CN114058224B - Photo-thermal response super-hydrophobic anti-icing composite coating and preparation method thereof - Google Patents
Photo-thermal response super-hydrophobic anti-icing composite coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a photo-thermal response super-hydrophobic anti-icing composite coating and a preparation method thereof. The preparation method comprises the steps of coating room temperature silicone rubber on the surface of a base material; dispersing the micron-sized particles and the nano-sized particles in a solvent and adding a dispersing agent to obtain a uniform mixture solution; spraying the mixture solution on the surface of a substrate by using a spray gun to obtain a super-hydrophobic coating; and obtaining the stable photo-thermal response super-hydrophobic anti-icing composite coating through heat treatment and fluorination treatment. The photothermal response super-hydrophobic anti-icing composite coating prepared by the invention has super-hydrophobicity, low adhesion, firmness and excellent photothermal characteristics, and is wide in application scene and strong in mechanical stability.
Description
Technical Field
The invention belongs to the technical field of material surface engineering, and particularly relates to a photo-thermal response super-hydrophobic anti-icing composite coating and a preparation method thereof.
Background
In nature, ice formation and accumulation are very common phenomena. Although the natural landscape formed by the ice is colorful, the formation of the ice has more negative influence on the production and living of people. Under certain conditions, the ice accumulation problem threatens the flight safety of the airplane, causes the collapse of a power transmission line and a communication base station, damages buildings and the like, and further causes the economic loss which is difficult to predict.
The conventional deicing methods include: mechanical deicing, electrothermal deicing, artificial deicing, microwave deicing and the like, but the technologies have the problems of high cost and low efficiency, and the chemical deicing agent deicing technology is one of effective deicing modes, can reduce the melting point of ice and snow to achieve the aim of deicing, but is not negligible for the damage of the environment and the structure. Compared with the prior art, the anti-icing coating prepared by the spraying method is simple and convenient, has low cost and is more suitable for large-scale popularization. The application of a super-hydrophobic coating to material surface anti-icing has been widely reported, and the super-hydrophobic property of the coating enables the material surface to reduce the adhesion of liquid on the surface and increase the bounce of the liquid on the surface, and the ice can be easily separated from the surface of the liquid due to the smaller contact area of the liquid after the liquid is frozen. In addition, the photothermal effect can promote the material to melt the ice coating on the surface in a low-temperature environment, so that the active deicing performance is achieved. In recent years, researchers have made many efforts to construct robust photothermal anti-icing surfaces, but robust anti-icing surfaces with superhydrophobic and photothermal effects are still in need of improvement.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a preparation method of a photo-thermal response super-hydrophobic anti-icing composite coating, and the super-hydrophobic anti-icing composite coating prepared by the preparation method overcomes the problems of insufficient mechanical resistance, insufficient corrosion resistance, poor photo-thermal performance and the like of the super-hydrophobic anti-icing composite coating in a severe environment. The preparation method adopts the polymer network to wrap photo-thermal particles to prepare the photo-thermal response super-hydrophobic anti-icing composite coating for the first time, and utilizes the spraying method to uniformly spray the mixture solution on the surface of the matrix, so that the Carbon Nanotubes (CNTs) stably exist in the whole coating system network, and the efficient photo-thermal anti-icing composite coating is constructed. The sprayed mixed solution utilizes Tetraethoxysilane (TEOS), methyl triacetoxysilane or tetrapropoxysilane and the like as a dispersing agent, so that the adhesion among the micro-nano particles is improved, and the agglomeration phenomenon of the micro-nano particles in the spraying process is reduced. The low surface energy fluoride treatment coating results in a low surface energy multi-level microstructure. The obtained coating has excellent super-hydrophobicity, greatly reduces the contact area of water on the surface of the coating, promotes liquid drops to easily slide off the surface of the coating, and prolongs the freezing time of the water. The low surface energy and multi-level microstructure allows water to form less ice adhesion in low temperature environments. Meanwhile, the coating after heat treatment forms a continuous 3D polymer network, so that the CNTs can be stably present in the whole coating volume. Under the irradiation of simulated sunlight, the stable coating structure enables the photothermal effect to more efficiently promote the ice to melt on the surface of the coating, so that the ice layer on the surface of the coating slides down and the liquid drops melt. The coating combines the passive anti-icing performance of the micro-nano structure and the active deicing performance of the photothermal effect, and has the advantages of stable mechanical property, strong corrosion resistance, simple and convenient method and the like.
The second purpose of the invention is to provide the photo-thermal response super-hydrophobic anti-icing composite coating prepared by the preparation method.
The primary purpose of the invention is realized by the following technical scheme:
a preparation method of a photo-thermal response super-hydrophobic anti-icing composite coating comprises the following steps:
(1) Preparation of mixed spray solution: carbon Nanotubes (CNTs), polyvinylidene fluoride (PVDF), absolute ethyl alcohol and a dispersing agent are mixed according to the mass volume ratio of 1g: 5-20 g: 20-30 ml: 2-4 ml, adding the Carbon Nano Tubes (CNTs) and the polyvinylidene fluoride (PVDF) into absolute ethyl alcohol, then adding a dispersing agent, magnetically stirring, and carrying out ultrasonic treatment to obtain a uniformly dispersed mixed spraying solution;
(2) Preparation of a spray substrate: firstly, placing a glass slide in absolute ethyl alcohol for ultrasonic treatment, taking out and airing; magnetically mixing vulcanized silicone rubber (RTV-SR) with n-hexane, tetraethoxysilane (TEOS) and a catalyst, and then magnetically stirring; then, silicon sulfide rubber (RTV-SR) is coated on the glass slide in a scraping way, and the glass slide is heated in an oven and then taken out of the semi-viscous state SR-glass slide;
(3) Preparation of hydrophobic anti-icing coating: vertically spraying the mixed spraying solution in the step (1) on the semi-viscous flow SR-glass slide in the step (2) to obtain a super-hydrophobic anti-icing composite coating;
(4) And (3) carrying out heat treatment on the photo-thermal response super-hydrophobic anti-icing composite coating: and (4) placing the semi-viscous SR-glass slide containing the photo-thermal response super-hydrophobic anti-icing composite coating obtained in the step (3) in an oven, placing the low-surface-energy fluoride on the lower side of the semi-viscous SR-glass slide, and heating to obtain the photo-thermal response super-hydrophobic anti-icing composite coating which is completely cured and has the surface attached with the low-surface-energy fluoride.
Preferably, the dispersant in step (1) is one of Tetraethoxysilane (TEOS), methyltriacetoxysilane and tetrapropoxysilane.
Preferably, in the step (1), the Carbon Nanotubes (CNTs), polyvinylidene fluoride (PVDF), anhydrous ethanol and a dispersing agent are mixed according to a mass-to-volume ratio of 1g:10g:20ml:4ml.
Preferably, when the dispersant is tetraethyl orthosilicate (TEOS), the mass fraction of the dispersant in the step (1) is 98%.
Preferably, the Carbon Nanotubes (CNTs) in step (1) have a diameter of 10 to 30nm and a length of 10 to 20 μm.
Preferably, the particle size of the polyvinylidene fluoride (PVDF) in the step (1) is 10-15 μm.
Preferably, the magnetic stirring time in the step (1) is 10-15 min, and the ultrasonic treatment time is 20-40 min.
Preferably, the catalyst in the step (2) is one of dibutyltin dilaurate or 2- (tri-n-butylstannyl) thiazole and 2- (tributyltin) -5-trifluoromethylpyridine.
Preferably, the mass volume ratio of the silicon sulfide rubber (RTV-SR), n-hexane, tetraethoxysilane (TEOS) and the catalyst in the step (2) is 5g:2ml:0.5ml:0.1ml.
Preferably, the oven temperature in the step (2) is 40-60 ℃, and the heating time is 30-40 min.
Preferably, the distance between the mixed solution sprayed by the spray gun and the base material in the spraying process in the step (3) is 15-20 cm; the pressure of the spray gun is 0.3-0.5 MPa.
Preferably, the oven temperature in the step (4) is 160-180 ℃, and the heating time is 10-30 min.
Preferably, the low surface energy fluoride in step (4) is one of alkane, dibasic acid ester and fatty acid.
Preferably, the low surface energy fluoride in step (4) is 1H, 2H-perfluorodecyltrimethoxysilane, which has the following structural formula:
the second purpose of the invention is realized by the following technical scheme:
the photo-thermal response super-hydrophobic anti-icing composite coating prepared by the preparation method.
The principle of the invention is as follows:
according to the invention, ethanol is used as a solvent to mix micro-nano particles, tetraethoxysilane (TEOS), methyltriacetoxysilane or tetrapropoxysilane is used as a dispersing agent, micro-nano particles which are gathered in a large range are dispersed by magnetic stirring, and the micro-nano particles are further dispersed by ultrasonic treatment, so that uniform dispersed phase is formed in a mixed solution. RTV-SR and curing agent dibutyltin dilaurate are mixed, and the mixed solution is sprayed on the surface of the RTV-SR when the RTV-SR is in a semi-viscous state. In the spraying method, gas is used as a driving force, so that micro-nano particles are more uniformly distributed on the surface of the substrate. CNTs with nano-scale size are wound on micron-scale particle PVDF, and the addition of the dispersing agent in the spraying process improves the bonding property between the two. The combination of the nano-sized CNTs with smaller sizes and the micron-sized PVDF particles forms a multi-layer micro-nano structure, so that water can exist on the surface of the multi-layer micro-nano structure in a more stable Cassie contact state, and a larger contact angle and a smaller contact area are formed. And performing heat treatment to enable PVDF on the surface of the coating to be mutually welded, and wrapping CNTs wound around the PVDF by a heated and melted polymer network to form a linked 3D (three-dimensional) network with a multi-level micro-nano structure. The peak-like structure formed between the particles forms a gap-bridge structure at the bottom after welding, so that a large amount of air is contained, the contact area of water and the coating is reduced, and the heat conduction between the water and the base material is enhanced due to the introduction of the air. The CNTs have excellent photo-thermal effect, the stable polymer network wraps the CNTs to form a firm photo-thermal anti-icing coating, and heat generated from the bottom under the irradiation of a light source causes frozen water drops on the surface and an ice layer to be rapidly melted. The CNTs are wrapped by the PVDF molten network and the CNTs are mutually overlapped, a good heat-conducting network is formed in the whole coating system, and heat generated by the photo-thermal effect is conducted to the volume of the coating network, so that the melting of ice is accelerated, and the adhesion of the ice is reduced.
The invention has the advantages that:
(1) The photothermal response super-hydrophobic anti-icing composite coating is prepared by coating room temperature silicone rubber on the surface of a base material; dispersing the micron-sized particles and the nano-sized particles in a solvent and adding a dispersing agent to obtain a uniform mixture solution; spraying the mixture solution on the surface of a substrate by using a spray gun to obtain a super-hydrophobic coating; and obtaining the stable photo-thermal response super-hydrophobic anti-icing composite coating through heat treatment and fluorination treatment. The preparation method is simple, scientific in process and wide in application scene;
(2) After the prepared photo-thermal response super-hydrophobic anti-icing composite coating is subjected to heat treatment and fluoride low surface energy treatment, the prepared coating contains a stable micro-nano multi-level structure, the coating has super-hydrophobic and low-adhesion characteristics by combining the multi-level structure and a fluorination strategy, the overall stability of the coating is greatly improved due to a 3D continuous network structure formed by polymer fusion, meanwhile, extra air is introduced as a heat insulation layer, the wear resistance, corrosion resistance and the like of the coating are enhanced, CNTs are bridged with each other due to the formation of the continuous network so as to penetrate through the volume of the whole coating, so that more excellent photo-thermal characteristics are exerted, and the coating can melt frozen water drops and ice on the surface under the irradiation of a light source;
(3) The photothermal response super-hydrophobic anti-icing composite coating is welded with the coating surface micro-nano structure under the heat effect to form a continuous network, the super-hydrophobic state is still kept after the linear friction, gravel impact and chemical erosion tests by using abrasive paper, the super-hydrophobic passive anti-icing performance and the photothermal effect passive anti-icing performance of the coating are combined, the firmness of the whole coating is improved, the coating performance is reliable, and the durability is enhanced.
Drawings
FIG. 1 is an SEM image of the surface of the photothermal response superhydrophobic anti-icing composite coating described in example 4;
FIG. 2 is a schematic view of the mechanical abrasion resistance of the photothermal response superhydrophobic anti-icing composite coating described in example 4; wherein (a) is a schematic representation of the coating under grit impact; (b) Change of contact angle and rolling angle of the coating after 50 times of grit impact; (c) A schematic diagram of a linear friction experiment is carried out on the coating under the friction action of abrasive paper; (d) Change of contact angle after 60 times of circulation under the action of linear friction of the abrasive paper;
FIG. 3 is a schematic diagram of the process of freezing water drops on the surface of the photothermal response superhydrophobic anti-icing composite coating described in example 4; wherein (a 1-a 6) is a water drop freezing process of the surface of the PVDF/CNTs coating with the mass ratio of 5; (b 1-b 6) is a water drop freezing process of the PVDF/CNTs coating surface with the mass ratio of 15; (c 1-c 6) a water drop freezing process of the PVDF/CNTs mass ratio of 20;
FIG. 4 is an EDS image of an F element on the surface of the photothermal response superhydrophobic anti-icing composite coating prepared in example 4; wherein (a, d) an EDS image of the F element on the surface of the coating prepared in example 4; (b, e) preparing an EDS image of an element F on the surface of the coating for example 4; (c, F) preparation of coating for example 4 surface F element EDS image after 50 grit impacts;
FIG. 5 is a graph showing the temperature change of the surface of the photo-thermal response superhydrophobic anti-icing composite coating prepared in example 4 with the time of illumination.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
For clarity, the present invention will be further described with reference to the following examples and drawings, which fully describe the preparation scheme and specific working procedures of the present invention.
In the disclosed embodiments, PVDF is an abbreviation for polyvinylidene fluoride; CNTs are an abbreviation for carbon nanotubes; RTV-SR is an abbreviation for room temperature vulcanized silicone rubber; TEOS is an abbreviation for tetraethoxysilane; FAS-17 is an abbreviation for low surface energy fluoride 1H, 2H-perfluorodecyltrimethoxysilane.
The following examples relate to the following test conditions: the water contact angle and the rolling angle are measured by a surface tension surface contact angle tester; ice adhesion and freezing delay time were measured in a climatic chamber (-20 ℃,30 RH%). The ice adhesion force testing platform consists of a force sensor and a stepping motor, and the value of the ice adhesion force testing platform is the practical maximum value of the force sensor in the process of the stepping motor. The freezing delay time is the time required for the single water drop to contact the surface of the coating from a liquid state until the single water drop is completely frozen, and the process is finished by shooting with a CCD industrial camera. The photothermal properties are generated by a solar simulator, and an infrared measuring instrument records the surface temperature change of the sample.
Example 1
Preparation of a hydrophobic anti-icing coating (PVDF) comprising the following steps:
(1) Preparation of mixed spray solution: firstly, 0.5g of PVDF (10-15 mu m in particle size, french Akoma Limited) is taken and added into 20ml of absolute ethyl alcohol (Tianjin Fuyu fine chemical industry Limited), 4ml of tetraethoxysilane (TEOS, produced by Shanghai Memclin biochemistry company, purity: 98%) is taken and added into the mixed solution, the mixture is magnetically stirred for 10min, and the mixture is further treated by ultrasonic for 30min to obtain evenly dispersed suspension liquid, thus obtaining mixed spraying solution;
(2) Preparation of a spray substrate: firstly, placing a glass slide (7101) in absolute ethyl alcohol for ultrasonic treatment for 10min, and then taking out and airing; magnetically mixing 5g of RTV-SR with 2ml of n-hexane (produced by Mecanol biochemicals, shanghai), 0.5ml of TEOS and 0.1ml of dibutyltin dilaurate, and magnetically stirring for 10min; then, coating an RTV-SR blade with the thickness of 2mm on a glass slide, placing the glass slide in a 50 ℃ oven for 30min, and taking out the semi-viscous flow state SR-glass slide;
(3) Vertically spraying the mixed spraying solution in the step (1) on the semi-viscous SR-glass slide in the step (2) by using a spray gun (Nippon Mingming Co., nozzle caliber is 2.0mm, spray gun pressure is 0.3 MPa), wherein the spraying distance is 20cm, so as to obtain a hydrophobic anti-icing coating;
(4) Heat treatment and fluoride FAS-17, (purity: 97% available from shanghai mclin biochemistry corporation) the photothermal response hydrophobic anti-icing composite coating described in step (3) was placed in an oven at 160, 170, 180 ℃ respectively, with the sample facing down and 50 microliters FAS-17 placed underneath, and heated for 30min to give a fully cured photothermal response hydrophobic anti-icing coating (PVDF) with low surface energy fluoride attached.
Example 2
A preparation method of a photo-thermal response super-hydrophobic anti-icing composite Coating (CNTs) comprises the following steps:
(1) Preparation of mixed spray solution: firstly, 0.05g of multi-walled carbon nanotubes (CNTs, the diameter of which is 10-30 nm, the length of which is 10-20 mu m, nanjing Xiancheng nano material science and technology Co., ltd.) are taken and added into 20ml of absolute ethyl alcohol (Tianjin Fuyu fine chemical Co., ltd.), 4ml of tetraethoxysilane (TEOS, produced by Shanghai Micheling biochemistry Co., ltd., purity of 98%) is taken and added into the mixed solution, the mixed solution is magnetically stirred for 10min, and the mixed solution is further subjected to ultrasonic treatment for 30min to obtain uniformly dispersed suspension liquid so as to obtain mixed spraying solution;
(2) Preparation of a spray substrate: firstly, placing a glass slide (7101) in absolute ethyl alcohol for ultrasonic treatment for 10min, taking out and airing, magnetically mixing 5g of RTV-SR with 2ml of n-hexane (produced by Shanghai Merlin biochemistry corporation), 0.5ml of TEOS and 0.1ml of dibutyltin dilaurate, then magnetically stirring for 10min, then scraping the RTV-SR to a thickness of 2mm on the glass slide, placing the glass slide in a 50 ℃ oven for 30min, and taking out a semi-viscous state SR-glass slide substrate;
(3) Vertically spraying the mixed spraying solution in the step (1) on the semi-viscous SR-glass slide in the step (2) by using a spray gun (Nippon Mingming Co., nozzle caliber is 2.0mm, spray gun pressure is 0.3 MPa), wherein the spraying distance is 20cm, so as to obtain a super-hydrophobic anti-icing coating;
(4) And (2) carrying out heat treatment and fluoride FAS-17, (produced by Meclin biochemistry Corp., shanghai, with the purity of 97%) on the photo-thermal response super-hydrophobic anti-icing composite coating in the step (3), placing the photo-thermal response super-hydrophobic anti-icing composite coating in an oven with the temperature of 170 ℃, placing a sample of the photo-thermal response super-hydrophobic anti-icing composite coating downwards and downwards on the sample, and heating for 30min to obtain the photo-thermal response super-hydrophobic anti-icing composite Coating (CNTs) with completely cured and attached low-surface energy fluoride.
The coating photothermal response test process comprises the following steps: the sample was placed under a solar simulator (medium-focus gold source technologies, inc., CELL-S500, simulating 0.5-1 sunlight intensity), and a thermal infrared imager (FLIR-E4 FILR, inc., USA) recorded the change of the surface temperature of the coating with the time of illumination.
Example 3
Preparation of a hydrophobic anti-icing coating (non-heat treated PVDF/CNTs coating) comprising the following steps:
(1) Preparation of mixed spray solution: firstly, 0.05g of multi-walled carbon nanotubes (CNTs, diameter of 10-30 nm, length of 10-20 microns, nanjing Xiancheng nanometer material science and technology Limited company) and 0.5g of PVDF (particle size of 10-15 microns, french Akoma Limited company) are added into 20ml of absolute ethyl alcohol (Tianjin Fuyu fine chemical industry Limited company), 4ml of tetraethoxysilane (TEOS, produced by Shanghai Michelin biochemistry company, purity of 98%) is added into the mixed solution, the mixed solution is stirred for 10min by magnetic force, and the mixed solution is obtained by further ultrasonic treatment for 30min and is evenly dispersed suspension;
(2) Obtaining a semi-viscous flow state SR-glass slide substrate in the same way as the step (2) in the example 1;
(3) And (3) vertically spraying the mixed solution in the step (1) on the semi-viscous SR-slide glass in the step (2) by using a spray gun (Nippon Mingmy company, the caliber of the spray nozzle is 2.0mm, and the pressure of the spray gun is 0.3 MPa), wherein the spraying distance is 20cm, so that the hydrophobic anti-icing coating is obtained.
In the embodiment, the hydrophobic anti-icing coating obtained in the step (3) is not heated, and a welded bridge is not formed between PVDF due to non-heating, but the hydrophobicity of the coating is improved by a composite-level microstructure formed by micron PVDF and nano CNTs compared with that of the coating in the embodiment 2.
The coating photothermal response test process comprises the following steps: the samples were placed under a solar simulator (Medium-Focus gold technology, inc., CELL-S500, simulating 0.5-1 intensity of sunlight) and a thermal infrared imager (FLIR-E4 FILR, inc., USA) recorded the change of the surface temperature of the coating with the time of illumination.
The wetting characteristics, icing delay time, and ice adhesion data of the hydrophobic anti-icing coating obtained in this example are shown in table 1 below.
Example 4
The preparation method of the photo-thermal response super-hydrophobic anti-icing composite coating (PVDF/CNTs coating) comprises the following steps:
(1) Preparation of mixed spray solution: firstly, 0.05g of multi-walled carbon nanotubes (CNTs, diameter of 10-30 nm, length of 10-20 microns, nanjing Xiancheng nanometer material science and technology Limited company) and 0.5g of PVDF (particle size of 10-15 microns, french Akoma Limited company) are added into 20ml of absolute ethyl alcohol (Tianjin Fuyu fine chemical industry Limited company), 4ml of tetraethoxysilane (TEOS, produced by Shanghai Michelin biochemistry company, purity of 98%) is added into the mixed solution, the mixed solution is stirred for 10min by magnetic force, and the mixed solution is obtained by further ultrasonic treatment for 30min and is evenly dispersed suspension;
(2) Obtaining a semi-viscous state SR-glass slide substrate in the same way as the step (2) in the embodiment 1;
(3) Vertically spraying the mixed solution in the step (1) on the semi-viscous SR-glass slide in the step (2) by using a spray gun (Nippon Mingmy company, the caliber of the spray nozzle is 2.0mm, and the pressure of the spray gun is 0.3 MPa), wherein the spraying distance is 20cm, so as to obtain a super-hydrophobic anti-icing coating;
(4) And (2) performing heat treatment and fluoride FAS-17, (produced by Shanghai Merlin biochemistry corporation, purity: 97%) treatment on the superhydrophobic anti-icing composite coating in the step (3), respectively placing the superhydrophobic anti-icing composite coating in ovens at 160, 170 and 180 ℃, placing a sample in the FAS-17 with the volume of 50 microliters downwards and downwards, and heating for 30min to obtain a completely cured and attached low-surface-energy fluoride photothermal response superhydrophobic anti-icing composite coating (PVDF/CNTs coating).
The coating photothermal response test process comprises the following steps: the samples were placed under a solar simulator (Medium-Focus gold technology, inc., CELL-S500, simulating 0.5-1 intensity of sunlight) and a thermal infrared imager (FLIR-E4 FILR, inc., USA) recorded the change of the surface temperature of the coating with the time of illumination.
Wherein, fig. 1 is an SEM image of the surface of the photo-thermal response superhydrophobic anti-icing composite coating described in example 4.
FIG. 2 is a schematic diagram of the mechanical abrasion resistance of the photothermal response superhydrophobic anti-icing composite coating described in example 4; wherein (a) is a schematic representation of the coating under grit impact; (b) Change of contact angle and rolling angle of the coating after 50 times of grit impact; (c) A schematic diagram of a linear friction experiment is carried out on the coating under the friction action of abrasive paper; (d) Change of contact angle after 60 cycles under linear friction of the abrasive paper; it was found that the coating remained superhydrophobic and low roll angle after 50 grit impacts and 60 linear rubs.
FIG. 3 is a schematic diagram of the process of freezing water droplets on the surface of the photothermal response superhydrophobic anti-icing composite coating according to example 4; wherein (a 1-a 6) is a water drop freezing process of the surface of the PVDF/CNTs coating with the mass ratio of 5; (b 1-b 6) a water drop freezing process of the PVDF/CNTs mass ratio of 15; (c 1-c 6) is the water drop freezing process of the coating surface with the PVDF/CNTs mass ratio of 20.
FIG. 4 is an EDS image of an F element on the surface of the photothermal response superhydrophobic anti-icing composite coating prepared in example 4; wherein (a, d) an EDS image of the F element on the surface of the coating prepared in example 4; (b, e) preparing an EDS image of an element F on the surface of the coating for example 4; (c, F) surface F element EDS images of the coating prepared for example 4 after 50 grit impacts.
FIG. 5 is a graph showing the photothermal effect of the photothermal response superhydrophobic anti-icing composite coating surface according to example 4 when being irradiated with light, and it can be found that the surface temperature rises to about 75 ℃ after being irradiated with light for 180 s;
the wetting characteristic, icing delay time and ice adhesion force data of the photo-thermal response super-hydrophobic anti-icing composite coatings obtained in the examples 1 to 4 are shown in the following table 1.
TABLE 1 wetting characteristics, icing delay time, ice adhesion data test results
The coatings exhibited different wetting properties after heat treatment at different temperatures. At 160 ℃, the PVDF cannot be completely welded to each other, and the formed bridge is not large enough to accommodate a large amount of air, which results in an increase in the contact area between water and the coating, a larger contact angle, and ice adhesion. The temperature is raised to 170 ℃, the fusion between PVDF forms a stable integral coating network, and the strong fusion bridge promotes the increase of the contact angle and the prolongation of the icing delay time. At further increases in temperature to 180 ℃, PVDF encapsulates large amounts of CNTs due to the melt flow effect, which results in coatings that do not contain enough air to support surface water droplets, exhibiting lower contact angles and greater ice adhesion.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (7)
1. The preparation method of the photo-thermal response super-hydrophobic anti-icing composite coating is characterized by comprising the following steps of:
(1) Preparation of mixed spray solution: mixing a carbon nano tube, polyvinylidene fluoride, absolute ethyl alcohol and a dispersing agent according to a mass-volume ratio of 1g: 5-20 g: 20-30 ml: 2-4 ml, adding the carbon nano tube and the polyvinylidene fluoride into absolute ethyl alcohol, adding a dispersing agent, magnetically stirring, and carrying out ultrasonic treatment to obtain a uniformly dispersed mixed spraying solution; the dispersing agent is one of ethyl orthosilicate, methyl triacetoxysilane or tetrapropoxysilane;
(2) Preparation of a spray substrate: firstly, placing a glass slide in absolute ethyl alcohol for ultrasonic treatment, taking out and drying; magnetically mixing vulcanized silicone rubber, normal hexane, ethyl orthosilicate and a catalyst, and then magnetically stirring to obtain a mixture containing the vulcanized silicone rubber; then scraping and coating the mixture containing the vulcanized silicone rubber on a glass slide, heating the glass slide in an oven, and taking out the semi-viscous flow SR-glass slide;
(3) Preparation of hydrophobic anti-icing coating: vertically spraying the mixed spraying solution in the step (1) on the semi-viscous flow SR-glass slide in the step (2) to obtain a photo-thermal response super-hydrophobic anti-icing composite coating;
(4) And (3) carrying out heat treatment on the photo-thermal response super-hydrophobic anti-icing composite coating: placing the semi-viscous SR-glass slide containing the photo-thermal response super-hydrophobic anti-icing composite coating obtained in the step (3) in an oven, placing low-surface-energy fluoride FAS-17 downwards and below the semi-viscous SR-glass slide, and heating to obtain a fully-cured photo-thermal response super-hydrophobic anti-icing composite coating with the low-surface-energy fluoride attached to the surface;
the temperature of the oven in the step (4) is 160-180 ℃, and the heating time is 10-30 min.
2. The method for preparing the photothermal response superhydrophobic anti-icing composite coating according to claim 1, wherein the carbon nanotubes in the step (1) have a diameter of 10 to 30nm and a length of 10 to 20 μm.
3. The preparation method of the photothermal response superhydrophobic anti-icing composite coating according to claim 1, wherein the particle size of the polyvinylidene fluoride in the step (1) is 10-15 μm.
4. The method for preparing the photothermal response superhydrophobic anti-icing composite coating according to claim 1, wherein the catalyst in the step (2) is one of dibutyltin dilaurate, 2- (tri-n-butylstannyl) thiazole and 2- (tributyltin) -5-trifluoromethylpyridine.
5. The preparation method of the photothermal response superhydrophobic anti-icing composite coating according to claim 1, wherein the mass-to-volume ratio of the silicon sulfide rubber, n-hexane, ethyl orthosilicate and the catalyst in the step (2) is 5g:2ml:0.5ml:0.1ml.
6. The method for preparing the photothermal response superhydrophobic anti-icing composite coating according to claim 1, wherein the distance between the spray gun spraying mixed solution and the substrate in the spraying process in the step (3) is 15-20 cm; the pressure of the spray gun is 0.3-0.5 MPa.
7. The photothermal response super-hydrophobic anti-icing composite coating prepared according to the preparation method of any one of claims 1 to 6.
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