CN114988719A - High-transparency hydrophobic-oleophobic self-cleaning coating and preparation method thereof - Google Patents

High-transparency hydrophobic-oleophobic self-cleaning coating and preparation method thereof Download PDF

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CN114988719A
CN114988719A CN202210710012.8A CN202210710012A CN114988719A CN 114988719 A CN114988719 A CN 114988719A CN 202210710012 A CN202210710012 A CN 202210710012A CN 114988719 A CN114988719 A CN 114988719A
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coating
self
cleaning coating
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陈若愚
孙琳
贾倩
王红宁
刘小华
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Changzhou University
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/06—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain multicolour or other optical effects
    • B05D5/061—Special surface effect
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/001—General methods for coating; Devices therefor
    • C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2506/00—Halogenated polymers
    • B05D2506/10—Fluorinated polymers
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/76—Hydrophobic and oleophobic coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/112—Deposition methods from solutions or suspensions by spraying
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase
    • C03C2218/152—Deposition methods from the vapour phase by cvd

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Abstract

The invention belongs to the technical field of coatings, and particularly relates to a high-transparency hydrophobic and oleophobic self-cleaning coating and a preparation method thereof. Pretreating a nano carbon material to obtain a carboxylated nano carbon material, taking the carboxylated nano carbon material as a template, adding a silicon source under an alkaline condition to modify polysiloxane, centrifuging, drying and redispersing the modified carbon nano tube to obtain a coating liquid; uniformly spraying the coating liquid on the surface of the base material, and carrying out annealing treatment to remove the nano carbon template; and finally, carrying out fluorination treatment on the substrate to obtain the high-transparency hydrophobic and oleophobic self-cleaning coating. The highest light transmittance of the coating prepared by the method can reach 85.02%, the water contact angle is 165 degrees, the rolling angle is less than 3 degrees, the ethylene glycol contact angle is 145 degrees, and the contact angle of the vegetable oil is 125 degrees. The coating has high transparency and self-cleaning performance, and has important significance in self-cleaning, antifouling, condensation, anti-icing and other applications.

Description

High-transparency double-hydrophobic self-cleaning coating and preparation method thereof
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a high-transparency hydrophobic and oleophobic self-cleaning coating and a preparation method thereof.
Background
Nowadays, the surfaces of materials suffer from various pollution problems, and the antifouling of building walls, container surfaces, automobile glass, and optical surfaces such as computers and mobile phones, which are common in life, are of considerable interest. The double-hydrophobic surface has important application value in the fields of self-cleaning, corrosion prevention, oil transportation, biological adhesion prevention devices, oil collection, pollution prevention, oil-water separation and the like. Therefore, the research on the antifouling transparent coating with the double-phobicity and the self-cleaning property has obvious practical significance.
Studies have shown that roughness and low surface energy are necessary to produce a super-amphiphobic surface, but the requirements for high surface roughness and high transparency on the coating structure are contradictory. Increasing the surface roughness to the micrometer scale hinders optical transparency, while decreasing the roughness to the nanometer scale decreases light scattering, increases light transmittance, but the performance of the coating in all respects is greatly reduced. Therefore, it is a great challenge to prepare a super-amphiphobic transparent coating in a simple and low-cost manner, and the prepared coating has good self-cleaning performance to resist severe environmental conditions for practical application.
Disclosure of Invention
In order to solve the problems pointed out in the background technology part, the invention provides a high-transparency hydrophobic-oleophobic self-cleaning coating and a preparation method thereof, wherein the high-transparency hydrophobic-oleophobic self-cleaning coating comprises the following steps: pretreating a nano carbon material to obtain a carboxylated nano carbon material, taking the carboxylated nano carbon material as a template, adding a silicon source under an alkaline condition to modify polysiloxane, centrifuging, drying and redispersing the modified carbon nano tube to obtain a coating liquid; uniformly spraying the coating liquid on the surface of the base material, and carrying out annealing treatment to remove the nano carbon template; and finally, carrying out fluorination treatment on the base material to obtain the amphiphobic coating. The preparation method mainly comprises the following steps:
(1) preparing concentrated sulfuric acid and concentrated nitric acid into mixed acid liquor according to the volume ratio of 3: 1, treating a nano-carbon material (carbon nanospheres or a mixture of multi-walled carbon nanotubes and carbon nanospheres) with the mixed acid liquor at 60 ℃ for 1h, carrying out vacuum filtration, washing with deionized water until the pH value of filtrate is 5-6, and then drying at 80 ℃ for 24h to obtain an acidized carboxylated nano-carbon material (CNs-COOH);
wherein, during treatment, the mass-volume ratio of the nano carbon material to the mixed acid solution is 1 g: 100 mL;
the diameter of the carbon nanosphere is as follows: 20-100 nm; the diameter of the multi-wall carbon nano tube is as follows: 30-50 nm;
when the nano carbon material is a mixture, the mass ratio of the multi-wall carbon nano tube to the carbon nano sphere is 1-4: 1.
(2) Dispersing CNs-COOH in ethanol (EtOH) and ammonia (NH) 4 OH), uniformly stirring, then adding a silicon source, and stirring for 6 hours at 25 ℃;
wherein, CNs-COOH, NH 4 The mass ratio of OH to EtOH is 1:110: 700;
the silicon source is more than one of tetraethyl orthosilicate (TEOS), Methyl Triethoxysilane (MTES) and hexadecyl trimethoxysilane (HDTMS), and the addition amount is 1 ml.
When silane is a mixed silicon source of HDTMS and TEOS, the molar ratio of the TEOS to the HDTMS is 1: 1.13;
when silane is a mixed silicon source of MTES and TEOS, the molar ratio of TEOS to MTES is 2: 1.
(3) Centrifuging the product obtained in the step (2), washing with EtOH to remove unreacted substances, drying at 60 ℃ for 12 hours to obtain polysiloxane modified CNs, and re-dispersing the CNs in a solvent through ultrasonic action;
wherein the redispersion solvent is n-octane or 2-isopropoxy ethanol, and the concentration of the solution after dispersion is 1 g/L.
(4) And (4) spraying the coating liquid obtained in the step (3) on a glass substrate, curing at 100 ℃ for 5min, then annealing in a muffle furnace, and carrying out fluoridation treatment on the annealed substrate by using fluorine-containing silane to obtain the transparent hydrophobic and oleophobic self-cleaning coating.
Wherein the annealing temperature is 550 ℃ and the time is 3 h; the fluorine-containing silane is as follows: 1H,1H,2H, 2H-Perfluorodecyltriethoxysilane (PFDTES) or 1H,1H,2H, 2H-Perfluorodecyltrichlorosilane (PFDTCS).
The fluorination method comprises the following steps: the film was placed in a vacuum desiccator, 500. mu.L FDTES or PFDTCS was added, chemical vapor deposited for 24h, and then cured at 80 ℃ for 20 min.
Compared with the prior art, the invention has the advantages that:
1. the preparation method disclosed by the invention is simple in preparation process, does not need strict process conditions and expensive equipment, improves the light transmittance after the template is removed, simultaneously retains the coarse structure of the nano-carbon material, and has obvious advantages in constructing the transparent double-hydrophobic self-cleaning coating.
2. The invention adopts the spraying method to prepare the coating, is not only suitable for the surface of glass, but also suitable for the surfaces of ceramics, metals and the like, and is expected to be used for large-scale production.
3. The coating prepared by the invention is oleophobic and hydrophobic, and has high light transmittance, the highest light transmittance reaches 85.02%, the highest water contact angle can reach 165 degrees, the rolling angle is less than 3 degrees, the highest ethylene glycol contact angle can reach 145 degrees, the vegetable oil contact angle can reach 125 degrees, and the double-hydrophobic effect is achieved.
4. The coating has good self-cleaning effect, can easily take away surface sand grains by only a small amount of water, does not leave stains on the surface of the coating, and can be used for self-cleaning, oil stain prevention and the like of the surfaces of equipment, vehicles, facilities and the like.
Description of the drawings:
FIG. 1 is a transmission electron microscope image of the coating obtained in example 9 of the present invention.
FIG. 2 is a scanning electron micrograph of the coating obtained in example 9 of the present invention.
FIG. 3 is a comparison of the self-cleaning process of the coated and blank glass sheets obtained in example 9 of the present invention, wherein a, b, c, and d are the glass sheet before self-cleaning, the coated sheet, and the glass sheet after self-cleaning, the coated sheet, respectively.
FIG. 4 is a static contact angle chart obtained in example 9 of the present invention, wherein a, b, and c are water, ethylene glycol, and vegetable oil, respectively.
Detailed Description
The present invention is further described below with reference to examples, but is not limited thereto.
Example 1
(1) Preparing concentrated sulfuric acid and concentrated nitric acid into mixed acid solution according to the volume ratio of 3: 1, and treating carbon nanospheres (with the diameter of 20nm) with the mixed acid solution at 60 ℃ for 1h, wherein the ratio of the carbon nanospheres to the mixed acid solution is 1 g: 100 mL; carrying out vacuum filtration, washing with deionized water until the pH value of the filtrate is 5-6, and then drying at 80 ℃ for 24h to obtain acidified CNs-COOH;
(2) 0.05g of CNs-COOH were dispersed in 35g of EtOH and 5.5g of NH 4 Uniformly stirring the OH mixed solution, then adding 1ml of silicon source, and stirring for 6 hours at 25 ℃;
wherein the silicon source is TEOS and HDTMS, and the molar ratio is 1: 1.13.
(3) And (3) centrifuging the product obtained in the step (2), washing with EtOH to remove unreacted substances, drying at 60 ℃ for 12 hours to obtain polysiloxane-modified CNs, and redispersing the polysiloxane-modified CNs in 50ml of n-octane solvent by ultrasonic action, wherein the concentration of the CNs is 1 g/L.
(4) And (4) spraying the coating liquid obtained in the step (3) on a glass substrate, curing at 100 ℃ for 5min, annealing at 550 ℃ for 3h in a muffle furnace, and performing PFDTES fluorination treatment on the annealed substrate to obtain the transparent hydrophobic-hydrophobic self-cleaning coating.
The fluorination method comprises the following steps: the film was placed in a vacuum desiccator, 500. mu.L FDTES was added, chemical vapor deposited for 24h, and then cured at 80 ℃ for 20 min. The maximum light transmittance of the coating was 78.63%, and a water contact angle of 112 ° was measured at 5 μ L.
Example 2
(1) CNs-COOH was prepared as in example 1;
wherein, the carbon nano material is: the mass ratio of the multi-wall carbon nano-tube (the diameter is 30-50nm) to the carbon nano-sphere (the diameter is 20nm) is 1:1.
(2) 0.05g of CNs-COOH were dispersed in 35g of EtOH and 5.5g of NH 4 Uniformly stirring the OH mixed solution, then adding 1ml of silicon source, and stirring for 6 hours at 25 ℃;
the silicon source is TEOS and HDTMS, and the molar ratio is 1: 1.13.
(3) The procedure for redispersing the polysiloxane-modified nanocarbon material was the same as in example 1.
(4) The procedure for preparing the transparent hydrophobic and oleophobic self-cleaning coating is the same as that of example 1. The maximum light transmittance of the coating was 87.65%, and a 5 μ L water contact angle of 125 ° and an ethylene glycol contact angle of 86 ° were measured.
Example 3
(1) CNs-COOH was prepared as in example 1;
wherein, the carbon nano material is: the mass ratio of the multi-wall carbon nano-tube (the diameter is 30-50nm) to the carbon nano-sphere (the diameter is 20nm) is 4: 1.
(2) 0.05g of CNs-COOH were dispersed in 35g of EtOH and 5.5g of NH 4 Uniformly stirring the OH mixed solution, then adding 1ml of silicon source, and stirring for 6 hours at 25 ℃;
the silicon source is TEOS and HDTMS, and the molar ratio is 1: 1.13.
(3) The procedure for redispersing the polysiloxane-modified nanocarbon material was the same as in example 1.
(4) The procedure for preparing the transparent hydrophobic and oleophobic self-cleaning coating is the same as that of example 1. The maximum light transmittance of the coating is 80.52%, and the measured contact angle of 5 microliter water is 135 degrees, the contact angle of ethylene glycol is 94 degrees, and the contact angle of edible oil is 91 degrees.
Example 4
(1) CNs-COOH was prepared as in example 1;
wherein, the carbon nano material is: carbon nanospheres (50 nm diameter).
(2) 0.05g of CNs-COOH were dispersed in 35g of EtOH and 5.5g of NH 4 Uniformly stirring the OH mixed solution, then adding 1ml of silicon source, and stirring for 6 hours at 25 ℃;
the silicon source is TEOS and HDTMS, and the molar ratio is 1: 1.13.
(3) The procedure for redispersing the polysiloxane-modified nanocarbon material was the same as in example 1.
(4) The procedure for preparing the transparent hydrophobic and oleophobic self-cleaning coating is the same as that of example 1. The maximum light transmittance of the coating was 80.32% and a water contact angle of 113 ° of 5 μ L was measured.
Example 5
(1) CNs-COOH was prepared as in example 1;
wherein, the carbon nano material is: a mixed material of multi-wall carbon nano-tubes (diameter of 30-50nm) and carbon nano-spheres (diameter of 50nm) with the mass ratio of 1:1.
(2) 0.05g of CNs-COOH were dispersed in 35g of EtOH and 5.5g of NH 4 OH mixed solution is evenly stirred, then 1ml of silicon source is added,stirring for 6h at 25 ℃;
the silicon source is TEOS and HDTMS, and the molar ratio is 1: 1.13.
(3) The procedure for redispersing the polysiloxane-modified nanocarbon material was the same as in example 1.
(4) The procedure for preparing the transparent hydrophobic and oleophobic self-cleaning coating is the same as that of example 1. The maximum light transmission of the coating was 84.6%, and a 5 μ L water contact angle of 137 ° and an ethylene glycol contact angle of 87 ° were measured.
Example 6
(1) CNs-COOH was prepared as in example 1;
wherein, the carbon nano material is: a mixed material of multi-wall carbon nano-tubes (diameter is 30-50nm) and carbon nano-spheres (diameter is 50nm) with the mass ratio of 4:1
(2) 0.05g of CNs-COOH were dispersed in 35g of EtOH and 5.5g of NH 4 Uniformly stirring the mixed solution of OH, then adding 1ml of silicon source, and stirring for 6 hours at 25 ℃;
the silicon source is TEOS and HDTMS, and the molar ratio is 1: 1.13.
(3) The procedure for redispersing the polysiloxane-modified nanocarbon material was the same as in example 1.
(4) The procedure for preparing the transparent hydrophobic and oleophobic self-cleaning coating is the same as that of example 1. The maximum light transmittance of the coating is 85.69%, and the measured contact angle of 5 microliter water is 144 degrees, the contact angle of ethylene glycol is 99 degrees, and the contact angle of edible oil is 97 degrees.
Example 7
(1) CNs-COOH was prepared as in example 1;
wherein, the carbon nano material is: carbon nanospheres (100 nm diameter).
(2) 0.05g of CNs-COOH were dispersed in 35g of EtOH and 5.5g of NH 4 Uniformly stirring the OH mixed solution, then adding 1ml of silicon source, and stirring for 6 hours at 25 ℃;
the silicon source is TEOS and HDTMS, and the molar ratio is 1: 1.13.
(3) The procedure for redispersing the polysiloxane-modified nanocarbon material was the same as in example 1.
(4) The procedure for preparing the transparent hydrophobic and oleophobic self-cleaning coating is the same as that of example 1. The maximum light transmittance of the coating is 84.32 percent, and the measured contact angle of 5 microliter of water is 112 degrees, the contact angle of ethylene glycol is 73 degrees, and the contact angle of edible oil is 67 degrees.
Example 8
(1) CNs-COOH was prepared as in example 1;
wherein the carbon nano material is a mixed material of multi-wall carbon nano tubes (the diameter is 30-50nm) and carbon nano spheres (the diameter is 100nm) in a mass ratio of 1: 1;
(2) 0.05g of CNs-COOH were dispersed in 35g of EtOH and 5.5g of NH 4 Uniformly stirring the mixed solution of OH, then adding 1ml of silicon source, and stirring for 6 hours at 25 ℃;
the silicon source is TEOS and HDTMS, and the molar ratio is 1: 1.13.
(3) The procedure for redispersing the polysiloxane-modified nanocarbon material was the same as in example 1.
(4) The procedure for preparing the transparent hydrophobic and oleophobic self-cleaning coating is the same as that of example 1. The maximum light transmittance of the coating is 86.27 percent, the measured water contact angle of 5 mul is 145 degrees, the rolling angle is less than 8 degrees, the ethylene glycol contact angle is 107 degrees, and the edible oil contact angle is 81 degrees.
Example 9
(1) CNs-COOH was prepared as in example 1;
wherein, the carbon nano material is: a mixed material of multi-walled carbon nano-tubes (with the diameter of 30-50nm) and carbon nano-spheres (with the diameter of 100nm) in a mass ratio of 4: 1;
(2) 0.05g of CNs-COOH were dispersed in 35g of EtOH and 5.5g of NH 4 Uniformly stirring the OH mixed solution, then adding 1ml of silicon source, and stirring for 6 hours at 25 ℃;
the silicon source is TEOS and HDTMS, and the molar ratio is 1: 1.13.
(3) The procedure for redispersing the polysiloxane-modified nanocarbon material was the same as in example 1.
(4) The procedure for preparing the transparent hydrophobic and oleophobic self-cleaning coating is the same as that of example 1. The maximum light transmittance of the coating is 85.02%, and the measured water contact angle of 5 mul is 165 degrees, the rolling angle is less than 3 degrees, the ethylene glycol contact angle is 145 degrees, and the edible oil contact angle is 125 degrees.
Example 10
(1) CNs-COOH was prepared as in example 1;
wherein, the carbon nano material is: a mixed material of multi-walled carbon nano-tubes (with the diameter of 30-50nm) and carbon nano-spheres (with the diameter of 100nm) in a mass ratio of 4: 1;
(2) 0.05g of CNs-COOH were dispersed in 35g of EtOH and 5.5g of NH 4 Uniformly stirring the OH mixed solution, then adding 1ml of silicon source, and stirring for 6 hours at 25 ℃;
the silicon source is TEOS and HDTMS, the molar ratio is 1:1.13, and the adding amount is 1 ml.
(3) The procedure for redispersing the polysiloxane-modified nanocarbon material was the same as in example 1.
Wherein the redispersion solvent is 2-isopropoxyethanol.
(4) The procedure for preparing the transparent hydrophobic-both self-cleaning coating is the same as in example 1. The maximum light transmittance of the coating is 81.47%, the measured water contact angle of 5 mul is 157 degrees, the rolling angle is less than 3 degrees, the ethylene glycol contact angle is 140 degrees, and the edible oil contact angle is 109 degrees.
Example 11
(1) CNs-COOH was prepared as in example 1;
wherein the carbon nano material is as follows: the mass ratio of the multi-wall carbon nano-tube (the diameter is 30-50nm) to the carbon nano-sphere (the diameter is 100nm) is 4: 1;
(2) 0.05g of CNs-COOH were dispersed in 35g of EtOH and 5.5g of NH 4 Uniformly stirring the mixed solution of OH, then adding 1ml of silicon source, and stirring for 6 hours at 25 ℃;
the silicon source is TEOS and MTES with a molar ratio of 2: 1.
(3) The procedure for redispersing the polysiloxane-modified nanocarbon material was the same as in example 1.
(4) The procedure for preparing the transparent hydrophobic and oleophobic self-cleaning coating is the same as that of example 1. The maximum light transmittance of the coating is 86.32%, and the measured contact angle of 5 mul water is 155 degrees, the rolling angle is less than 3 degrees, the contact angle of ethylene glycol is 130 degrees, and the contact angle of edible oil is 87 degrees.
Example 12
(1) CNs-COOH was prepared as in example 1;
wherein, the carbon nano material is: the mass ratio of the multi-wall carbon nano-tube (diameter of 30-50nm) to the carbon nano-sphere (diameter of 100nm) is 4: 1.
(2) 0.05g of CNs-COOH were dispersed in 35g of EtOH and 5.5g of NH 4 Uniformly stirring the OH mixed solution, then adding 1ml of silicon source, and stirring for 6 hours at 25 ℃;
the silicon source is TEOS and HDTMS, and the molar ratio is 1: 1.13.
(3) The procedure for redispersing the polysiloxane-modified nanocarbon material was the same as in example 1.
(4) And (4) spraying the coating liquid obtained in the step (3) on a glass substrate, curing for 5min at 100 ℃, then annealing in a muffle furnace, and carrying out fluorination treatment on the annealed substrate by using 1H,1H,2H, 2H-perfluorodecyl trichlorosilane (PFDTCS) to obtain the transparent hydrophobic-oleophobic self-cleaning coating.
Wherein the annealing temperature is 550 ℃ and the time is 3 h; the fluorination method comprises the following steps: the film was placed in a vacuum desiccator, 500. mu.L PFDTCS was added, chemical vapor deposited for 24h, and then cured at 80 ℃ for 20 min. The maximum light transmittance of the coating is 84.59%, and the measured contact angle of 5 mul water is 152 degrees, the rolling angle is less than 3 degrees, the contact angle of ethylene glycol is 136 degrees, and the contact angle of edible oil is 119 degrees.
Comparative example 1
(1) CNs-COOH was prepared as in example 1;
(2) 0.05g of CNs-COOH were dispersed in 35g of EtOH and 5.5g of NH 4 Uniformly stirring the OH mixed solution, then adding 1ml of silicon source, and stirring for 6 hours at 25 ℃;
wherein, the carbon nano material is: the mass ratio of the multi-wall carbon nano-tube (the diameter is 30-50nm) to the carbon nano-sphere (the diameter is 100nm) is 4:1, and the silicon source is TEOS.
(3) The procedure for redispersing the polysiloxane-modified nanocarbon material was the same as in example 1.
(4) The procedure for preparing the transparent hydrophobic and oleophobic self-cleaning coating is the same as that of example 1. The maximum light transmittance of the coating is 75.96%, and the measured contact angle of 5 mul water is 152 degrees, the rolling angle is less than 5 degrees, the contact angle of ethylene glycol is 131 degrees, and the contact angle of edible oil is 75 degrees.
Comparative example 2
(1) CNs-COOH was prepared as in example 1;
(2) dispersing 0.05g of CNs-COOH into a mixed solution of 35g of EtOH and 5.5g of NH4OH, uniformly stirring, then adding 1ml of silicon source, and stirring for 6h at 25 ℃;
wherein the carbon nano material is as follows: the mass ratio of the multi-wall carbon nano-tube (the diameter is 30-50nm) to the carbon nano-sphere (the diameter is 100nm) is 4:1, the silicon source is TEOS and HDTMS, and the molar ratio is 1: 1.13.
(3) The procedure for redispersing the polysiloxane-modified nanocarbon material was the same as in example 1.
(4) And (4) spraying the coating liquid obtained in the step (3) on a glass substrate, solidifying for 5min at 100 ℃, then annealing in a muffle furnace, and cooling to room temperature after annealing to obtain the coating.
Wherein the annealing temperature is 550 ℃ and the time is 3 h. The maximum light transmittance of the coating was 89.96%, and a water contact angle of 21 ° was measured at 5 μ L.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.

Claims (10)

1. A preparation method of a high-transparency hydrophobic-oleophobic self-cleaning coating is characterized by comprising the following steps:
(1) treating the nano-carbon material with mixed acid liquor at 60 ℃ for 1h, carrying out vacuum filtration, washing with deionized water until the pH value of filtrate is 5-6, and then drying at 80 ℃ for 24h to obtain an acidized carboxylated nano-carbon material (CNs-COOH);
(2) dispersing CNs-COOH in ethanol (EtOH) and ammonia (NH) 4 OH), uniformly stirring, then adding a silicon source, and stirring for 6 hours at 25 ℃;
(3) centrifuging the product obtained in the step (2), washing with EtOH to remove unreacted substances, drying at 60 ℃ for 12h to obtain polysiloxane-modified CNs, and re-dispersing the polysiloxane-modified CNs in a solvent through ultrasonic action to obtain a coating solution;
(4) and (4) spraying the coating liquid obtained in the step (3) on a glass substrate, curing at 100 ℃ for 5min, then annealing in a muffle furnace, and carrying out fluoridation treatment on the annealed substrate by using fluorine-containing silane to obtain the transparent hydrophobic and oleophobic self-cleaning coating.
2. The method of preparing a highly transparent amphiphobic self-cleaning coating of claim 1, wherein: the mixed acid liquid in the step (1) is prepared by mixing concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 3: 1, and the mass volume ratio of the nano-carbon material to the mixed acid liquid is 1 g: 100 mL; the nano carbon material is carbon nanosphere or mixture of multi-wall carbon nanotube and carbon nanosphere.
3. The method of preparing a highly transparent amphiphobic self-cleaning coating as claimed in claim 2, characterized in that: the diameter of the carbon nanosphere is as follows: 20-100 nm; the diameter of the multi-wall carbon nano tube is as follows: 30-50 nm; the mass ratio of the multi-wall carbon nano-tube to the carbon nano-sphere is 1-4: 1.
4. The method of preparing a highly transparent amphiphobic self-cleaning coating of claim 1, wherein: CNs-COOH, NH in step (2) 4 The mass ratio of OH to EtOH is 1:110: 700.
5. The method of preparing a highly transparent amphiphobic self-cleaning coating of claim 1, wherein: in the step (2), the silicon source is more than one of tetraethyl orthosilicate (TEOS), Methyltriethoxysilane (MTES) and hexadecyl trimethoxy silane (HDTMS), and the adding amount of the silane is 1 ml.
6. The method of preparing a highly transparent amphiphobic self-cleaning coating of claim 5, wherein: the molar ratio of TEOS to HDTMS was 1:1.13 and the molar ratio of TEOS to MTES was 2: 1.
7. The method of preparing a highly transparent amphiphobic self-cleaning coating of claim 1, wherein: in the step (3), the redispersion solvent is n-octane or 2-isopropoxyethanol.
8. The method of preparing a highly transparent amphiphobic self-cleaning coating of claim 1, wherein: the annealing temperature in the step (4) is 550 ℃, and the time is 3 h; the fluorine-containing silane is 1H,1H,2H, 2H-perfluorodecyl triethoxysilane (PFDTES) or 1H,1H,2H, 2H-perfluorodecyl trichlorosilane (PFDTCS).
9. The method of preparing a highly transparent amphiphobic self-cleaning coating of claim 1, wherein: the specific fluorination treatment method in the step (4) comprises the following steps: the film was placed in a vacuum desiccator, 500. mu.L FDTES or PFDTCS was added, chemical vapor deposited for 24h, and then cured at 80 ℃ for 20 min.
10. A highly transparent amphiphobic self-cleaning coating prepared by the process of any one of claims 1 to 9.
CN202210710012.8A 2022-06-22 2022-06-22 High-transparency hydrophobic-oleophobic self-cleaning coating and preparation method thereof Pending CN114988719A (en)

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CN103524053A (en) * 2012-07-03 2014-01-22 中国科学院兰州化学物理研究所 Preparation method of transparent super-hydrophobic coatings
CN103965673A (en) * 2014-05-05 2014-08-06 江南大学 Preparation method of super-hydrophobic, super-oleophobic and high transparency triple-function coating film
CN105562314A (en) * 2015-12-17 2016-05-11 上海必定化工有限公司 Preparation method of transparent super-amphiphobic hot water and hot oil coating
CN110386761A (en) * 2019-08-02 2019-10-29 常州大学 A kind of super-hydrophobic anti-reflection with high transparency penetrates the preparation method of coating
CN112063202A (en) * 2020-09-11 2020-12-11 中国人民解放军军事科学院防化研究院 Super-amphiphobic carbon nanotube coating and preparation method thereof
CN113174167A (en) * 2021-05-10 2021-07-27 中山大学 Preparation method of transparent super-amphiphobic material
CN113185898A (en) * 2021-05-18 2021-07-30 南昌航空大学 Method for preparing super-hydrophobic dual-functional coating by adopting spraying method
CN113754308A (en) * 2021-09-30 2021-12-07 常州大学 Preparation method of super-amphiphobic antifouling transparent coating

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103524053A (en) * 2012-07-03 2014-01-22 中国科学院兰州化学物理研究所 Preparation method of transparent super-hydrophobic coatings
CN103965673A (en) * 2014-05-05 2014-08-06 江南大学 Preparation method of super-hydrophobic, super-oleophobic and high transparency triple-function coating film
CN105562314A (en) * 2015-12-17 2016-05-11 上海必定化工有限公司 Preparation method of transparent super-amphiphobic hot water and hot oil coating
CN110386761A (en) * 2019-08-02 2019-10-29 常州大学 A kind of super-hydrophobic anti-reflection with high transparency penetrates the preparation method of coating
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