagonal silica. The perfluorosilane solution is a cyclohexane solution of 1H,1H,2H,2H-perfluorooctyltrichlorosilane; The photosensitive adhesive is an epoxy resin adhesive.

[0023] Example 2 A super wear-resistant coating, characterized in that: it includes a photosensitive adhesive and a double super-hydrophobic powder, and the double super-hydrophobic powder is composed of fluorinated octagonal silica.

[0024] The preparation method of the fluorinated octagonal silica is as follows: S1, 1.65 g of dodecylammonium chloride is dissolved in a mixed solution of 130 mL of deionized water and 68 mL of 8.5 mol / L hydrochloric acid, and stirred and mixed evenly under an ice bath to obtain a mixed solution I; S2. Add 2.9 mL of tetraethyl orthosilicate dropwise to the mixed solution I, react for 35 min under an ice bath, stir and react for 11 h at room temperature. After the reaction is complete, centrifuge and wash the precipitate in the reaction solution with deionized water, and dry the precipitate at 78 °C to obtain octagonal silica powder; S3. Calcinate 4 g of octagonal silica powder at 525 °C for 7 h, then put it into 6.5 mL of a perfluorosilane solution with a concentration of 1.3 wt%, dry it naturally, and then dry it at 100 °C for 1 h to obtain fluorinated octagonal silica. The perfluorosilane solution is a cyclohexane solution of 1H,1H,2H,2H-perfluorodecyltrichlorosilane; The photosensitive adhesive is an acrylate adhesive.

[0025] Example 3 A super wear-resistant coating, characterized in that it comprises a photosensitive adhesive and a double super-hydrophobic powder, and the double super-hydrophobic powder is composed of fluorinated octagonal silica.

[0026] The preparation method of the fluorinated octagonal silica is as follows: S1. Dissolve 1.8 g of dodecylammonium chloride in a mixed solution of 140 mL of deionized water and 75 mL of 9 mol / L hydrochloric acid, stir and mix evenly under an ice bath to obtain a mixed solution I; S2. Add 3.1 mL of tetraethyl orthosilicate dropwise to the mixed solution I, react for 40 min under an ice bath, stir and react for 12 h at room temperature. After the reaction is complete, centrifuge and wash the precipitate in the reaction solution with deionized water, and dry the precipitate at 80 °C to obtain octagonal silica powder; S3. Calcinate 5 g of octagonal silica powder at 550 °C for 8 h, then put it into 8 mL of a perfluorosilane solution with a concentration of 1.5 wt%, dry it naturally, and then dry it at 100 °C for 1 h to obtain fluorinated octagonal silica. The perfluorosilane solution is a cyclohexane solution of 1H,1H,2H,2H-perfluorooctyltriethoxysilane; The photosensitive adhesive is an acrylate resin adhesive.

[0027] The preparation method of the glass with the super wear-resistant coating includes the following steps: uniformly coat the photosensitive adhesive on the surface of the glass substrate, control the thickness of the photosensitive adhesive to be about 50 microns by the coating speed, then cover a large amount of fluorinated octagonal silica on the photosensitive adhesive bonding layer on the glass substrate, press the powder tightly, and put the pressed glass under an ultraviolet lamp for irradiation curing, and remove the excess powder on the surface to obtain the super wear-resistant coating glass.

[0028] Comparative Example 1 The same as Example 2, except that the amount of dodecylammonium chloride is adjusted to be 1.45 g less.

[0029] Comparative Example 2 Same as Example 2, except that the concentration of hydrochloric acid is adjusted to 11 mol / L.

[0030] Comparative Example 3 Same as Example 2, except that the amount of tetraethyl orthosilicate is adjusted to 3.2 mL.

[0031] Comparative Example 4 The double-superhydrophobic glass was prepared by the sol-gel method: 3.1 mL of tetraethyl orthosilicate, 80 mL of absolute ethanol, and 50 mL of deionized water were mixed evenly, 68 mL of 8.5 mol / L hydrochloric acid was added, and the mixture was stirred evenly to cause the hydrolysis reaction of tetraethyl orthosilicate to form a silica sol. 0.08 g of 1H,1H,2H,2H-perfluorodecyltrichlorosilane was added to the sol, and stirring was continued for 20 min to make it fully mixed. The sol was evenly coated on the glass surface by the spraying method, dried at room temperature for 24 h, and then cured at 80 °C for 3 h.

[0032] Performance test a. To facilitate seeing the structure of octagonal silica on the glass coating, the coated glass was first prepared by the spraying method: 0.5 g of octagonal silica prepared in Example 2 and Comparative Examples 1-3 was ultrasonically dispersed in 60 mL of ethanol, and 5 mL was sprayed on a glass substrate (3×3 cm 2 ) at 5 mL / min at 200 °C. After spraying, the coated glass was sintered in air at 525 °C for 1 h and cooled naturally. Then, a transmission electron microscope (TEM) and a scanning electron microscope (SEM) were used to observe the surface particles. The results are as Figure 1 shown.

[0033] From Figure 1 it can be seen that in d, the TEM image of Example 2 shows that it is obvious to see nanowire materials, with a morphology of an octagonal shape with a diameter of about 800 nanometers and a length of about dozens of micrometers; in a, the amount of dodecylammonium chloride added in Comparative Example 1 is less, and the TEM image shows that it is a large-particle agglomerated material with a size of about a dozen micrometers and no obvious morphology, and the SEM image shows that the coating surface has a rough feeling; in b, the amount of hydrochloric acid added in Comparative Example 2 increases, and the TEM image shows that there are fewer octagonal wire materials and a thicker diameter, and the SEM image shows that the coating is composed of a mixture of wire materials and particle materials; in c, the content of tetraethyl orthosilicate increases, and its TEM image shows a certain amount of octagonal wire materials with a slightly thicker diameter.

[0034] b. The sintered coated glass in a was immersed in a cyclohexane solution containing 1.3 wt% of 1H,1H,2H,2H-perfluorodecyltrichlorosilane for 2 minutes, air-dried naturally for 25 minutes, and then the air-dried coated glass was placed on a heating platform at 450 °C and heated for 5 minutes. The contact angles of olive oil, water, dodecane, and hexadecane on the glass coating were measured at room temperature using a contact angle tester. The results are as Figure 2 shown.

[0035] As can be seen from Figure 2 , for all the coated glasses of Example 2 and Comparative Examples 1 - 3, the coating surfaces can be superhydrophobic and oleophobic to olive oil. The contact angles of all coatings with hexadecane and dodecane are less than 150°. The superhydrophobic ability of the coating in Example 2 is relatively good. The reason why the coating in Comparative Example 1 can be superoleophobic is that there are a large number of micron-sized protrusions on its coating surface, and there are many nano-sized secondary structures on the surface of the protrusions, and at the same time, it has a large pore structure, and there is an inward concave tendency at the edge of the micron protrusions. The superoleophobic properties of the coatings in Comparative Example 2, Comparative Example 3, and Example 2 should be related to the structure of their special octagonal prism-shaped linear materials. The octagonal prism has an inward concave surface, and its edge is easy to form an inward concave structure. The inward concave structure will generate an upward force F on the liquid surface, which balances the force of the liquid penetrating downward, so that the liquid droplet can be suspended on the rough interface. At the same time, the oil droplet has a certain spread on the protrusion surface, and the liquid droplet is easy to form a transition state between Cassie and Wenzel on the coating surface, showing a double superhydrophobic state (as Figure 3 shown).

[0036] c. The superwear-resistant coated glass obtained by applying photosensitive glue to the fluorinated octagonal prism-shaped silica in Example 2 and the double superhydrophobic glass prepared by the sol-gel method in Comparative Example 4 were subjected to a friction resistance test (test conditions: pressure of 6 Kpa, sandpaper of 2000 mesh, friction speed of 25 times per minute), and the contact angles of the coating with water were measured at different friction times. The results are as Figure 4 shown.

[0037] As can be seen from Figure 4 , after 1000 times of friction, the contact angle of the coating of the superwear-resistant coated glass prepared in Example 2 is still greater than 150°, showing excellent abrasion resistance. However, for the coating of the double superhydrophobic glass prepared in Comparative Example 4, after about 500 times of friction, its contact angle is less than 150°, losing the superhydrophobic function.

[0038] d. After the superwear-resistant coated glass obtained by applying photosensitive glue to the fluorinated octagonal prism-shaped silica in Example 2 was subjected to the friction resistance test described in c, the coating morphology was observed by scanning electron microscopy, and the results are as Figure 5 shown.

[0039] As can be seen from Figure 5As can be seen from a, the protruding part of the coating is friction-damaged, while other parts are intact. This may be because during the preparation process, the photosensitive glue is imprinted by powder, making the coating surface have a very rough structure, so that the coating surface is not flat, but part of it is concave and part is convex, and it remains intact during the friction process. As shown in b, when the coating is not damaged, one end or one side of the octagonal fluorinated silica is glued by glue. As shown in c, after the coating is friction-damaged, there are obvious scratches. The protruding part is friction-damaged, but a large amount of octagonal fluorinated silica can still be bonded to the photosensitive glue at the bottom without being damaged, so it still has superhydrophobic function. In addition, after testing, when the friction is 1000 times, a 30 μL droplet can roll away at about 9°.

[0040] Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A super wear-resistant coating, characterized in that: It includes a photosensitive adhesive and double super-hydrophobic and super-oleophobic powder, and the double super-hydrophobic and super-oleophobic powder is composed of fluorinated octahedral silica.

2. The super wear-resistant coating according to claim 1, characterized in that: The preparation method of the fluorinated octahedral silica is as follows: S1. Dodecylammonium chloride is dissolved in a mixed solution of deionized water and hydrochloric acid, and stirred and mixed evenly under an ice bath to obtain a mixed solution I; S2. Tetraethyl orthosilicate is added dropwise to the mixed solution I, and the reaction is carried out for 30 - 40 min under an ice bath and then stirred at room temperature for 10 - 12 h. After the reaction is complete, the precipitate in the reaction solution is centrifuged and washed with deionized water, and the precipitate is dried at 75 - 80 °C to obtain octahedral silica powder; S3. The octahedral silica powder is calcined at 500 - 550 °C for 5 - 8 h, then put into a perfluorosilane solution, and after natural drying, it is dried to obtain fluorinated octahedral silica.

3. The super wear-resistant coating according to claim 2, characterized in that: In S1, the dosage ratio of dodecylammonium chloride, deionized water and hydrochloric acid is (1.5 - 1.8) g : (120 - 140) mL : (60 - 75) mL; the concentration of hydrochloric acid is 8 - 9 mol / L.

4. The super wear-resistant coating according to claim 2, characterized in that: In S2, the dosage ratio of tetraethyl orthosilicate to dodecylammonium chloride is (2.7 - 3.1) mL : (1.5 - 1.8) g.

5. The super wear-resistant coating according to claim 2, characterized in that: In S3, the dosage ratio of the octahedral silica powder to the perfluorosilane solution is (3 - 5) g : (5 - 8) mL.

6. The super wear-resistant coating according to claim 2, characterized in that: In S3, the perfluorosilane solution is a cyclohexane solution containing one or more of 1H,1H,2H,2H-perfluorooctyltrichlorosilane, 1H,1H,2H,2H-perfluorodecyltrichlorosilane, 1H,1H,2H,2H-perfluorooctyltriethoxysilane, and 1H,1H,2H,2H-perfluorododecyltrimethoxysilane.

7. The super wear-resistant coating according to claim 2, characterized in that: In S3, the concentration of the perfluorosilane in the perfluorosilane solution is 1.2 - 1.5 wt%.

8. The super wear-resistant coating according to claim 1, characterized in that: The photosensitive adhesive is an acrylate adhesive or an epoxy resin adhesive.

9. A method for preparing the super wear-resistant coating according to any one of claims 1-8, characterized in that: It includes the following steps: The photosensitive adhesive is evenly coated on the surface of the glass substrate, then a large amount of fluorinated octahedral silica is covered on the photosensitive adhesive bonding layer on the glass substrate, the powder is pressed tightly, the pressed glass is placed under an ultraviolet lamp for irradiation curing, and the excess powder on the surface is removed. The coating on the obtained glass surface is the super wear-resistant coating.

10. A glass applying the super wear-resistant coating according to any one of claims 1-8, characterized in that: It is prepared by the following steps: The photosensitive adhesive is evenly coated on the surface of the glass substrate, then a large amount of fluorinated octahedral silica is covered on the photosensitive adhesive bonding layer on the glass substrate, the powder is pressed tightly, the pressed glass is placed under an ultraviolet lamp for irradiation curing, and the excess powder on the surface is removed to obtain super wear-resistant coating glass.

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