CN107116017B - Preparation method of super-amphiphobic coating capable of resisting icing for long time - Google Patents

Preparation method of super-amphiphobic coating capable of resisting icing for long time Download PDF

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CN107116017B
CN107116017B CN201710263704.1A CN201710263704A CN107116017B CN 107116017 B CN107116017 B CN 107116017B CN 201710263704 A CN201710263704 A CN 201710263704A CN 107116017 B CN107116017 B CN 107116017B
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epoxy resin
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CN107116017A (en
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王成毓
刘峰
胡海涛
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Harbin Yuqian Technology Co.,Ltd.
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Heilongjiang Kaienqi New Material Technology Co ltd
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    • 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
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B05D7/544—No clear coat specified the first layer is let to dry at least partially before applying the second layer
    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
    • 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
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
    • 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
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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
    • B05D2504/00—Epoxy polymers

Abstract

The invention relates to the field of preparation of super-hydrophobic or super-amphiphobic coatings, in particular to a preparation method of a super-amphiphobic coating capable of resisting icing for a long time, which specifically comprises the following steps: step 1, cleaning and sandblasting coarsening treatment is carried out on the surface of a base material; step 2, blending epoxy resin, an epoxy resin curing agent and a first solvent to obtain an epoxy resin solution; step 3, dispersing the sub-micron particles and the nano-particles in a second solvent, and then adding fluorosilane to obtain a particle composite suspension; step 4, spraying the epoxy resin solution obtained in the step 2 on the surface of the substrate treated in the step 1, and semi-curing the epoxy resin adhesive; step 5, spraying the particle composite suspension obtained in the step 3 on the surface of the base material obtained in the step 4, and completely curing; and 6, obtaining the super-amphiphobic coating which can resist the icing for a long time. The invention has the beneficial effects that: the super-amphiphobic coating prepared on the surface of each substrate has good durability and firmness, and has durable anti-icing performance.

Description

Preparation method of super-amphiphobic coating capable of resisting icing for long time
Technical Field
The invention relates to the field of preparation of super-hydrophobic or super-amphiphobic coatings, in particular to a preparation method of a super-amphiphobic coating capable of resisting icing for a long time.
Background
Surface wettability is one of the important characteristics of a solid surface, and can be measured by the contact angle of water on the surface; superhydrophobic surfaces have attracted great interest in academia and industry because of their contact angle with water of greater than 150 °, rolling angle of less than 10 °, and their self-cleaning properties. In nature, leaves and petals of many plants, wings of insects, feathers of birds and the like are natural super-hydrophobic materials. The self-cleaning function of a superhydrophobic surface, i.e. surface contaminants such as dust and the like, can be carried away by rolling water droplets without leaving any marks. The self-cleaning coating has the advantages of water saving, energy saving, environmental protection and the like, is more and more attracted by people, and is one of the hot spots of the current material subject research.
Along with the increasing research interest of people on the super-hydrophobic and super-amphiphobic surfaces, especially in recent years, the loss of rain, snow and ice disasters to different degrees caused by power transmission communication circuits, aviation, navigation or high-speed rail transportation increases the research strength of people on the anti-icing and anti-icing of the super-hydrophobic or super-amphiphobic surfaces. In a practical environment, such as a wire suspended in the air, an airplane wing flying in a cloud layer, a wing of a wind driven generator, and the like, the surface is often easily frozen under the conditions of low temperature and high humidity, thereby causing great economic loss. Therefore, it is very important to enhance the super-hydrophobic or super-amphiphobic properties of the solid surface in the anti-icing aspect.
Compared with the traditional ice melting and deicing method, the important application of the super-hydrophobic technology is the resistance to icing and frosting, namely the accumulation of the frost on solids is delayed, reduced and even completely prevented, and the problem can be better solved. Numerous studies have demonstrated that superhydrophobicity of a surface reduces the adhesion strength of ice on the surface. However, recent studies have shown that most of the prepared superhydrophobic or superamphiphobic surfaces are not durable against icing: especially when the superhydrophobic surface is subjected to extremely low ambient temperature and high humidity, the resistance of the superhydrophobic surface to icing is not ideal, and sometimes even the surface is more difficult to remove once it has been frozen.
Based on the problems, the invention provides a preparation method of a super-amphiphobic coating capable of resisting icing durably, the super-amphiphobic coating prepared by the invention can still be transported in a low-temperature and high-humidity environment, and the durable anti-icing performance of the super-amphiphobic coating is realized.
Disclosure of Invention
The invention provides a preparation method of a super-amphiphobic coating capable of resisting freezing for a long time.
The purpose of the invention is mainly realized by the following technical scheme:
a preparation method of a super-amphiphobic coating capable of resisting icing for a long time specifically comprises the following steps:
step 1, cleaning and sandblasting coarsening treatment are carried out on the surface of a base material to obtain a treated base material;
step 2, blending the epoxy resin, the curing agent and the first solvent to obtain an epoxy resin solution;
3, dispersing the sub-micron particles and the nano particles in a second solvent, adding fluorosilane after ultrasonic treatment and stirring, and continuing ultrasonic treatment and stirring to obtain a particle composite suspension;
step 4, spraying the epoxy resin solution obtained in the step 2 on the surface of the base material treated in the step 1, drying the base material, and semi-curing the epoxy resin adhesive;
step 5, spraying the particle composite suspension obtained in the step 3 on the surface of the base material obtained in the step 4, and drying the base material for complete curing;
and 6, washing the surface of the base material obtained in the step 5 to obtain the super-amphiphobic coating capable of resisting the ice for a long time.
Further, in the step 1, the substrate is a silicon wafer, metal, glass, plastic, wood or stone with a plane, a curved surface or an irregular shape; the surface of the base material is cleaned by sequentially cleaning acetone, deionized water and ethanol.
The preparation method of the invention is not influenced by the shape, size and type of the base material, and is not limited to the base material, meanwhile, the metal base material can be iron, aluminum or aluminum alloy, but is not limited to the base materials, and the glass base material can be quartz or common glass; the substrate of the invention may be paperboard, which only needs to be scrubbed.
Further, in the step 1, the process parameters of the sandblasting roughening treatment are as follows: the air pressure is 0.5-1.0 MPa, the sand blasting time is 10 seconds-1 minute, and the mesh number of sand pills for sand blasting is 40-200 meshes.
The surface of the substrate is subjected to sand blasting roughening treatment, so that the roughness of the surface of the substrate can be increased, the bonding strength of the coating and the substrate is improved, and the firmness and durability of the surface of the super-amphiphobic coating are further improved.
Further, in the step 2, the mass ratio of the epoxy resin, the curing agent and the first solvent is (4-10): (2-10): 100.
further, the epoxy resin is one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin and novolac epoxy resin; the curing agent is alicyclic amine curing agent; the first solvent is one or more mixed solvents of toluene, xylene, acetone, methyl ethyl ketone, butanone, ethyl acetate, n-butyl acetate and tert-butyl acetate.
In order to construct a super-hydrophobic or super-amphiphobic surface on a smooth surface, a method which is commonly used at present is to blend inorganic nanoparticles and fluorine-containing polymer or to fluorinate the nanoparticles, and then to coat the fluorinated nanoparticles on the surface of a material so as to construct the super-hydrophobic or super-amphiphobic surface. In these methods, the polymer and inorganic particles are difficult to bond with the substrate by chemical bonding, and the bonding force is weak only by physical adsorption, so that the constructed super-hydrophobic or super-amphiphobic surface is weak in friction resistance and washing resistance. The super-amphiphobic coating is prepared by adopting the primer coating and the surface coating, wherein the primer coating adopts two-component epoxy resin, the epoxy resin has the function of universal glue, on one hand, the epoxy resin can be firmly adhered to the surface of a substrate, on the other hand, the epoxy resin firmly adheres inorganic silicon dioxide particles and plays a role of an intermediate adhesive body, and the construction of a coarse structure required by super-amphiphobic is realized, so that the constructed super-amphiphobic coating has good durability and firmness, and meanwhile, the super-amphiphobic coating has durable anti-icing performance.
Further, in the step 3, the sub-micron particles and the nano-particles are dispersed in a second solvent, and after being subjected to ultrasonic treatment and stirred for 1 to 3 hours, fluorosilane is added, and the ultrasonic treatment and the stirring are continued for 1 to 3 hours, so that a particle composite suspension is obtained; in the step 4, the base material is dried at the temperature of 25-80 ℃ for 0.5-2 h for semi-curing; and in the step 5, the base material is dried for 0.5-24 hours at the temperature of 25-80 ℃ for complete curing.
Further, the sub-micron particles are silicon dioxide particles with the particle size of 200-500 nm; the nano particles are hydrophilic fumed silica particles with the particle size of 7-40 nm, and the second solvent is one or more mixed solvents of acetone, ethanol, n-hexane, methyl acetate and carbon tetrachloride.
In the invention, 200-500 nm submicron silica and 7-40 nm fumed silica particles are dispersed in a surface layer solution, and a fine binary coarse micro-nano structure is formed on the surface of a base material and the surface of an epoxy resin layer after spraying; when the coating only contains the small-particle-size silicon dioxide, the small-particle-size silicon dioxide is easily dispersed by external force when the external force is applied to the coating, so that the super-amphiphobic performance is lost; when only the silicon dioxide with large particle size is used, the surface of the coating cannot reach a super-amphiphobic micro-nano fine structure, so that super-amphiphobic treatment of the surface of the substrate cannot be realized; according to the invention, the two silicon dioxide particles with the particle sizes are mutually crossed and bound together, when external force is applied to the coating, the submicron silicon dioxide particles with the large particle size have a certain dispersion effect on the force applied to the nanometer fumed silica with the small particle size, so that the durability and the firmness of the coating can be improved by the structure, and the service life of the coating is prolonged.
Further, the mass ratio of the sub-micron particles, the nano-particles, the fluorosilane and the second solvent is (1-3): (1-3): (2-10): 100.
preferably, the mass ratio of the nanoparticles to the submicron particles is (1-0.5): (0.5-0.1).
In the invention, the gas phase silicon dioxide with the grain diameter of 7-40 nm and the submicron silicon dioxide with the grain diameter of 200-500 nm are controlled to be (1-0.5): (0.5-0.1), and the prepared super-amphiphobic coating has the characteristics of super-hydrophobicity and non-adhesion to water mist. When the atomized water mist is continuously sprayed on the surface of a sample by a spray gun, under the condition of high humidity, small water drops of the water mist on the surface of the coating can roll or bounce away from the coating quickly and cannot be condensed into large water drops, so that the anti-fog effect of the surface of the coating is realized; when the coating is placed in a low-temperature environment of minus 10 ℃, and the atomized water mist is continuously sprayed on the surface of the coating by the spray gun, small water drops of the water mist on the surface of the coating can still roll or bounce away from the coating rapidly and are not condensed into large water drops, after the spraying is continuously carried out for 200 minutes, the surface of the coating is not frozen, and finally the coating achieves the anti-icing effect and performance.
Further, the fluorosilane is one or more of perfluorosilane of which the carbon chain length is more than 4 and the end group is methoxy, ethoxy or chloro.
Preferably, the fluorosilane is one or more of perfluorodecyltrimethoxysilane, perfluorodecyltriethoxysilane, perfluorodecyltrichlorosilane, perfluorooctyltrimethoxysilane, perfluorooctyltriethoxysilane, and perfluorooctyltrichlorosilane.
Further, in the step 3, the total mass ratio of the fluorosilane to the two kinds of particle size silica is more than 1: 1.
the invention has strict requirements on the proportion control of the fluorosilane, and the total mass ratio of the fluorosilane to the silicon dioxide with two particle sizes is more than 1: 1, under the proportion, the fluorosilane can not only completely graft the surface of the silicon dioxide with long-chain hydrophobic and oleophobic groups, but also partially remain in the solvent; when the surface spraying is carried out on the silicon dioxide particle composite suspension, the residual fluorosilane in the solvent can carry out condensation reaction with the epoxy group of the semi-cured epoxy resin layer sprayed before, so that a layer of fluorinated film can be formed on the surface of the substrate together with the fluorine group on the surface of the silicon dioxide particle while the surface energy of the epoxy resin layer is reduced, and the durability, the firmness and the anti-icing durability of the surface of the super-amphiphobic coating are further improved.
Further, in the step 4 and the step 5, a spray gun is used for spraying, the spray gun is a commercial spray gun with the diameter of 0.5-2 mm, compressed air is used as a carrier, a spray spot is adjusted to be fan-shaped, the spray distance between the spray nozzle and the substrate is 10-20 cm, the spray nozzle and the substrate are perpendicular to form an angle of 90 degrees, the base materials are sequentially sprayed at the speed of 2-5 cm/s from left to right, the spraying pressure is 30-100 psi, and the base materials are repeatedly sprayed for 2-5 times.
Further, the step 6 is washed by ethanol or acetone.
The raw materials of the super-amphiphobic coating prepared by the preparation method mainly comprise an epoxy resin solution and a particle composite suspension, wherein the epoxy resin solution comprises 4-10 parts of epoxy resin, 2-10 parts of a curing agent and 100 parts of a first solvent; the particle composite suspension comprises 1-3 parts of submicron particles, 1-3 parts of nanoparticles, 2-10 parts of fluorosilane and 100 parts of a second solvent.
The invention has the following beneficial effects:
(1) according to the super-amphiphobic coating prepared on the surface of each substrate, the contact angle between the super-amphiphobic coating and water, glycerol, edible oil, crude oil and the like is larger than 150 degrees, and the rolling angle is smaller than 10 degrees, so that the substrate has excellent super-amphiphobic performance of super-hydrophobicity and super-lipophobicity, and good self-cleaning performance.
(2) The super-amphiphobic coating prepared on the surface of each substrate has good durability and firmness, and has durable anti-icing performance.
(3) The super-amphiphobic coating capable of resisting icing durably prepared by the invention has excellent aging resistance and acid-base corrosion resistance, and can withstand certain impact resistance; after the paint is placed in a natural environment for one year, the appearance and the color of the coating have no obvious change, and the excellent super-amphiphobic property and the anti-icing property can be still protected.
(4) The super-amphiphobic coating capable of resisting icing durably can be applied to most surfaces needing icing prevention, such as electric wires hung in the high air outdoors, airplane wings flying in clouds, wings of wind driven generators and the like.
(5) All reagents used in the method can use industrial reagents, the adopted method has simple operation process, common commercial raw materials are simply diluted and dispersed and are sequentially sprayed on the base material through a spraying technology, the required coating can be directly obtained, the cost is low, the method is green and environment-friendly, complex treatment steps are not needed, expensive instruments and equipment are not needed, the method is suitable for preparing a large-batch super-amphiphobic coating on the surface of the related base material, the application prospect of large-scale industrialization is realized, and great economic benefits can be created.
Drawings
FIG. 1 is a graph showing the super-hydrophobic and super-oleophobic macroscopic effect of the super-amphiphobic aluminum alloy surface of example 1 of the present invention on water and oil.
FIG. 2 is a diagram showing the super-hydrophobic and super-oleophobic macroscopic effect of the surface of the super-amphiphobic poplar board on water and oil in example 2 of the invention.
Fig. 3 is a graph showing the super-hydrophobic and super-oleophobic macroscopic effect of the surface of the super-amphiphobic corrugated cardboard of example 3 of the invention on water and oil.
FIG. 4 is a graph showing the super-hydrophobic and super-oleophobic macroscopic effect of the super-amphiphobic red brick surface of example 4 of the present invention on water and oil.
Fig. 5 is a contact angle test chart of the super-amphiphobic aluminum alloy surface coating and water drops in example 1 of the invention.
Fig. 6 is a contact angle test chart of the super-amphiphobic aluminum alloy surface coating and glycerol in the embodiment 1 of the invention.
FIG. 7 is a schematic diagram of a sand leakage experiment in the impact resistance test of the super-amphiphobic coatings of examples 1-4 of the present invention.
In the figure, 1-water, 2-soybean oil, 3-glycerol, 4-hydraulic oil, 5-sand falling flow, 6-super-amphiphobic coating, 7-sand collector and 8-sand collector are 30cm away from the super-amphiphobic coating.
Detailed Description
The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which form a part hereof, and which together with the embodiments of the invention serve to explain the principles of the invention.
Example 1
In the embodiment, the base material is an aluminum alloy plate with a thickness of about 200 x 3mm, the aluminum alloy plate can be of a type of shanghai wisdom trades ltd-2014, and the preparation method of the super-amphiphobic aluminum alloy plate capable of resisting ice for a long time is carried out according to the following steps:
(1) taking an aluminum alloy plate as a base material, cleaning the aluminum alloy plate by using water and clean cotton cloth, and then carrying out sand blasting roughening treatment on the surface of a matrix by using 80-mesh brown corundum sand, wherein the air pressure is 0.5MPa, and the sand blasting time is 1 minute; then sequentially cleaning the surface of the substrate by using acetone, ethanol and deionized water, and drying at room temperature for later use;
(2) dissolving 5g of epoxy resin (Nantong star synthetic materials Co., Ltd., Phoenix brand, epoxy resin (E-44)) and 5g of alicyclic amine curing agent in a mixed solvent of 50mL of acetone, 30mL of xylene and 20mL of tert-butyl acetate by ultrasonic stirring to prepare epoxy resin glue solution;
(3) weighing 3g of hydrophilic fumed silica with the particle size of 7-40 nm and 3g of silica with the average particle size of 200nm, stirring and ultrasonically dispersing in 100mL of acetone for 1 hour; then 8g of perfluorodecyl trichlorosilane is added, and the mixture is continuously stirred and subjected to ultrasonic treatment for 1 hour to prepare a particle composite solution;
(4) spraying the epoxy resin glue solution prepared in the step (2) on the surface of the aluminum alloy plate base material by a spray gun: a commercial spray gun with the nozzle diameter of 0.5mm is used, compressed air is used as a carrier, spray spots are adjusted to be in a fan shape, the spray distance between the nozzle and the base material is 15cm, the nozzle and the base material are perpendicular to form an angle of 90 degrees, the spray pressure is unchanged at 30psi, and the base material is sprayed from left to right at the speed of 5 cm/s; repeating the steps for 2 times; semi-curing for 1 hour at normal temperature to obtain a required semi-cured epoxy resin adhesive layer on the aluminum alloy plate substrate;
(5) spraying the particle composite solution in the step (3) on the surface of the semi-cured epoxy resin adhesive layer in the step (4) by adopting the same spraying technology as that in the step (4), and repeatedly spraying for 3 times; then placing the mixture at normal temperature for 5 hours to be completely cured;
(6) and (5) washing the surface of the base material obtained in the step (5) by using ethanol or acetone to obtain the durable anti-icing super-amphiphobic aluminum alloy plate.
Meanwhile, the invention detects the performance of the prepared super-amphiphobic aluminum alloy plate:
(1) detecting the super-hydrophobic and super-oleophobic performances:
measuring 5 mu L of water and oil by using a micro-syringe at room temperature, horizontally dropping the water and oil on the surface of a sample, standing for 5s, measuring by using a JC2000C type contact angle measuring instrument of the Shanghai Zhongchen digital technology equipment Limited company, reading the contact angle value of the water and the oil, and measuring the rolling angle of the surface of the coating by using an inclined plate method; the test result shows that the contact angle of the coating to water reaches 161 degrees, and the rolling angle is 3 degrees; the contact angle of the oil to the glycerol reaches 154 degrees, and the rolling angle is 5 degrees.
(2) The anti-icing performance is detected:
the anti-icing performance of the super-amphiphobic coating is measured by a self-made instrument: the aluminum alloy plate sample prepared in this example 1 was placed on a platform, the platform was allowed to stand horizontally at an angle of 30 degrees, the surface temperature of the platform was cooled to-10 ℃, and when the temperature of the platform reached the set value and stabilized, atomized water droplets (about 0.5mm in diameter) were horizontally sprayed on the surface of the sample coating by a spray gun and continuously sprayed for 200 minutes. Observation in the continuous spraying process shows that when the small water drops are sprayed to the surface of the base material, the small water drops are instantly flicked away, and the staying time of the water drops on the surface of the base material is extremely short; no small water drops are hung on the surface of the sample, and the phenomenon of icing does not occur after 200 minutes.
The method for preparing the aluminum alloy plate coating of the five comparative examples is disclosed in the invention, namely the five comparative examples are comparative examples 1-5, experimental data are shown in a table 1, the comparative example 1 is that the two kinds of silicon dioxide with the grain diameter in the step (3) in the embodiment 1 are changed into the hydrophilic fumed silica with the grain diameter of 7-40 nm, and other steps are not changed; finally preparing the surface of the super-amphiphobic aluminum alloy plate; the contact angle of water measured by a contact angle measuring instrument reaches 166 degrees, and the rolling angle is 2 degrees; the contact angle of the glycerol is 158 degrees, the rolling angle is 4 degrees, and the result proves that the super-amphiphobic coating can be realized only by using the fumed silica with small particle size; but the surface is tested for anti-icing performance, when atomized small water drops (about 0.5mm in diameter) are sprayed on the surface of the substrate, the small water drops are firstly condensed into large water drops of about 2mm and then roll off on the surface of the substrate, so that the residence time of the water drops on the surface is increased; after the spraying was continued for 20 minutes, a thick layer of ice was formed on the surface of the aluminum alloy sheet, indicating that the surface of the aluminum alloy sheet prepared in comparative example 1 was not anti-icing.
Comparative example 2 is obtained by changing two kinds of silica having particle diameters in the step (3) in the present example 1 to those having particle diameters of 200nm only, and the other steps are not changed; finally preparing the surface of the super-amphiphobic aluminum alloy plate; the contact angle of water measured by a contact angle measuring instrument reaches 154 degrees, and the rolling angle is 6 degrees; the contact angle of glycerol is 150 degrees, the rolling angle is 8 degrees, and the super-amphiphobic coating can be realized only by using silicon dioxide with the particle size of 200 nm. The surface is also tested for anti-icing performance, when atomized small water drops (about 0.5mm in diameter) are sprayed on the surface of the substrate, the small water drops are firstly condensed into large water drops of about 3mm and then roll off the surface of the substrate, so that the residence time of the water drops on the surface is increased; when the spraying was continued for 5 minutes, a thick layer of ice formed on the surface of the aluminum alloy sheet, indicating that the surface of the aluminum alloy sheet prepared in comparative example 2 was also not anti-icing.
And comparative examples 3 to 5 were tested by changing the mass ratio of the hydrophilic fumed silica of 7 to 40nm to the silica of 200nm particle size, as shown in Table 1.
Table 1 experimental data for the anti-icing performance test of example 1
Figure BDA0001275431020000101
(3) And (3) detecting acid and alkali corrosion resistance:
the super-amphiphobic aluminum alloy sheet prepared in example 1 was sprayed on both front and back sides, and immersed in a sulfuric acid solution having a pH of 1 and a NaOH solution having a pH of 14 for 50 hours, respectively, to test the acid resistance and alkali resistance of the coating. After 50 hours of immersion, no signs of damage were observed on the surface of the coating; and measuring the water contact angle and the oil contact angle of the coating, wherein the water contact angle is 160 degrees, the water rolling angle is 4 degrees, the glycerol contact angle is 152 degrees and the rolling angle is 5 degrees after the acid resistance test; after alkali resistance test, the water contact angle is 159 degrees, the water rolling angle is 4 degrees, the glycerol contact angle is 152 degrees, and the rolling angle is 6 degrees; the super-amphiphobic coating prepared on the surface of the aluminum alloy plate in the embodiment 1 has good acid and alkali corrosion resistance.
(4) And (3) detecting the impact resistance:
example 1 utilization ofThe mechanical property of the super-amphiphobic coating on the surface of the aluminum alloy plate is verified through a sand leakage experiment, a state diagram of the sand leakage experiment is shown in figure 7, the super-amphiphobic aluminum alloy plate prepared in the example 1 is horizontally placed at an angle of 45 degrees, a container is placed at a position 30cm away from the center of the super-amphiphobic aluminum alloy plate prepared in the example 1, and 2kg of sand grains with the grain diameter of 100-300 mu m are placed in the container; the sand grains are leaked from the container and collide with the super-amphiphobic coating on the surface of the inclined super-amphiphobic aluminum alloy plate prepared in the example 1, the sand leakage speed is about 1g/s, and the collision area is about 1cm2(ii) a After the sand grains are completely leaked, lightly washing away the sand on the surface of the aluminum alloy plate by using deionized water, and then measuring that the water contact angle of the coating still can reach 158 degrees and the rolling angle reaches 4 degrees; the glycerol contact angle is 151 degrees, the rolling angle reaches 6 degrees, and the super-amphiphobic coating on the surface of the aluminum alloy plate has good impact resistance; meanwhile, after the surface of the aluminum alloy plate subjected to the sand leakage experiment is placed in an environment with the temperature of-10 ℃ for water spraying, the surface of the aluminum alloy plate is still free of icing after spraying for 200 minutes.
Meanwhile, after the sand leakage experiment of the comparative example 1 and the comparative example 2 is carried out under the same conditions as the example 1, the contact angles of water and oil are obviously reduced, and the rolling angles are also obviously increased, and the specific experimental data are shown in the table 2. Meanwhile, the antifogging performance detection of the sprayed and atomized water mist shows that condensed large water drops appear on the surfaces of the coatings of the comparative example 1 and the comparative example 2 after the sand leakage experiment at the moment that the water mist is sprayed on the surfaces, and the large water drops can roll off from the surfaces only when being condensed into 3-5 mm water drops; when the sample was exposed to a water spray at-10 c, it was found that a distinct ice layer was formed on the surface of the coating by continuing the water spray for only 5 minutes.
The invention also prepares a comparative example 6, the preparation method of the comparative example 6 is to directly spray the composite particle solution on the aluminum alloy plate instead of spraying the epoxy resin adhesive layer in the step (2) in the embodiment 1, other steps are the same as the embodiment 1, and the sand leakage resistance experiment which is completely the same as the embodiment 1 is carried out on the surface of the aluminum alloy plate cured in the comparative example 6; after the sand leakage experiment is completed, the composite particle coating on the surface of the aluminum alloy plate is found to be completely knocked off, the aluminum alloy is exposed, and the super-amphiphobicity of the aluminum alloy plate is completely lost, and specific data are shown in table 2.
Table 2 experimental data of the impact resistance test in example 1
Figure BDA0001275431020000121
From the above tests on the impact resistance of the coatings of comparative examples 1, 2 and 6, it is found that the epoxy resin glue layer can be firmly adhered to the surface of the substrate on one hand, and on the other hand, the epoxy resin glue layer firmly adheres the inorganic silica particles to serve as an intermediate adhesive body, which plays a key role in the durability, stability and sustainable anti-icing property of the super-amphiphobic coating; in addition, because the two types of silica particles are mutually cross bound, when external force is applied to the coating, the submicron silica particles with large particle size have certain dispersion effect on the force applied to the nanometer fumed silica with small particle size, and the combined action of the two types of particles also plays a key role in the durability, the stability and the sustainable anti-icing performance of the super-amphiphobic coating.
The experimental data of the comparative example further illustrate that the super-amphiphobic coating prepared on the surface of the aluminum alloy plate in the embodiment 1 has good impact resistance and can resist the icing for a long time.
(5) Detecting the ultrasonic resistance:
soaking the super-amphiphobic aluminum alloy plate prepared in the embodiment 1 in absolute ethyl alcohol or acetone, wherein the absolute ethyl alcohol or the acetone has good wettability on a coating, and then performing ultrasonic treatment for 200min by using a Jie 'S JP-080S-type ultrasonic cleaning machine (Jie' S cleaning equipment Co., Ltd., Shenzhen), so that the water contact angle after ultrasonic treatment can still reach 158 degrees, and the rolling angle can reach 4 degrees; the contact angle of glycerol is 151 degrees, the rolling angle reaches 6 degrees, which shows that the super-amphiphobic coating prepared on the surface of the aluminum alloy plate in the embodiment 1 has good ultrasonic resistance.
(6) And (3) detecting the aging resistance:
the aging resistance of the super-amphiphobic coating prepared by the invention is tested by a xenon lamp aging instrument, the super-amphiphobic coating aluminum alloy plate prepared in the example 1 is placed in the xenon lamp aging instrument, the temperature is 38 ℃,irradiation intensity at 340nm of 0.51W/m2After 2000 hours of irradiation, the coating has no obvious change, the water contact angle reaches 159 degrees, the rolling angle reaches 4 degrees, the glycerol contact angle reaches 153 degrees and the glycerol rolling angle reaches 6 degrees, which shows that the super-amphiphobic coating prepared on the surface of the aluminum alloy plate in the embodiment 1 has good aging resistance.
Example 2
In this example, a poplar board with a thickness of about 200 × 15mm was selected as the base material, and the method for preparing a super-amphiphobic poplar board with durable anti-icing properties was performed according to the following steps:
(1) cleaning a poplar board serving as a base material by using water and clean cotton cloth, and then performing sand blasting roughening treatment on the surface of the base body by using 200-mesh brown corundum sand, wherein the air pressure is 2.0MPa, and the sand blasting time is 30 s; then sequentially cleaning the surface of the substrate by using acetone, ethanol and deionized water, and drying at room temperature for later use;
(2) dissolving 8g of epoxy resin (Nantong star synthetic materials Co., Ltd., Phoenix brand, epoxy resin (E-51)) and 5g of alicyclic amine curing agent in a mixed solvent of 50mL of acetone, 35mL of toluene and 15mL of ethyl acetate by ultrasonic stirring to prepare epoxy resin glue solution;
(3) weighing 2.4g of hydrophilic fumed silica with the particle size of 7-40 nm and 1.6g of silica with the average particle size of 500nm, stirring and ultrasonically dispersing in 100mL of absolute ethyl alcohol, and ultrasonically treating for 1.5 hours; then 6g of perfluorodecyl trioxysilane is added, and after continuous stirring and ultrasonic treatment for 1.5 hours, a particle composite solution is prepared;
(4) spraying the epoxy resin glue solution obtained in the step (2) on the surface of the poplar board substrate by a spray gun: a commercial spray gun with the nozzle diameter of 0.5mm is used, compressed air is used as a carrier, spray spots are adjusted to be in a fan shape, the spray distance between the nozzle and the base material is 20cm, the nozzle and the base material are perpendicular to form an angle of 90 degrees, the spray pressure is unchanged at 50psi, and the base material is sprayed from left to right at the speed of 5 cm/s; repeating the above steps for 3 times; semi-curing the poplar board substrate for 2 hours at normal temperature to obtain a required semi-cured epoxy resin adhesive layer;
(5) spraying the particle composite solution in the step (3) on the surface of the semi-cured epoxy resin adhesive layer in the step (4) by adopting the same spraying technology as that in the step (4), and repeatedly spraying for 5 times; then placing the mixture at normal temperature for 5 hours to be completely cured;
(6) and (5) washing the surface of the base material obtained in the step (5) by using ethanol or acetone to obtain the durable anti-icing super-amphiphobic poplar board.
The invention detects the performance of the poplar board prepared in the embodiment 2, and the method specifically comprises the following steps:
(1) detecting the super-hydrophobic and super-oleophobic performances of the poplar board:
measuring 5 mu L of water and oil by using a micro-syringe at room temperature, horizontally dropping the water and oil on the surface of a sample, standing for 5s, measuring by using a JC2000C type contact angle measuring instrument of the Shanghai Zhongchen digital technology equipment Limited company, reading the contact angle value of the water and the oil, and measuring the rolling angle of the surface of the coating by using an inclined plate method; the test result shows that the contact angle of the coating to water reaches 166 degrees, and the rolling angle is 2 degrees; the contact angle of the oil to the glycerol reaches 156 degrees, and the rolling angle is 4 degrees.
(2) Detecting the anti-icing performance of the poplar board:
the anti-icing performance of the super-amphiphobic coating is measured by a self-made instrument: the poplar board sample prepared in the embodiment 2 is placed on a platform, the platform is horizontally placed at an angle of 30 degrees, the surface temperature of the platform is cooled to-10 ℃, and when the temperature of the platform reaches the set value and is stable, atomized water drops (about 0.5mm in diameter) are horizontally sprayed on the surface of a sample coating through a spray gun and continuously sprayed for 200 minutes; observation in the continuous spraying process shows that when the small water drops are sprayed to the surface of the base material, the small water drops are instantly flicked away, and the staying time of the water drops on the surface of the base material is extremely short; no small water drops are hung on the surface of the sample, and the phenomenon of icing does not occur after 200 minutes.
Comparative example 7 and comparative example 8 were prepared, in comparative example 7, the two kinds of silica having particle sizes in step (3) in example 2 were changed to hydrophilic fumed silica having particle sizes of 7 to 40nm, and the other steps were not changed; finally, the surface of the super-amphiphobic poplar wood plate is prepared, and the comparative example 7 is detected by a contact angle measuring instrument to obtain that the contact angle of the super-amphiphobic poplar wood plate to water reaches 167 degrees and the rolling angle is 2 degrees; the contact angle of glycerol is 158 degrees, the rolling angle is 3 degrees, and the fact that only fumed silica with small particle size is used is proved that the super-amphiphobic coating can be realized. But the surface is tested for anti-icing performance, when atomized small water drops (about 0.5mm in diameter) are sprayed on the surface of the poplar board substrate, the small water drops are firstly condensed into large water drops of about 2mm and then roll off on the surface of the poplar board substrate, so that the residence time of the water drops on the surface is increased; after spraying for 20 minutes, a thick layer of ice is formed on the surface of the poplar board, which indicates that the poplar board prepared in the comparative example 7 is not anti-icing on the surface.
Comparative example 8 is a case where two kinds of silica having particle diameters in the step (3) of this example 2 were changed to only silica having particle diameter of 500nm, and the other steps were not changed; finally, the surface of the super-amphiphobic poplar board is prepared. The contact angle of water measured by a contact angle measuring instrument reaches 152 degrees, and the rolling angle is 8 degrees; the contact angle of glycerol was 146 °, the rolling angle was 10 °, demonstrating that only 500nm particle size silica was used, while super-hydrophobic was achieved, but not super-oleophobic. Similarly, the anti-icing performance of the surface of the poplar board substrate prepared in the comparative example 8 is detected, when atomized small water drops (about 0.5mm in diameter) are sprayed on the surface of the substrate, the small water drops are firstly condensed into large water drops of about 2-5 mm and then roll off the surface of the substrate, so that the residence time of the water drops on the surface is also increased; after the spraying is continuously carried out for 5 minutes, a thick layer of ice is formed on the surface of the poplar board, which shows that the surface of the poplar board prepared by the comparative experiment is not anti-icing.
(3) And (3) detecting acid and alkali corrosion resistance:
samples of the super-amphiphobic poplar wood panels prepared in example 2 were soaked in a sulfuric acid solution having a pH of 1 and a NaOH solution having a pH of 14 for 50 hours, respectively, and the acid resistance and alkali resistance of the coatings were tested. After 50 hours of immersion, no signs of damage were observed on the surface of the coating; and testing the water contact angle and the oil contact angle of the soaked coating, wherein the water contact angle reaches 164 degrees, the water rolling angle reaches 3 degrees, the glycerol contact angle reaches 155 degrees and the rolling angle reaches 6 degrees after the acid resistance test; after the alkali resistance test, the water contact angle reaches 163 degrees, the water rolling angle reaches 3 degrees, the glycerol contact angle reaches 154 degrees, and the rolling angle reaches 6 degrees. The super-amphiphobic coating prepared on the surface of the poplar board in the embodiment 2 is proved to have good acid and alkali corrosion resistance.
(4) And (3) detecting the impact resistance:
the mechanical properties of the super-amphiphobic coating on the surface of the poplar board are verified by using a sand leakage experiment in the embodiment 2, and are shown in fig. 7: horizontally placing the poplar board base material at an angle of 45 degrees, and placing a container at a position 30cm away from the center of the poplar board base material, wherein 2kg of sand grains with the grain diameter of 100-300 mu m are placed in the container; the sand grains are leaked from the container and collide with the super-amphiphobic coating on the surface of the inclined poplar board substrate, the sand leakage speed is about 1g/s, and the collision area is about 1cm2(ii) a After the sand grains are completely leaked, lightly washing off the sand on the surface of the poplar board by using deionized water, and then measuring that the water contact angle of the coating still can reach 160 degrees and the rolling angle reaches 4 degrees; the contact angle of the glycerol reaches 152 degrees, and the rolling angle reaches 6 degrees; the super-amphiphobic coating prepared on the surface of the poplar board in the embodiment 2 has good impact resistance; meanwhile, after the surface of the poplar wood board subjected to the sand leakage experiment is placed in an environment with the temperature of-10 ℃ for water spraying, the surface of the poplar wood board is still not obviously frozen after the poplar wood board is continuously sprayed for 200 minutes.
(5) Aging resistance detection performance:
the aging resistance of the super-amphiphobic coating prepared in the example 2 is tested by a xenon lamp aging instrument, a sample is placed in the xenon lamp aging instrument, and the irradiation intensity at 38 ℃ and 340nm is 0.51W/m2After 2000 hours of irradiation, the coating has no obvious change, the water contact angle reaches 164 degrees, the rolling angle reaches 3 degrees, the glycerol contact angle reaches 154 degrees, and the glycerol rolling angle is 5 degrees; the super-amphiphobic coating prepared on the surface of the poplar board in the embodiment 2 has good aging resistance.
Example 3
In this embodiment, the method for manufacturing super-amphiphobic corrugated cardboard with durable anti-icing performance is carried out according to the following steps:
(1) the corrugated board is used as a base material, and is wiped clean by clean cotton cloth for later use;
(2) dissolving 5g of epoxy resin (NPEL-128) from south Asia plastics industries, Ltd.) and 2g of alicyclic amine curing agent in a mixed solvent of 40mL of acetone, 40mL of xylene and 20mL of tert-butyl acetate by ultrasonic stirring to prepare an epoxy resin glue solution;
(3) weighing 1.1g of hydrophilic fumed silica with the particle size of 7-40 nm and 0.9g of silica with the average particle size of 300nm, stirring and ultrasonically dispersing in 100mL of n-hexane for 1.5 hours; then 4g of perfluorooctyl trichlorosilane is added, and after continuous stirring and ultrasonic treatment for 1.5 hours, a particle composite solution is prepared;
(4) spraying the epoxy resin glue solution in the step (2) on the surface of the corrugated board base material by a spray gun: a commercial spray gun with the nozzle diameter of 0.5mm is used, compressed air is used as a carrier, spray spots are adjusted to be in a fan shape, the spray distance between the nozzle and the base material is 15cm, the nozzle and the base material are perpendicular to form an angle of 90 degrees, the spray pressure is unchanged at 30psi, and the base material is sprayed from left to right at the speed of 5 cm/s; repeating the steps for 2 times; after semi-curing for 2 hours at normal temperature, the corrugated board substrate obtains a needed semi-cured epoxy resin adhesive layer;
(5) spraying the particle composite solution in the step (3) on the surface of the semi-cured epoxy resin adhesive layer in the step (4) by adopting the same spraying technology as that in the step (4), and repeatedly spraying for 6 times; then placing the mixture at normal temperature for 5 hours to be completely cured;
(6) and (5) washing the surface of the base material obtained in the step (5) by using ethanol or acetone to obtain the super-amphiphobic corrugated board with the lasting anti-icing property.
The invention detects the performance of the super-amphiphobic corrugated board prepared in the embodiment 3, and concretely comprises the following steps:
(1) the super-hydrophobic and super-oleophobic performances of the super-amphiphobic corrugated board prepared in example 3 were tested:
measuring 5 mu L of water and oil by using a micro-syringe at room temperature, horizontally dropping the water and oil on the surface of a sample, standing for 5s, measuring by using a JC2000C type contact angle measuring instrument of the Shanghai Zhongchen digital technology equipment Limited company, reading the contact angle value of the water and the oil, and measuring the rolling angle of the surface of the coating by using an inclined plate method; the test result shows that the contact angle of the coating to water reaches 164 degrees, and the rolling angle is 3 degrees; the contact angle of the oil to the glycerol reaches 156 degrees, and the rolling angle is 5 degrees.
(2) The anti-icing performance of the super-amphiphobic corrugated board prepared in example 3 was tested:
the anti-icing performance of the super-amphiphobic coating is measured by a self-made instrument: the corrugated cardboard sample prepared in this example 3 was placed on a platform, the platform was allowed to stand horizontally at an angle of 30 degrees, the surface temperature of the platform was cooled to-10 ℃, and when the temperature of the platform reached the set value and stabilized, atomized water droplets (about 0.5mm in diameter) were horizontally sprayed on the surface of the sample coating by a spray gun and continuously sprayed for 200 minutes. Observation in the continuous spraying process shows that when the small water drops are sprayed to the surface of the base material, the small water drops are instantly flicked away, and the staying time of the water drops on the surface of the base material is extremely short; no small water drops are hung on the surface of the sample, and the phenomenon of icing does not occur after 200 minutes.
Comparative example 9 and comparative example 10 were prepared, in comparative example 9, the two kinds of silica having particle diameters in step (3) in example 3 were changed to hydrophilic fumed silica having particle diameters of 7 to 40nm, and the other steps were not changed; finally, the surface of the super-amphiphobic corrugated paperboard is prepared. The contact angle of the surface of the super-amphiphobic corrugated paperboard prepared in the comparative example 9 to water is measured to be 166 degrees and the rolling angle is 2 degrees by a contact angle measuring instrument; the contact angle of glycerol is 157 degrees and the rolling angle is 4 degrees, which proves that the super-amphiphobic coating can be realized only by using fumed silica with small grain diameter; but the surface is tested for anti-icing performance, when atomized small water drops (about 0.5mm in diameter) are sprayed on the surface of the substrate, the small water drops are firstly condensed into large water drops of about 2mm and then roll off on the surface of the substrate, so that the residence time of the water drops on the surface is increased; after spraying for 20 minutes, the surface of the corrugated cardboard became a thick layer of ice, indicating that the surface of the corrugated cardboard prepared in comparative example 9 was not anti-icing.
Comparative example 10 is a case where two kinds of silica having particle diameters in the step (3) in this example were changed to only silica having particle diameter of 300nm, and the other steps were not changed; finally, preparing the surface of the super-amphiphobic corrugated paperboard; the contact angle of water measured by a contact angle measuring instrument reaches 153 degrees, and the rolling angle is 5 degrees; the contact angle of glycerin is 151 degrees, the rolling angle is 7 degrees, and the super-amphiphobic coating can be realized only by using silicon dioxide with the particle size of 300 nm; the surface is also tested for anti-icing performance, when atomized small water drops (about 0.5mm in diameter) are sprayed on the surface of the substrate, the small water drops are firstly condensed into large water drops of about 3mm and then roll off the surface of the substrate, so that the residence time of the water drops on the surface is increased; after 5 minutes of continuous spraying, the surface of the corrugated cardboard became a thick layer of ice, indicating that the surface of the corrugated cardboard prepared in this comparative example 10 was also not resistant to ice.
(3) The impact resistance of the super-amphiphobic corrugated board prepared in example 3 was tested:
in this embodiment 3, the mechanical properties of the super-amphiphobic coating on the surface of the corrugated board are verified by using a sand leakage experiment, which is shown in fig. 7: horizontally placing a sample at an angle of 45 degrees, and placing a container at a position 30cm away from the center of the sample, wherein 2kg of sand particles with the particle size of 100-300 mu m are placed in the container; the sand grains are leaked from the container and collide with the super-amphiphobic coating on the surface of the inclined sample, the sand leakage speed is about 1g/s, and the collision area is about 1cm2. After the sand particles are completely leaked, lightly washing away the sand on the surface of the corrugated paperboard by using deionized water, and then measuring that the water contact angle of the coating still can reach 159 degrees and the rolling angle reaches 5 degrees; the contact angle of the glycerol is also 152 degrees, and the rolling angle reaches 7 degrees; it is demonstrated that the super-amphiphobic coating prepared on the surface of the corrugated paperboard in the embodiment 3 has good impact resistance. Meanwhile, after the corrugated board after the sand leakage experiment is placed in an environment at the temperature of-10 ℃ for water spraying, the obvious icing phenomenon on the surface of the sample still does not occur after the spraying is continuously carried out for 200 minutes.
(4) The aging resistance of the super-amphiphobic corrugated board prepared in example 3 was tested:
the aging resistance of the super-amphiphobic coating prepared in the embodiment 3 is tested by a xenon lamp aging instrument, a sample is placed in the xenon lamp aging instrument, and the irradiation intensity at 38 ℃ and 340nm is 0.51W/m2After 2000 hours of irradiation, the coating has no obvious change, the water contact angle reaches 161 degrees, the rolling angle reaches 4 degrees, the glycerol contact angle reaches 153 degrees and the glycerol rolling angle reaches 7 degrees; the super-amphiphobic coating prepared on the surface of the corrugated paperboard in the embodiment 3 has good aging resistance.
Example 4
In this example, the method for preparing super-amphiphobic red bricks with durable anti-icing properties, in which red bricks with a thickness of about 200 × 100 × 50mm are selected as the base material, was carried out as follows:
(1) the red brick is used as a base material, is cleaned by water and clean cotton cloth, and then is subjected to sand blasting roughening treatment on the surface of the matrix by adopting 80-mesh brown corundum sand, wherein the air pressure is 1.0MPa, and the sand blasting time is 1 minute; then sequentially cleaning the surface of the substrate by using acetone, ethanol and deionized water, and drying at room temperature for later use;
(2) dissolving 5g of epoxy resin (NPEF-170) from south Asia plastics industries, Ltd.) and 5g of alicyclic amine curing agent in a mixed solvent of 50mL of acetone, 30mL of xylene and 20mL of tert-butyl acetate by ultrasonic stirring to prepare epoxy resin glue solution;
(3) weighing 2g of hydrophilic fumed silica with the particle size of 7-40 nm and 2g of silica with the average particle size of 200nm, stirring and ultrasonically dispersing in 100mL of acetone for 1 hour; then adding 6g of perfluorooctyl triethoxysilane, continuing stirring and carrying out ultrasound treatment for 1 hour to prepare a particle composite solution;
(4) spraying the epoxy resin glue solution in the step (2) on the surface of the red brick base material through a spray gun: a commercial spray gun with the nozzle diameter of 0.5mm is used, compressed air is used as a carrier, spray spots are adjusted to be in a fan shape, the spray distance between the nozzle and the base material is 15cm, the nozzle and the base material are perpendicular to form an angle of 90 degrees, the spray pressure is unchanged at 30psi, and the base material is sprayed from left to right at the speed of 5 cm/s; repeating the steps for 2 times; semi-curing for 1 hour at normal temperature to obtain a required semi-cured epoxy resin adhesive layer on the red brick substrate;
(5) spraying the particle composite solution in the step (3) on the surface of the semi-cured epoxy resin adhesive layer in the step (4) by adopting the same spraying technology as that in the step (4), and repeatedly spraying for 5 times; then placing the mixture at normal temperature for 5 hours to be completely cured;
(6) and (3) washing the surface of the base material obtained in the step (5) by using ethanol or acetone to obtain the durable anti-icing super-amphiphobic red brick plate.
The invention detects the performance of the super-amphiphobic red brick plate prepared in the embodiment 4, and concretely comprises the following steps:
(1) the super-hydrophobic and super-oleophobic performance detection is carried out on the super-amphiphobic red brick plate prepared in the example 4:
measuring 5 mu L of water and oil by using a micro-syringe at room temperature, horizontally dropping the water and oil on the surface of a sample, standing for 5s, measuring by using a JC2000C type contact angle measuring instrument of the Shanghai Zhongchen digital technology equipment Limited company, reading the contact angle value of the water and the oil, and measuring the rolling angle of the surface of the coating by using an inclined plate method; the test result shows that the contact angle of the coating to water reaches 165 degrees, and the rolling angle is 3 degrees; the contact angle of the oil to glycerin reaches 158 degrees, and the rolling angle is 4 degrees.
(2) And (3) detecting the anti-icing performance:
the anti-icing performance of the super-amphiphobic coating is measured by a self-made instrument: the marble slab sample prepared in this example 4 was placed on a platform, the platform was allowed to stand horizontally at an angle of 30 degrees, the surface temperature of the platform was cooled to-10 ℃, and when the platform temperature reached this set value and stabilized, atomized water droplets (about 0.5mm in diameter) were sprayed horizontally on the surface of the sample coating by a spray gun and continued spraying for 200 minutes. Observation in the continuous spraying process shows that when the small water drops are sprayed to the surface of the base material, the small water drops are instantly flicked away, and the staying time of the water drops on the surface of the base material is extremely short; no small water drops are hung on the surface of the sample, and the phenomenon of icing does not occur after 200 minutes.
Comparative example 11 and comparative example 12 were prepared, in comparative example 11, the two kinds of silica having particle diameters in step (3) of example 4 were changed to hydrophilic fumed silica having particle diameters of 7 to 40nm, and the other steps were not changed; finally preparing the surface of the super-amphiphobic red brick; the contact angle of water in comparative example 11 measured by a contact angle measuring instrument reaches 166 degrees, and the rolling angle is 2 degrees; the contact angle of the glycerol is 158 degrees, the rolling angle is 4 degrees, and the result proves that the super-amphiphobic coating can be realized only by using the fumed silica with small particle size; but the surface is tested for anti-icing performance, when atomized small water drops (about 0.5mm in diameter) are sprayed on the surface of the substrate, the small water drops are firstly condensed into large water drops of about 2mm and then roll off on the surface of the substrate, so that the residence time of the water drops on the surface is increased; after spraying for 20 minutes, a thick layer of ice formed on the surface of the red brick substrate, indicating that the surface of the red brick substrate prepared in comparative example 11 is not anti-icing.
Comparative example 12 is a case where two kinds of silica having particle diameters were used instead of silica having particle diameters of 200nm in the step (3) in this example 4, and the other steps were not changed; finally preparing the surface of the super-amphiphobic red brick plate; the contact angle of water measured by a contact angle measuring instrument reaches 154 degrees, and the rolling angle is 6 degrees; the contact angle of glycerol is 150 degrees, the rolling angle is 8 degrees, and the result proves that the performance of the super-amphiphobic coating can be realized only by using silicon dioxide with the particle size of 200 nm; the surface is also tested for anti-icing performance, when atomized small water drops (about 0.5mm in diameter) are sprayed on the surface of the substrate, the small water drops are firstly condensed into large water drops of about 3mm and then roll off the surface of the substrate, so that the residence time of the water drops on the surface is increased; after 5 minutes of continuous spraying, the surface of the red brick substrate became a thick layer of ice, indicating that the surface of the red brick substrate prepared in comparative example 12 was also not anti-icing.
(3) And (3) detecting acid and alkali corrosion resistance:
the sample of the super-amphiphobic red brick board prepared in the embodiment 4 is sprayed on the whole surface, and is respectively soaked in a sulfuric acid solution with the pH value of 1 and a NaOH solution with the pH value of 14 for 50 hours, and the acid resistance and the alkali resistance of the coating are tested; after 50 hours of immersion, no signs of damage were observed on the surface of the coating; and measuring the water contact angle and the oil contact angle of the coating, wherein the water contact angle reaches 162 degrees, the water rolling angle is 5 degrees, the glycerol contact angle is 156 degrees, and the rolling angle is 6 degrees after the acid resistance test; after alkali resistance test, the water contact angle reaches 160 degrees, the water rolling angle is 5 degrees, the glycerol contact angle is 155 degrees, and the rolling angle is 6 degrees; the super-amphiphobic coating prepared on the surface of the red brick base material in the embodiment 4 has good acid and alkali corrosion resistance.
(4) And (3) detecting the impact resistance:
in this example 4, the mechanical properties of the super-amphiphobic coating on the surface of the marble plate are verified by using a sand leakage experiment, which is shown in fig. 7: horizontally placing a sample at an angle of 45 degrees, and placing a container at a position 30cm away from the center of the sample, wherein 2kg of sand particles with the particle size of 100-300 mu m are placed in the container; the sand grains are leaked from the container and collide with the super-amphiphobic coating on the surface of the inclined sample, the sand leakage speed is about 1g/s, and the collision area is about 1cm2(ii) a When the sand is completely leaked out, useSlightly washing away sand on the surface of the marble plate by deionized water, and measuring that the water contact angle of the coating still can reach 158 degrees and the rolling angle reaches 5 degrees; the contact angle of the glycerol is 151 degrees, and the rolling angle reaches 6 degrees; the super-amphiphobic coating prepared on the surface of the red brick base material in the embodiment 4 has good impact resistance. Meanwhile, after the red brick after the sand leakage experiment is placed in an environment with the temperature of-10 ℃ for water spraying, the surface of the sample still has no obvious icing phenomenon after the spraying is continued for 200 minutes.
(5) Detecting the ultrasonic resistance:
soaking the sample of the super-amphiphobic red brick plate prepared in the embodiment 4 in absolute ethyl alcohol or acetone, wherein the absolute ethyl alcohol or acetone has good wettability on a coating, and then performing ultrasonic treatment for 200min by using a Jie JP-080S-type ultrasonic cleaning machine (Jie cleaning equipment Limited, Shenzhen), so as to measure that the water contact angle after ultrasonic treatment can still reach 159 degrees and the rolling angle can reach 4 degrees; the contact angle of the glycerol reaches 154 degrees, and the rolling angle reaches 6 degrees; the super-amphiphobic coating prepared on the surface of the red brick in the embodiment 4 has good ultrasonic resistance.
(6) And (3) detecting the aging resistance:
the aging resistance of the super-amphiphobic coating prepared by the invention is tested by a xenon lamp aging instrument, a sample is placed in the xenon lamp aging instrument, the irradiation intensity at 38 ℃ and 340nm is 0.51W/m2After 2000 hours of irradiation, the coating has no obvious change, the water contact angle reaches 163 degrees, the rolling angle reaches 4 degrees, the glycerol contact angle reaches 156 degrees, and the glycerol rolling angle is 5 degrees; the super-amphiphobic coating prepared on the surface of the red brick base material in the embodiment 4 has good aging resistance.
In conclusion, the invention provides a preparation method of the super-amphiphobic coating capable of resisting ice for a long time, and different base materials can have excellent super-hydrophobic and super-oleophobic performances and good self-cleaning performance; meanwhile, the super-amphiphobic coating prepared by the invention has antifogging and anti-icing performances, good durability and firmness, has a large-scale industrial application prospect, and can create great economic benefits.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.

Claims (4)

1. A preparation method of a super-amphiphobic coating capable of resisting icing durably is characterized by comprising the following steps:
step 1, cleaning and sandblasting coarsening treatment are carried out on the surface of a base material to obtain a treated base material; the surface of the base material is cleaned by sequentially cleaning acetone, deionized water and ethanol; the technological parameters of the sand blasting coarsening treatment are as follows: the air pressure is 0.5-1.0 MPa, the sand blasting time is 10 seconds-1 minute, and the mesh number of sand pills for sand blasting is 40-200 meshes;
step 2, blending the epoxy resin, the curing agent and the first solvent to obtain an epoxy resin solution; the epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin and novolac epoxy resin; the curing agent is alicyclic amine curing agent; the first solvent is one or more mixed solvents of toluene, xylene, acetone, methyl ethyl ketone, butanone, ethyl acetate, n-butyl acetate and tert-butyl acetate;
3, dispersing the sub-micron particles and the nano particles in a second solvent, carrying out ultrasonic treatment and stirring for 1-3 hours, adding fluorosilane, and continuing the ultrasonic treatment and stirring for 1-3 hours to obtain a particle composite suspension; the submicron particles are silicon dioxide particles with the particle size of 200-500 nm; the nano particles are hydrophilic fumed silica particles with the particle size of 7-40 nm, and the second solvent is one or more mixed solvents of acetone, ethanol, n-hexane, methyl acetate and carbon tetrachloride;
the mass ratio of the sub-micron particles, the nano particles, the fluorosilane and the second solvent is (1-3): (1-3): (2-10): 100, respectively; the total mass ratio of the fluorosilane to the two kinds of particle size silicon dioxide is more than 1: 1;
step 4, spraying the epoxy resin solution obtained in the step 2 on the surface of the base material treated in the step 1, drying the base material, and semi-curing the epoxy resin adhesive;
step 5, spraying the particle composite suspension obtained in the step 3 on the surface of the base material obtained in the step 4, and drying the base material for complete curing;
step 6, washing the surface of the base material obtained in the step 5 to obtain the super-amphiphobic coating which can resist the ice for a long time;
in the step 4, the base material is dried at the temperature of 25-80 ℃ for 0.5-2 h for semi-curing; and in the step 5, the base material is dried for 0.5-24 hours at the temperature of 25-80 ℃ for complete curing.
2. The method for preparing the super-amphiphobic coating capable of being durably anti-icing according to claim 1, wherein in the step 2, the mass ratio of the epoxy resin to the curing agent to the first solvent is (4-10): (2-10): 100.
3. the method for preparing a super-amphiphobic coating capable of being durably anti-icing according to claim 1, wherein the fluorosilane is one or more of perfluorosilane of which the carbon chain length is more than 4 and the end group is methoxy, ethoxy or chloro.
4. The super-amphiphobic coating prepared by the preparation method of the super-amphiphobic coating capable of resisting icing durably according to one of claims 1 to 3, wherein raw materials mainly comprise an epoxy resin solution and a particle composite suspension, and the epoxy resin solution comprises 4-10 parts of epoxy resin, 2-10 parts of a curing agent and 100 parts of a first solvent; the particle composite suspension comprises 1-3 parts of submicron particles, 1-3 parts of nanoparticles, 2-10 parts of fluorosilane and 100 parts of a second solvent.
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