CN115197613B - Coated substrate with anti-ice coating and preparation method thereof - Google Patents
Coated substrate with anti-ice coating and preparation method thereof Download PDFInfo
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- CN115197613B CN115197613B CN202210717042.1A CN202210717042A CN115197613B CN 115197613 B CN115197613 B CN 115197613B CN 202210717042 A CN202210717042 A CN 202210717042A CN 115197613 B CN115197613 B CN 115197613B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention discloses a coating base material containing an anti-ice coating and a preparation method thereof, and particularly discloses an anti-ice coating, which comprises graphene nanosheets and a liquid medium containing fluorine resin, wherein the concentration of the graphene nanosheets is 2-5 mg/ml. The invention also provides a preparation method and application of the anti-ice coating, a method for forming an anti-ice coating on the surface of a substrate by applying the anti-ice coating, and the prepared coated substrate. According to the anti-ice coating, the graphene nanosheet and the fluorine-containing resin are applied to the substrate under the synergistic effect to form the anti-ice coating, so that the high adhesion of the substrate to the surface of the coating and the extremely low ice adhesion of the surface of the coating are realized, and the icing time is delayed to a certain extent.
Description
Technical Field
The invention belongs to the technical field of functional material preparation, and particularly relates to a coated substrate containing an anti-ice coating and a preparation method thereof.
Background
In various fields such as aviation, electric power transportation, communication, ground transportation and the like, icing has a very adverse effect on industrial facilities including traffic systems, telecommunication systems and energy systems, and often causes catastrophic safety problems and huge economic losses.
In the related art, the anti-icing/deicing modes mainly include an active mode and a passive mode, the active deicing mainly includes active deicing and deicing realized by applying traditional methods such as chemical agents (ice melting agents), thermal force (steam heating, electric heating deicing), mechanical force (mechanical vibration) and the like, however, the active deicing mode usually faces the problems of high cost, low time efficiency, high energy consumption, complex design, environmental pollution and the like.
In recent years, passive anti-icing/deicing materials and surfaces with zero energy consumption have received great attention, and in the related art, the main technical means are as follows:
(1) A smooth liquid is injected into the porous surface. For example, researchers have simulated the smooth leaves of terrestrial plants (e.g., nepenthes) and developed a series of smooth porous surfaces impregnated with lubricating oils and waxy organogels that greatly reduce the adhesion of ice so that it can be easily separated by gravity or air flow. However, this method suffers from the disadvantages of expensive cost of the injected lubricant, susceptibility to damage due to mechanical wear or multiple icing/de-icing cycles, and the need for frequent repair and oil replenishment, and is limited in practical use.
(2) Hygroscopic polymers are used to prepare highly hydrated icephobic coatings and hydrogels. The water-containing lubricating layer can obviously reduce the adhesion degree of ice, thereby inhibiting the ice accumulation under the action of wind. However, such coatings or gels are relatively complex to prepare and are highly susceptible to damage in humid or other extreme climates.
(3) A superhydrophobic structure or coating; in combination with each stage in the freezing process, supercooled liquid droplets firstly wet the solid surface and then are rapidly frozen into ice, under the condition, the super-hydrophobic surface can be called as an ideal anti-ice surface, for example, in the related art, a hydrophobic surface prepared by modification treatment of a low surface energy reagent such as silane and the like, a super-hydrophobic structure surface prepared by micro-nano structure design and the like. On the one hand, it can remove supercooled droplets by simply tilting the surface, bouncing the droplets off the surface, etc., reducing the probability of their nucleation on the surface; on the other hand, heat transfer between the coated surface and the supercooled droplets is significantly suppressed, thereby lowering the freezing temperature and delaying the freezing time. However, most of the super-hydrophobic coatings in the related art are brittle, and due to the low adhesion of low surface energy materials, the coatings are easily damaged by various machines such as peeling, abrasion and dynamic impact, and the preparation process is generally complex, and cannot meet the strict requirements of industrial application.
Disclosure of Invention
The present invention has been made to solve at least some of the technical problems of the related art, and it is therefore an object of embodiments of the present invention to provide an anti-ice coating material and a method for preparing the same.
It is a further object of embodiments of the present invention to provide the use of the above-described anti-ice coating for improving the ice adhesion properties of a substrate.
It is another object of embodiments of the present invention to provide a coated substrate containing an anti-ice coating and a method of making the same.
The embodiment of the invention provides an anti-ice coating, which comprises a graphene nanosheet and a liquid medium containing fluororesin, wherein the concentration of the graphene nanosheet is 2-5 mg/ml.
According to the anti-ice coating disclosed by the embodiment of the invention, the anti-ice coating is applied to the substrate through the synergistic effect of the graphene nanosheets and the fluorine-containing resin to form the anti-ice coating, so that the high adhesion of the substrate to the surface of the coating and the extremely low ice adhesion of the surface of the coating are realized, and the icing time is delayed to a certain extent.
In some embodiments, the graphene nanoplatelets have a platelet diameter of 1 to 10 μm and a thickness of 1 to 10nm. More preferably, the graphene nanoplatelets have a diameter of 2 to 3 μm and a thickness of 1 to 2nm.
In some embodiments, the liquid medium of the fluororesin has a solids content of 1 to 50 wt%.
In some embodiments, the fluororesin is one of an amorphous fluoropolymer, polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), or polyvinylidene fluoride (PVDF). Preferably, the fluorine-containing resin is an amorphous fluorine-containing polymer.
In some embodiments, when the fluorine-containing resin is an amorphous fluorine-containing polymer, the liquid medium of the fluorine-containing resin is a solution of the amorphous fluorine-containing polymer dissolved in a fluorine-based solvent at a concentration of 1 to 10 wt%.
In some embodiments, when the fluorine-containing resin is polytetrafluoroethylene, polychlorotrifluoroethylene, or polyvinylidene fluoride, the liquid medium of the fluorine-containing resin is a mixture according to (1-2): (1-2) a dispersion obtained by dissolving any one of a polytetrafluoroethylene emulsion, a polychlorotrifluoroethylene emulsion, and a polyvinylidene fluoride emulsion having a solid content of 50-60 wt% in a diluting solvent.
The embodiment of the invention also provides a preparation method of the anti-icing paint, which comprises the following steps: adding the graphene nanosheets into a liquid medium containing fluorine resin to obtain a mixture, and carrying out ultrasonic treatment on the mixture at the temperature of 20-50 ℃ for 6-8 h to uniformly disperse the graphene nanosheets in the liquid medium containing fluorine resin to obtain the anti-icing coating.
In some embodiments, the frequency of the sonication is between 20 and 30kHz.
The embodiment of the invention also provides application of the anti-ice coating in improving the ice adhesion performance of the substrate. The anti-ice coating is the anti-ice coating or the anti-ice coating prepared by the method.
The embodiment of the invention also provides a coated substrate containing the anti-ice coating, which comprises a substrate and the anti-ice coating formed on at least one surface of the substrate, wherein the anti-ice coating is formed by applying the anti-ice coating on the surface of the substrate and then curing the anti-ice coating, and the anti-ice coating is the anti-ice coating or the anti-ice coating prepared by the method.
In some embodiments, the anti-ice coating has a thickness of 10 to 30 μm. In some embodiments, the anti-ice coating has a thickness of 10 to 20 μm.
In some embodiments, the substrate is glass, silicon wafer, metal, plastic, or ceramic.
In some embodiments, the substrate is an Al sheet, high chromium bearing steel, stainless steel, glass, or silicon sheet.
In some embodiments, the substrate is an Al sheet.
The embodiment of the invention also provides a preparation method of the coated substrate with the anti-ice coating, which comprises the following steps:
(1) Pretreating at least one surface of the substrate;
(2) And (3) coating the anti-ice coating on the surface of the pretreated substrate obtained in the step (1) to obtain a wet coating, heating for curing, and cooling to obtain the anti-ice coating on the surface of the substrate, thus obtaining the coated substrate containing the anti-ice coating.
The preparation method of the coated substrate containing the anti-ice coating provided by the embodiment of the invention has the advantages of simple process, short production period and high repeatability, and is beneficial to large-scale industrial production.
In some embodiments, the pretreatment is grit blasting to provide a substrate surface roughness of 1 to 8 μm.
In some embodiments, the heat curing treatment temperature is 100-120 ℃ and the time is 1-2 h.
In some embodiments, the cooling may be air cooling for 8-10 h.
In some embodiments, the coating is spin coating, dip coating, or spray coating.
The embodiment of the invention has the advantages and beneficial effects that:
(1) According to the anti-ice coating provided by the embodiment of the invention, the anti-ice coating is applied to the substrate through the synergistic effect of the graphene nanosheets and the fluorine-containing resin to form the anti-ice coating, so that the high adhesion of the substrate to the surface of the coating and the extremely low ice adhesion of the surface of the coating are realized, and the icing time is delayed to a certain extent.
(2) The coated substrate containing the anti-ice coating effectively solves the problems that in the related technology, a super-hydrophobic surface prepared by modifying a low-surface-energy reagent, a deicing surface prepared by a hygroscopic polymer and the like are poor in adhesive capacity and are easily damaged by various mechanical damages such as peeling, abrasion, dynamic impact and the like.
(3) The coated substrate of the embodiment of the invention containing the anti-icing coating has extremely low ice adhesion and certain anti-icing delay time on the surface, and the anti-icing surface of the substrate has wide practical application significance on vehicles, equipment and buildings which work under the condition of the north pole.
(4) The preparation method of the coated substrate containing the anti-ice coating provided by the embodiment of the invention has the advantages of simple process, short production period and high repeatability, and is beneficial to large-scale industrial production.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Description of the drawings:
the above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic representation of the variation in icing retarding capability of a substrate with and without an anti-ice coating; wherein the icing sign is the generation of a peach-tip shaped solid shadow.
Fig. 2 is a schematic view of an ice adhesion testing apparatus used in an embodiment of the present invention.
FIG. 3 is a graph showing the variation of ice adhesion strength between a sample of specular Al sheet with an anti-ice coating and a sample of specular Al sheet without an anti-ice coating prepared in example 1 of the present disclosure.
Fig. 4 is a graph illustrating the change in ice adhesion strength between sheets of high chromium bearing steel (GCr 15) with ice-resistant coating and sheets of high chromium bearing steel (GCr 15) without ice-resistant coating that were only grit blasted alone, prepared in example 2 of the present disclosure.
FIG. 5 is a graph showing the change in ice adhesion strength between a 304 stainless steel sheet having an anti-ice coating prepared according to example 3 of the present disclosure and a 304 stainless steel sheet that is not coated with an anti-ice coating but was sand blasted alone.
FIG. 6 is a graph showing the variation of ice adhesion strength between a specular Al sheet with an anti-ice coating and a specular Al sheet without an anti-ice coating, prepared in example 4 of the present disclosure.
FIG. 7 is a graph showing the variation of ice adhesion strength between the specular Al sheet with anti-ice coating and the specular Al sheet without anti-ice coating prepared in example 5 of the present disclosure.
Detailed Description
The embodiments of the present invention will be described in detail below, and the embodiments described below by referring to the drawings are exemplary and intended to be used for explaining the present invention, and should not be construed as limiting the present invention.
The embodiment of the invention provides an anti-ice coating, which comprises a graphene nanosheet and a liquid medium containing fluorine resin, wherein the concentration of the graphene nanosheet is 2-5 mg/ml. Non-limiting examples are: the concentration of the graphene nanosheet is 2mg/ml, 2.5mg/ml, 3mg/ml, 4mg/ml, 5mg/ml, or the like.
According to the anti-ice coating disclosed by the embodiment of the invention, the anti-ice coating is applied to the substrate through the synergistic effect of the graphene nanosheets and the fluorine-containing resin to form the anti-ice coating, so that the high adhesion of the substrate to the surface of the coating and the extremely low ice adhesion of the surface of the coating are realized, and the icing time is delayed to a certain extent.
It can be understood that: the embodiment of the invention comprises the following steps: the "liquid medium of the fluorine-containing resin" includes a solution, a dispersion, an emulsion and the like.
In some embodiments, the graphene nanoplatelets have a platelet diameter of 1 to 10 μm and a thickness of 1 to 10nm. More preferably, the graphene nanoplatelets have a sheet diameter of 2 to 3 μm and a thickness of 1 to 2nm.
In some embodiments, the graphene nanoplatelets have a platelet diameter of 2 to 3 μm and a thickness of 1 to 2nm. In other embodiments, the graphene nanoplatelets have a platelet size of 5 to 10 μm and a thickness of 3 to 10nm, and in still other embodiments, the graphene nanoplatelets have a platelet size of 1 to 3 μm and a thickness of 1 to 5nm.
In some embodiments, the purity of the graphene nanoplatelets is greater than or equal to 98%.
In some embodiments, the liquid medium of the fluororesin has a solids content of 1 to 50 wt%. Non-limiting examples are: the solid content is 1wt%, 1.5wt%, 5wt%, 10wt%, 15wt%, 20wt%, 23wt%, 30wt%, 35wt%, 40wt%, 45wt%, 48wt%, 50wt%, etc.
In some embodiments, the fluororesin is one of an amorphous fluoropolymer, polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), or polyvinylidene fluoride (PVDF). Preferably, the fluororesin is an amorphous fluoropolymer.
In some embodiments, when the fluoropolymer is an amorphous fluoropolymer, the liquid medium of the fluoropolymer is a 1 to 10wt% solution of the amorphous fluoropolymer in a fluorine-based solvent. Non-limiting examples of concentrations are: 1wt%, 1.5wt%, 3wt%, 6wt%, 8wt%, 10wt%, etc. Non-limiting examples of amorphous fluoropolymers are Teflon TM AF series, e.g. Teflon TM AF1601、Teflon TM AF2400, etc.
In some embodiments, the fluorine-based solvent may be: perfluoro (2-butenyl tetrahydrofuran), perfluoro (tributylamine), perfluorohexane, perfluorooctylethylene, perfluorooctane, an FC-40 fluorinated liquid (3 m mfluorinorttm electron fluorinated liquid), and the like.
In some embodiments, the liquid medium of the fluororesin may be directly selected from commercially available products, such as Teflon TM AF1601XSOL 6, FC-40, etc.
In some embodiments, when the fluororesin is polytetrafluoroethylene, polychlorotrifluoroethylene, or polyvinylidene fluoride, the liquid medium of the fluororesin is a mixture according to (1-2): (1-2) a dispersion obtained by dissolving any one of a polytetrafluoroethylene emulsion, a polychlorotrifluoroethylene emulsion, and a polyvinylidene fluoride emulsion having a solid content of 50-60 wt% in a diluting solvent.
In some embodiments, the dilution solvent is a volatile reagent containing only C, H, and O elements.
In some embodiments, the dilution solvent is ethyl acetate, propyl acetate, or the like.
The embodiment of the invention also provides a preparation method of the anti-ice coating, which comprises the following steps: adding the graphene nanosheets into a liquid medium containing fluorine resin to obtain a mixture, and carrying out ultrasonic treatment on the mixture at the temperature of 20-50 ℃ for 6-8 h to uniformly disperse the graphene nanosheets in the liquid medium containing fluorine resin to obtain the anti-ice coating.
In some embodiments, the frequency of sonication is between 20 and 30kHz.
The embodiment of the invention also provides application of the ice-resistant coating in improving the ice adhesion performance of the substrate. In this application, the anti-ice coating is the anti-ice coating or the anti-ice coating prepared by the method.
The embodiment of the invention also provides a coated substrate containing an anti-ice coating, which comprises a substrate and the anti-ice coating formed on at least one surface of the substrate, wherein the anti-ice coating is formed by applying the anti-ice coating on the surface of the substrate and then curing the anti-ice coating, and the anti-ice coating is the anti-ice coating or the anti-ice coating prepared by the method.
In some embodiments, the thickness of the anti-ice coating is 10 to 30 μm. In some embodiments, the anti-ice coating has a thickness of 10 to 20 μm.
In some embodiments, the substrate is glass, silicon wafer, metal, plastic, or ceramic.
In some embodiments, the substrate is an Al sheet, high chromium bearing steel, stainless steel, glass, or silicon sheet.
In some embodiments, the substrate is an Al sheet.
Embodiments of the present invention further provide a method for preparing a coated substrate having an anti-icing coating, comprising the steps of:
(1) Pretreating at least one surface of the substrate;
(2) And (3) coating the anti-ice coating on the surface of the pretreated base material obtained in the step (1) to obtain a wet coating, heating for curing, and cooling to obtain the anti-ice coating on the surface of the base material, thereby obtaining the coated base material containing the anti-ice coating.
The preparation method of the coated substrate containing the anti-ice coating provided by the embodiment of the invention has the advantages of simple process, short production period and high repeatability, and is beneficial to large-scale industrial production.
In some embodiments, the pretreatment is grit blasting to provide a substrate surface roughness of 1 to 8 μm.
In some embodiments, the heat curing treatment temperature is 100 to 120 ℃ and the time is 1 to 2 hours.
In some embodiments, the cooling may be air cooling for 8-10 h.
In some embodiments, the coating is spin coating, dip coating, or spray coating.
The following are non-limiting examples of the invention.
In the examples of the present invention, the graphene nanoplatelets used in examples 1 to 5 were obtained from Nanjing Xiancheng nanomaterial science and technology Co.
In the examples of the present invention, the liquid medium of the fluororesin used in examples 1 to 3 was FC-40% as AF1601X SOL 6 manufactured by Chemours, USA.
In the embodiment of the present invention, the liquid medium of the fluorine-containing resin used in embodiment 4 is a mixed solution of polytetrafluoroethylene emulsion and ethyl acetate in a volume ratio of 1.
In the embodiment of the present invention, the liquid medium of the fluorine-containing resin used in embodiment 5 is a mixed solution of polychlorotrifluoroethylene emulsion and ethyl acetate in a volume ratio of 1.
In examples 1 to 5 of the present invention, an ice adhesion strength was tested by using an ice adhesion testing apparatus. As shown in FIG. 2, the ice adhesion testing apparatus includes an ambient temperature control cabinet, a cooling stage,
An ice column model, a stepping push rod and a force measuring sensor,
in the test process, the temperature of a cooling table is controlled to be-20 ℃, the temperature of an environmental temperature control cabinet is set to be-10 ℃, a sample and an ice column mold are placed on the surface of the cooling table, and 1ml of water is dripped into an ice column model; and placing for 5min, after water cooling and freezing, adjusting a stepping push rod carrying a force transducer to the section of the icicle model, wherein the center of a push rod head is 1-2 mm away from the section, and the height is 1mm away from the surface of the sample.
Starting the test, controlling the step push rod and the force sensor to move at the speed of 0.2mm/s until the ice column generates interface shear fracture movement, stopping the push rod, analyzing and calculating the obtained force measurement data, and dividing the peak value of the instant force during the fracture by the icing area of the ice column (the step (b) (c))
Area of circle) to obtain ice adhesion strength data.
Example 1:
(1) Selecting a mirror surface Al sheet with the size of 1.5cm x 1mm as a base material, and performing sand blasting treatment to ensure that the roughness of the surface of the base material is 5 mu m grade;
(2) Adding high-quality thin-layer graphene (XF 182-1) with the sheet diameter of 2-3 mu m and the thickness of about 2nm into an AF1601 fluororesin solution (American Chemours), wherein the concentration of the high-quality thin-layer graphene in the AF1601 fluororesin solution is 2mg/ml, and carrying out ultrasonic treatment at 30 ℃ and 20kHz for 6h to uniformly disperse the high-quality thin-layer graphene in the AF1601 fluororesin solution to obtain the anti-icing coating;
(3) And (2) spin-coating 500 mu l of ice-resistant coating on the surface of the sand-blast-treated Al sheet obtained in the step (1) to obtain a wet coating, heating and curing at 120 ℃ for 1h, and cooling in the air for 12h to obtain an ice-resistant coating with the thickness of 16-19 mu m.
Comparative example 1:
specular Al sheets with dimensions of 1.5cm x 1mm, marked in fig. 1: and (5) mirror Al sheets.
Comparative example 2:
a specular Al sheet with a dimension of 1.5cm x 1mm was selected as a base material, and sandblasting was performed to make the roughness of the base material surface on the order of 5 μm. Identified in fig. 1 as: sand blasting (5 μm) of Al sheets.
Comparative example 3:
(1) Selecting a mirror surface Al sheet with the size of 1.5cm x 1mm as a base material, and performing sand blasting treatment to ensure that the roughness of the surface of the base material is 5 mu m grade;
(2) And (3) spin-coating 500 μ l of AF1601 fluorine-containing resin solution (Chemours, USA) on the surface of the sand blasting Al sheet obtained in the step (1) to obtain a wet coating, heating and curing at 120 ℃ for 1h, and cooling in air for 12h to obtain an anti-ice coating with the thickness of 16-19 μm.
The icing delay time of the anti-icing coatings prepared in example 1 of the present invention and comparative examples 1 to 3 was measured using a cryogenically cooled stage and a video contact angle measuring instrument, as shown in fig. 1, the temperature of the cryogenically cooled stage was set to-10 ℃, and comparative tests were performed on a mirror Al sheet, a sand blasted (5 μm) Al sheet, and a sand blasted (5 μm) Al sheet coated with only AF1601 fluororesin solution, in which the mirror Al sheet was iced for about 0.8min and the sand blasted (5 μm) Al sheet coated with only AF1601 fluororesin solution was iced for 1.5min, and the icing time of the sand blasted (5 μm) Al sheet coated with only AF1601 fluororesin solution was extended to 8.8min due to the generation of hydrophobicity, while the anti-icing coating prepared in example 1 of the present invention was able to extend the icing time to 21.3min. The icing time can be prolonged to a greater extent.
The samples prepared in inventive example 1 and comparative examples 1 to 3 were placed on a low-temperature cooling stage set at a temperature of-20 c, the samples were frozen after cooling for 10min, and the ice adhesion test was performed using an ice adhesion test apparatus, and as a result, as shown in fig. 3, it can be seen from fig. 3 that the ice adhesion strength of inventive example 1 was reduced by more than 97% as compared to the test performed by directly freezing the samples under the same cooling conditions of the specular Al sheet, indicating that the ice-resistant coating prepared on the substrate using the inventive example had extremely low ice adhesion.
Example 2:
(1) Selecting a mirror surface high chromium bearing steel (GCr 15) sheet with the size of 1.5cm x 1mm as a base material, and performing sand blasting treatment to enable the roughness of the surface of the base material to be in the grade of 1 mu m;
(2) Adding high-quality thin-layer graphene (XF 182-1) with the sheet diameter of 2-3 mu m and the thickness of about 2nm into an AF1601 fluororesin solution (American Chemours), wherein the concentration of the high-quality thin-layer graphene in the AF1601 fluororesin solution is 3mg/ml, and carrying out ultrasonic treatment at 35 ℃ and 30kHz for 6h to uniformly disperse the high-quality thin-layer graphene in the AF1601 fluororesin solution to obtain the anti-icing coating;
(3) And (3) spin-coating 500 mu l of ice-resistant coating on the surface of the sand-blasting high-chromium bearing steel (GCr 15) sheet obtained in the step (1) to obtain a wet coating, heating and curing at 120 ℃ for 1h, and cooling in air for 12h to obtain an ice-resistant coating with the thickness of 9-12 mu m.
A sample of the high chromium bearing steel (GCr 15) sheet with an anti-ice coating prepared in example 2 was placed on a cryocooling stage set at a temperature of-20 c, the sample was cooled for 10min to ice, and tested using an ice adhesion testing apparatus. Results as shown in fig. 4, the ice adhesion strength decreased by over 98% compared to the ice adhesion strength of a high chromium bearing steel (GCr 15) sheet grit blasted alone when tested under the same cooling conditions.
Example 3:
(1) Selecting a 304 stainless steel sheet with the size of 1.5cm x 1mm as a base material, and performing sand blasting treatment to enable the surface roughness of the base material to be 2 mu m grade;
(2) Adding graphene nanosheets (XF 022-1) with the plate diameter of 1-3 mu m and the thickness of 1-5 nm into AF1601 fluorine-containing resin solution (American Chemours), enabling the concentration of the graphene nanosheets in the AF1601 fluorine-containing resin solution to be 3mg/ml, and carrying out ultrasonic treatment for 8 hours at 15kHz at 30 ℃ so as to uniformly disperse the graphene nanosheets in the AF1601 fluorine-containing resin solution, thereby obtaining the anti-ice coating;
(3) And (3) taking 500ul of ice-resistant coating to spin-coat the surface of the sand-blast-treated 304 stainless steel sheet obtained in the step (1) to obtain a wet coating, heating and curing the wet coating at 100 ℃ for 1h, and cooling the wet coating in air for 12h to obtain an ice-resistant coating with the thickness of 12-16 mu m.
The 304 stainless steel sheet sample having the anti-icing coating prepared in this example 3 was placed on a low temperature cooling stage at a temperature of-20 c, the sample was cooled for 10min to ice, and the test was performed using an ice adhesion testing apparatus. As a result, as shown in FIG. 5, the ice adhesion strength was reduced by over 96% as compared to the test in which the sample of 304 stainless steel sheet subjected to only the blast treatment alone was frozen under the same cooling condition.
Example 4:
(1) Selecting a mirror surface Al sheet with the size of 1.5cm x 1mm as a base material, and performing sand blasting treatment to enable the surface roughness of the base material to be 4 mu m grade;
(2) Mixing ethyl acetate and Polytetrafluoroethylene (PTFE) according to a volume ratio of 1;
(3) Adding a graphene nanosheet (XF 022-1) with the diameter of 1-3 mu m and the thickness of 1-5 nm into the polytetrafluoroethylene diluted in the step (2) to ensure that the concentration of the graphene nanosheet in the diluted polytetrafluoroethylene is 3mg/ml, and carrying out ultrasonic treatment at 50 ℃ and 30kHz for 8 hours to uniformly disperse the graphene nanosheet in the diluted polytetrafluoroethylene to obtain the anti-icing coating;
(4) And (3) spin-coating 500 mu l of ice-resistant coating on the surface of the sand-blast-treated mirror surface Al obtained in the step (1) to obtain a spin-coating layer, heating and curing at 100 ℃ for 1h, and cooling in air for 8h to obtain an ice-resistant coating layer with the thickness of about 30 mu m.
The mirror Al sheet sample with anti-ice coating prepared in this example 4 was placed on a cryogenically cooled stage at a temperature of-20 ℃ to freeze the sample for 10min and tested using an ice adhesion testing apparatus. As shown in FIG. 6, the ice adhesion strength was reduced by about 90.0% as compared to the test in which the specular Al sheet sample was frozen under the same cooling conditions.
Example 5:
(1) Selecting a mirror surface Al sheet with the size of 1.5cm by 1mm as a base material, and performing sand blasting treatment to ensure that the surface roughness of the base material is in the level of 4 mu m;
(2) And mixing ethyl acetate and Polychlorotrifluoroethylene (PCTFE) according to a ratio of 1.
(3) Adding a graphene nanosheet (XF 022-1) with the diameter of 5-10 mu m and the thickness of 3-10 nm into diluted polychlorotrifluoroethylene to ensure that the volume mass concentration of the graphene nanosheet in the polychlorotrifluoroethylene is 3mg/ml, and carrying out ultrasonic treatment at 50 ℃ and 30kHz for 8 hours to uniformly disperse the graphene nanosheet in the diluted polychlorotrifluoroethylene to obtain an anti-icing coating;
(4) And (3) spin-coating 500 mu l of an anti-ice coating on the surface of the sand-blast-treated mirror surface Al obtained in the step (1) to obtain a wet coating, heating and curing at 100 ℃ for 1h, and cooling in air for 8h to obtain an anti-ice coating with the thickness of about 30 mu m.
The mirror surface Al sheet sample with the anti-ice coating prepared in this example 5 was placed on a cryogenically cooled stage at a temperature of-20 ℃ to freeze the sample for 10min, and tested using an ice adhesion testing apparatus. As shown in FIG. 7, the ice adhesion strength was reduced by about 83.4% compared to the test in which the specular Al sheet sample was frozen under the same cooling conditions.
As can be seen from fig. 3 to 7, graphene nanoplates of different sizes and types dispersed in the AF1601 fluororesin solution and coated and cured on the surface of a substrate made of several materials have a good effect of reducing ice adhesion strength, and the reduction amplitude exceeds 96%, which can be mainly attributed to that the coating of the AF1601 fluororesin solution after high-temperature curing is thin, wherein a large number of graphene nanoplates are in an embedded state, the edge hydrogen bond precedence effect of the embedded graphene retards the formation of hydrogen bonds in water to delay the formation of ice and reduce the adhesion of ice, and the hydrophobicity of the high-temperature cured coating of the AF1601 fluororesin solution also reduces the retention time of water droplets on the surface and reduces the adhesion of ice; the polytetrafluoroethylene and polychlorotrifluoroethylene used in examples 4 and 5 had a thicker surface hydrophobic layer after curing at a high temperature, and the graphene functioned relatively poorly as in examples 1 to 3, and the ice adhesion was reduced mainly by the hydrophobicity of the coating, so the extent of the reduction in ice adhesion strength was smaller than in examples 1 to 3.
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are exemplary and not to be construed as limiting the present invention, and that changes, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (9)
1. The coated substrate containing the anti-icing coating is characterized by comprising a substrate and the anti-icing coating formed on at least one surface of the substrate, wherein the anti-icing coating is formed by applying an anti-icing coating on the surface of the substrate and then curing the anti-icing coating, the substrate is glass, a silicon wafer, metal, plastic or ceramic, the anti-icing coating consists of graphene nanosheets and a liquid medium of fluorine-containing resin, the concentration of the graphene nanosheets is 2-5 mg/ml, the fluorine-containing resin is amorphous fluorine-containing polymer AF1601, and the liquid medium of the fluorine-containing resin is a solution of amorphous fluorine-containing polymer dissolved in a fluorine solvent and having a concentration of 1-10wt%.
2. The coated substrate containing the anti-ice coating layer as claimed in claim 1, wherein the graphene nanoplatelets have a diameter of 1 to 10 μm and a thickness of 1 to 10nm.
3. The coated substrate containing the anti-ice coating layer as claimed in claim 2, wherein the graphene nanoplatelets have a diameter of 2 to 3 μm and a thickness of 1 to 2nm.
4. The coated substrate containing the ice-resistant coating as claimed in any one of claims 1 to 3, wherein the preparation method of the ice-resistant coating comprises the following steps: adding the graphene nanosheets into a liquid medium of the fluorine-containing resin to obtain a mixture, and carrying out ultrasonic treatment on the mixture at the temperature of 20-50 ℃ for 6-8h to obtain the anti-ice coating.
5. A coated substrate with an ice-resistant coating according to claim 1, characterised in that the ice-resistant coating has a thickness of 10 to 30 μm.
6. A process for the preparation of a coated substrate according to any one of claims 1 to 5 containing an ice-resistant coating, characterised in that it comprises the following steps:
(1) Pretreating at least one surface of the substrate;
(2) And (3) coating the anti-ice coating on the surface of the pretreated base material obtained in the step (1) to obtain a wet coating, heating for curing, cooling, and obtaining the anti-ice coating on the surface of the base material to obtain the coated base material containing the anti-ice coating.
7. The preparation method according to claim 6, wherein the pretreatment is sand blasting so that the roughness of the surface of the base material is 1 to 8 μm.
8. The method according to claim 6 or 7, wherein the heat curing is carried out at a temperature of 100 to 120 ℃ for 1 to 2h.
9. The method of claim 6, wherein the coating is spin coating, dip coating, or spray coating.
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