CN112852191B - Preparation method of tungsten trioxide super-smooth coating with long-term stability and applicable to mist collection - Google Patents
Preparation method of tungsten trioxide super-smooth coating with long-term stability and applicable to mist collection Download PDFInfo
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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- 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
- B05D3/06—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 exposure to radiation
- B05D3/061—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 exposure to radiation using U.V.
- B05D3/065—After-treatment
- B05D3/067—Curing or cross-linking the coating
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- 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
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- 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
- B05D7/14—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 to metal, e.g. car bodies
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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
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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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
- B05D2202/00—Metallic substrate
- B05D2202/40—Metallic substrate based on other transition elements
- B05D2202/45—Metallic substrate based on other transition elements based on Cu
Abstract
The invention discloses a preparation method of a tungsten trioxide super-slip coating with long-term stability and capable of being used for mist collection. The ultra-smooth coating has excellent lyophobic performance, and water drops and various organic matter drops all have a sliding angle of less than 10 degrees on the surface of the ultra-smooth coating. After a series of damages such as high-speed centrifugation, long-term storage, acidic solution erosion, multiple cold and hot cycles and the like, the ultra-smooth coating still has good sliding performance. The surface of the super-smooth coating can quickly realize the capture, water drop expansion, water drop removal and the like of micro liquid drops, so that the super-smooth coating has high efficiency of mist collection. The preparation method of the coating is simple, low in cost, convenient for large-scale preparation and wide in application prospect.
Description
Technical Field
The invention belongs to the technical field of preparation of oil-filled ultra-smooth surfaces, and particularly relates to a preparation method of a tungsten trioxide ultra-smooth coating with long-term stability and capable of being used for mist collection.
Background
The preparation of the porous oiling surface is inspired by the behavior of clathra grass in nature to catch small animals. The lipleaf of pitcher plant is composed of hydrophilic components with micro-rough structure, so the surface of the lipleaf is very easy to be wetted by water to form a water film, and the small animal staying on the lipleaf can easily slide into the digestive system at the bottom of the lipleaf. The preparation of the super-smooth surface can be realized by constructing a rough structure similar to the surface structure of the pitcher plant on the surface of the substrate and then pouring proper lubricating oil. Ultra-smooth surfaces have many excellent properties: delay icing, self-cleaning, anti-fouling, control of droplet movement and the like, so that the method has great application prospects in various fields.
The artificial super-smooth surface can realize good surface lyophobic property by injecting organic lubricating oil. In addition, the ultra-smooth surface has superior mist collection performance compared to the super-hydrophobic surface because the lubricating oil has a higher thermal conductivity than gas and negligible contact angle hysteresis. However, in the face of extreme conditions and long-term water collection applications, the lubricant gradually runs off, the rough surface is exposed, and the ultra-smooth surface sliding properties become poor, thereby reducing the mist collection efficiency. Furthermore, when using fluorine and other harmful substances as lubricating oil, large losses of lubricating oil increase the risk of use of the collected water. Therefore, it is of great importance to prepare ultra-smooth surfaces with good durability.
Disclosure of Invention
The invention aims to provide a preparation method for preparing an ultra-smooth surface with good lyophobic property, which is simple and efficient in process. A hollow zinc oxide nano structure is constructed on a zinc sheet by a hydrothermal method, and the preparation of the ultra-smooth surface is realized after low surface energy substance modification and oil filling. The liquid drops have smaller sliding angles on the super-smooth surface, and the surface has better characteristics of acid and alkali resistance, self-cleaning, corrosion resistance, freezing resistance and the like.
The technical scheme for realizing the purpose of the invention is as follows: a preparation method of a tungsten trioxide super-slip coating with long-term stability and applicable to mist collection is characterized by comprising the following steps:
A. preparation in the early stage of the experiment: cutting a copper sheet into a certain size, respectively ultrasonically cleaning the copper sheet in acetone, ethanol and deionized water, and then putting the copper sheet into an oven to be dried for later use;
B. preparing tungsten trioxide nanoparticles: firstly, adding a certain amount of tungstic acid into a certain amount of 12 wt% hydrogen peroxide, wherein the mass ratio of the tungstic acid to the hydrogen peroxide is 3.5-4.0%, carrying out heat treatment on the mixed solution, stirring for a period of time until the mixed solution is completely dissolved, and cooling to room temperature; adding deionized water into the mixed solution for dilution, wherein the volume of the diluted solution is 2.0-3.5 times that of the original solution, adding a certain amount of ammonium acetate, and the molar ratio of tungstic acid to ammonium acetate is 5-7; then transferring the mixed solution into a reaction kettle, and reacting for 11-13 h at 170-190 ℃; repeatedly cleaning the precipitate obtained after the reaction with deionized water, and calcining for 1-3 h at 290-310 ℃ to obtain tungsten trioxide nanoparticles;
C. preparation of aluminum phosphate inorganic binder: adding a certain amount of aluminum hydroxide powder into a certain amount of 60% phosphoric acid solution, wherein the mass ratio of the aluminum hydroxide to the phosphoric acid solution is 0.15-0.16, and carrying out heat treatment and stirring on the mixed solution for a period of time to obtain a transparent and clean aluminum phosphate solution;
D. preparing the ultra-smooth coating: adding a certain amount of the aluminum phosphate inorganic binder obtained in the step C into a certain amount of deionized water, wherein the mass ratio of the inorganic binder to the deionized water is 0.15-0.25, then adding a certain amount of the tungsten trioxide nano particles obtained in the step B into the solution, wherein the mass ratio of the inorganic binder to the tungsten trioxide nano particles is 0.8-1.2, finally adding a certain amount of ethanol, and fully mixing to obtain a spraying solution, wherein the mass ratio of the tungsten trioxide to the ethanol is 0.05-0.1; spraying the mixed solution on a substrate, and respectively curing for 1-3 h and 0.5-1.5 h at 110-130 ℃ and 230-250 ℃ to obtain a sprayed surface; and (3) dropwise adding a certain amount of dimethyl silicone oil to the prepared spraying surface, and irradiating for a certain time under ultraviolet light to realize the grafting of the dimethyl silicone oil, thereby obtaining the super-smooth surface.
Further, in step A, the length and width of the copper sheet are 2cm × 2 cm.
Further, in the step B, the heat treatment temperature and the stirring time of the mixed solution of tungstic acid and hydrogen peroxide are respectively as follows: 90-100 ℃ and 2-4 h.
Further, in the step C, the reaction temperature and the reaction time of the aluminum hydroxide solution and the phosphoric acid solution are respectively as follows: 90-110 ℃ and 2-4 h.
Further, in the step D, the ultraviolet illumination time is 0.5 h-1.5 h.
Tungsten trioxide nano particles are prepared by a hydrothermal method, then the nano particles are sprayed on a substrate, and silicone oil is poured to prepare the tungsten trioxide super-smooth coating. In the coating preparation process, an inorganic binder is used, so that a stronger binding force between the coating and the substrate is ensured. In addition, the lubricating oil can be firmly fixed on a smooth surface due to strong intermolecular acting force between the silicone oil and the dimethyl siloxane molecular brush and the hierarchical structure of the super-smooth coating. Therefore, after the ultra-smooth surface is subjected to high-speed centrifugation, strong acid erosion, long-term storage and multiple cold and hot cycles, the sliding angle is slightly increased, good sliding stability is still achieved, and after oil is refilled, the sliding angle is reduced again, so that the ultra-smooth surface can be repeatedly used. And the collection efficiency is basically unchanged in the continuous 6-hour water collection process. In addition, after high-speed centrifugation, long-term storage and multiple times of cold and hot circulation, the mist collection efficiency is slightly reduced, and the mist collection efficiency is still good. After continuous water collection, the oil content in the water is only 28mg/L, and the water is harmless to human bodies. Therefore, the tungsten trioxide coating having long-term stability, which can be used for mist collection, can be widely used.
The invention has the beneficial effects that: compared with the prior art, the invention has the advantages that:
1. the preparation process is efficient, environment-friendly and low in cost.
2. The prepared super-smooth coating has good lyophobic property.
3. The prepared ultra-smooth coating has excellent chemical stability and mechanical durability.
4. The prepared super-smooth coating has high mist collection efficiency, and has good mist collection performance even under some extreme conditions.
5. The prepared super-smooth coating has strong bonding force with the substrate and long service life.
Drawings
FIG. 1: in example 1, the contact angles of the original copper sheet, the sprayed surface, the dimethyl siloxane grafted surface and the ultra-smooth surface, the scanning electron microscope image of the surface of the original copper sheet and the sprayed tungsten trioxide coating, and the transmission electron microscope image and the optical photograph of the tungsten trioxide nanoparticles prepared by the hydrothermal method. Wherein, the figure a is an SEM image of the surface of an original copper sheet. Figures b-d are SEM images of tungsten trioxide coatings. Graph e shows the static contact angle of water for the original copper sheet, the sprayed surface, the grafted surface and the ultra-smooth surface, respectively, from top to bottom. FIGS. f-g are TEM images of tungsten trioxide nanoparticles prepared by a hydrothermal method. Fig. h is an optical photograph of the prepared tungsten trioxide nanoparticles.
FIG. 2: x-ray diffraction pattern (XRD), X-ray photoelectron spectroscopy (XPS) of the tungsten trioxide nanocoating after spray coating in example 2. Wherein, the figure a is an XRD pattern of the tungsten trioxide nano-coating. Panel b is XPS spectra before and after grafting of dimethylsiloxane with tungsten trioxide nanocoating. FIG. c is an XPS analysis of the W4 f coated surface after grafting. FIG. d is an XPS analysis of the O1 s on the surface of the coating after grafting.
FIG. 3: the change in surface contact angle and sliding angle of water on a super-slippery surface after a series of stability tests in example 3. Graph a shows the contact angle and sliding angle of a water droplet on an ultra-smooth surface after 30s at different spin coating speeds. Panel b shows the contact angle and sliding angle of a water drop on a super-smooth surface after standing at room temperature for different days. Graph c shows the contact angle and sliding angle of water drops with different pH values on a super-smooth surface. And d is the contact angle and sliding angle of the water drop on the ultra-smooth surface after multiple hot and cold cycles.
FIG. 4: example 4, water mist collection pattern for superhydrophobic surface and super-slippery surface. Wherein, the graph a is a fog capture optical photo of the super-hydrophobic surface and the super-smooth surface within 15 s. Panel b is a fog collection optical photograph of a superhydrophobic surface and a super-slippery surface over 10 min. Graph c is the weight of water collected within 6h for the pristine copper sheet, the sprayed surface, the superhydrophobic surface, and the ultra-smooth surface. Graph d is the weight of water collected over 1h for the pristine copper sheet, the post-spray surface, the superhydrophobic surface, and the ultra-smooth surface.
FIG. 5: the efficiency of mist collection from ultra-smooth surfaces and the surface lubricant weight after various speed centrifugation tests, multiple hot and cold cycles, and long storage in example 5. Wherein the plots a-b are the mist collection efficiency and surface oil loss for an ultra-smooth surface after centrifugal testing at different speeds. Figure c is the mist collection efficiency of the ultra-smooth surface after 7 days at room temperature. Figure d is the mist collection efficiency of the ultra-smooth surface after multiple cycles of cooling and heating.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples. Various changes or modifications may be effected therein by one skilled in the art and such equivalents are intended to be within the scope of the invention as defined by the claims appended hereto.
Example 1
1. Preparation in the early stage of the experiment: cutting the copper sheet to a proper size, ultrasonically cleaning the copper sheet in acetone, ethanol and deionized water for multiple times, and then drying the copper sheet in an oven for later use.
2. Preparing tungsten trioxide acid nanoparticles: firstly, 4g of tungstic acid is added into 110ml of hydrogen peroxide (12 wt%), the mixed solution is stirred for 2h at 90 ℃ until the tungstic acid is completely dissolved, and the mixed solution is cooled to room temperature. The mixed solution was diluted to 220ml, 0.25g of ammonium acetate was added, and then the resultant mixed solution was transferred to a reaction vessel and reacted at 170 ℃ for 11 hours. And (3) repeatedly cleaning the precipitate obtained after the reaction with deionized water, and calcining the precipitate at 290 ℃ for 1h to obtain the tungsten trioxide nanoparticles.
3. Preparation of aluminum phosphate inorganic binder: 15g of aluminum hydroxide powder was added to 95g of phosphoric acid solution (60%), and the mixed solution was stirred at 90 ℃ for 2 hours to obtain a clear and clean aluminum phosphate solution.
4. Preparing the ultra-smooth coating: 0.5g of inorganic binder was dissolved in 3ml of deionized water, then 0.5g of tungsten trioxide nanoparticles was added to the above solution, and finally 10ml of ethanol was added, followed by thorough mixing to obtain a spray solution. And spraying the mixed solution on the surface of a copper sheet, and respectively curing for 1h and 0.5h at 110 ℃ and 230 ℃ to obtain a sprayed surface. And dropwise adding a certain amount of silicone oil to the prepared spraying surface, and illuminating for 0.5h under ultraviolet light to obtain the ultra-smooth surface.
5. After ultraviolet irradiation, tetrahydrofuran is used for washing away unreacted dimethyl silicone oil on the super-smooth surface, and the super-hydrophobic surface is obtained.
Example 2
1. Preparation in the early stage of the experiment: cutting the copper sheet to a proper size, ultrasonically cleaning the copper sheet in acetone, ethanol and deionized water for multiple times, and then drying the copper sheet in an oven for later use.
2. Preparing tungsten trioxide acid nanoparticles: firstly, 4.2g of tungstic acid is added into 115ml of hydrogen peroxide (12 wt%), the mixed solution is stirred for 2.5h at the temperature of 92 ℃ until the tungstic acid is completely dissolved, and the mixed solution is cooled to the room temperature. The mixed solution was diluted to 250ml, 0.24g of ammonium acetate was added, and the resulting mixed solution was transferred to a reaction vessel and reacted at 175 ℃ for 11.5 hours. And repeatedly washing the precipitate obtained after the reaction with deionized water, and calcining at 295 ℃ for 1.5h to obtain the tungsten trioxide nanoparticles.
3. Preparation of aluminum phosphate inorganic binder: 15.2g of aluminum hydroxide powder was added to 96g of phosphoric acid solution (60%), and the mixed solution was stirred at 95 ℃ for 2.5 hours to obtain a transparent and clean aluminum phosphate solution.
4. Preparing the ultra-smooth coating: 0.8g of inorganic binder was dissolved in 4ml of deionized water, then 0.8g of tungsten trioxide nanoparticles was added to the above solution, and finally 13ml of ethanol was added, followed by thorough mixing to obtain a spray solution. And spraying the mixed solution on the surface of a copper sheet, and curing at 115 ℃ and 235 ℃ for 1.5h and 0.8h respectively to obtain a sprayed surface. And dropwise adding a certain amount of silicone oil to the prepared spraying surface, and illuminating for 0.8h under ultraviolet light to obtain the super-smooth surface.
5. When in characterization, unreacted dimethyl silicone oil on the super-smooth surface is washed away by tetrahydrofuran.
Example 3
1. Preparation in the early stage of the experiment: cutting the copper sheet to a proper size, ultrasonically cleaning the copper sheet in acetone, ethanol and deionized water for multiple times, and then drying the copper sheet in an oven for later use.
2. Preparing tungsten trioxide acid nanoparticles: firstly, 4.5g of tungstic acid is added into 120ml of hydrogen peroxide (12 wt%), the mixed solution is stirred for 3 hours at 95 ℃ until the tungstic acid is completely dissolved, and the mixed solution is cooled to room temperature. The mixed solution was diluted to 300ml, 0.23g of ammonium acetate was added, and then the resultant mixed solution was transferred to a reaction vessel and reacted at 180 ℃ for 12 hours. And (3) repeatedly cleaning the precipitate obtained after the reaction with deionized water, and calcining the precipitate at 300 ℃ for 2 hours to obtain the tungsten trioxide nanoparticles.
3. Preparation of aluminum phosphate inorganic binder: 15.6g of aluminum hydroxide powder was added to 98g of phosphoric acid solution (60%), and the mixed solution was stirred at 100 ℃ for 3 hours to obtain a transparent and clean aluminum phosphate solution.
4. Preparing the ultra-smooth coating: dissolving 1g of inorganic binder in 5ml of deionized water, then adding 1g of tungsten trioxide nanoparticles into the solution, finally adding 15ml of ethanol, and fully mixing to obtain a spraying solution. And spraying the mixed solution on the surface of a copper sheet, and respectively curing for 2h and 1h at 120 ℃ and 240 ℃ to obtain a sprayed surface. And dropwise adding a certain amount of silicone oil to the prepared spraying surface, and irradiating for 1h under ultraviolet light to obtain the super-smooth surface.
5. Ultra-smooth coating chemical stability and mechanical durability test: measuring the surface contact angle and the sliding angle after the centrifugal roller is placed for 7 days at room temperature and 30 times of cooling and heating cycles of 150 ℃/20 ℃ at different centrifugal speeds, and finding that the sliding angle is slightly increased and the surface still has excellent sliding performance; the different pH acidic solution also has a low sliding angle on the surface thereof, and thus the surface has excellent acid resistance.
Example 4
1. Preparation in the early stage of the experiment: cutting the copper sheet to a proper size, ultrasonically cleaning the copper sheet in acetone, ethanol and deionized water for multiple times, and then drying the copper sheet in an oven for later use.
2. Preparing tungsten trioxide acid nanoparticles: firstly, 4.8g of tungstic acid is added into 125ml of hydrogen peroxide (12 wt%), the mixed solution is stirred for 3.5h at the temperature of 98 ℃ until the tungstic acid is completely dissolved, and the mixed solution is cooled to the room temperature. The mixed solution was diluted to 350ml, 0.228g of ammonium acetate was added, and then the mixed solution of tungstic acid and ammonium acetate was transferred to a reaction vessel and reacted at 185 ℃ for 12.5 hours. And repeatedly washing the precipitate obtained after the reaction with deionized water, and calcining the precipitate at 305 ℃ for 2.5 hours to obtain the tungsten trioxide nanoparticles.
3. Preparation of aluminum phosphate inorganic binder: 15.8g of aluminum hydroxide powder was added to 99g of phosphoric acid solution (60%), and the mixed solution was stirred at 105 ℃ for 3.5 hours to obtain a transparent and clean aluminum phosphate solution.
4. Preparing the ultra-smooth coating: 1.3g of inorganic binder was dissolved in 6ml of deionized water, and then 1.3g of tungsten trioxide nanoparticles was added to the above solution, and finally 18ml of ethanol was added, followed by thorough mixing to obtain a spray solution. And spraying the mixed solution on the surface of a copper sheet, and curing at 125 ℃ and 245 ℃ for 2.5h and 1.3h respectively to obtain a sprayed surface. And dropwise adding a certain amount of silicone oil to the prepared spraying surface, and irradiating for 1.3h under ultraviolet light to obtain the ultra-smooth surface.
5. The state of water drops on the super-hydrophobic surface and the super-smooth surface: and (3) spraying water mist to the surfaces of different samples by using a commercial humidifier, and shooting the attachment state of the water mist on the samples by using a digital camera at different time periods. The ultra-smooth surface can quickly realize the capture of micro liquid drops, the expansion of water drops, the removal of water drops and the like, thereby having high-efficiency mist collection efficiency. In the same time, the water mist collection quality of the ultra-smooth surface is obviously higher than that of other surfaces, and the water collection efficiency of the ultra-smooth surface is improved by 233.1 percent compared with that of the original copper sheet.
Example 5
1. Preparation in the early stage of the experiment: cutting the copper sheet to a proper size, ultrasonically cleaning the copper sheet in acetone, ethanol and deionized water for multiple times, and then drying the copper sheet in an oven for later use.
2. Preparing tungsten trioxide acid nanoparticles: firstly, 5g of tungstic acid is added into 130ml of hydrogen peroxide (12 wt%), the mixed solution is stirred for 4 hours at 100 ℃ until the tungstic acid is completely dissolved, and the mixed solution is cooled to room temperature. The mixed solution was diluted to 400ml, 0.22g of ammonium acetate was added, and then the resultant mixed solution was transferred to a reaction vessel and reacted at 190 ℃ for 13 hours. And (3) repeatedly cleaning the precipitate obtained after the reaction with deionized water, and calcining the precipitate at 310 ℃ for 3 hours to obtain the tungsten trioxide nanoparticles.
3. Preparation of aluminum phosphate inorganic binder: 16g of aluminum hydroxide powder was added to 100g of phosphoric acid solution (60%), and the mixed solution was stirred at 110 ℃ for 4 hours to obtain a clear and clean aluminum phosphate solution.
4. Preparing the ultra-smooth coating: 1.5g of inorganic binder was dissolved in 7ml of deionized water, and then 1.5g of tungsten trioxide nanoparticles was added to the above solution, and finally 20ml of ethanol was added, followed by thorough mixing to obtain a spray solution. And spraying the mixed solution on the surface of a copper sheet, and curing for 3 hours and 1.5 hours at the temperature of 130 ℃ and 250 ℃ respectively to obtain a sprayed surface. And dropwise adding a certain amount of silicone oil to the prepared spraying surface, and irradiating for 1.5 hours under ultraviolet light to obtain the ultra-smooth surface.
5. Water mist collection performance test under extreme conditions: after high-speed centrifugation, long-term storage and multiple cold-hot cycles, the fog collection quality on the ultra-smooth surface is slightly reduced, the fog collection efficiency is slightly reduced, and the fog collection efficiency is still good.
To summarize: the invention obtains inspiration from the mechanism of catching insects by the plant nepenthes in nature, and carries out bionic design on the unique super-lubricity of the nepenthes. The method comprises the steps of preparing tungsten trioxide nano particles, spraying a mixed solution of the tungsten trioxide nano particles and an inorganic binder, grafting dimethyl siloxane and the like. The ultra-smooth coating has excellent lyophobic performance, and water drops and various organic matter drops all have a sliding angle of less than 10 degrees on the surface of the ultra-smooth coating. On the basis of a hierarchical structure, strong intermolecular force exists between the silicone oil and the dimethyl siloxane, so that a stable lubricating oil layer is formed, and the loss of the lubricant in the mist collection process can be inhibited. Therefore, after a series of damages such as high-speed centrifugation, long-term storage, acidic solution erosion, multiple cold and hot cycles and the like, the sliding angle of the ultra-smooth coating is slightly increased, and the ultra-smooth coating still has good sliding performance. The ultra-smooth surface can quickly realize the capture of micro liquid drops, the expansion of water drops, the removal of water drops and the like, thereby having high-efficiency mist collection efficiency. After continuous water collection, the oil content in the water is only 28mg/L, and the water is harmless to human bodies. Moreover, the mist collection efficiency of the ultra-smooth coating is slightly reduced after high shear, long-term storage and multiple cooling and heating cycles, and still has excellent mist collection efficiency. The preparation method of the coating is simple, low in cost, convenient for large-scale preparation and wide in application prospect.
Finally, it should be noted that the above-mentioned contents are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, and that the simple modifications or equivalent substitutions of the technical solutions of the present invention by those of ordinary skill in the art can be made without departing from the spirit and scope of the technical solutions of the present invention.
Claims (4)
1. A preparation method of a tungsten trioxide super-slip coating with long-term stability and applicable to mist collection is characterized by comprising the following steps:
A. preparation in the early stage of the experiment: cutting a copper sheet into a certain size, respectively ultrasonically cleaning the copper sheet in acetone, ethanol and deionized water, and then putting the copper sheet into an oven to be dried for later use;
B. preparing tungsten trioxide nanoparticles: firstly, adding a certain amount of tungstic acid into a certain amount of 12 wt% hydrogen peroxide, wherein the mass ratio of the tungstic acid to the hydrogen peroxide is 3.5-4.0%, carrying out heat treatment on the mixed solution, stirring for a period of time until the mixed solution is completely dissolved, and cooling to room temperature; adding deionized water into the mixed solution for dilution, wherein the volume of the diluted solution is 2.0-3.5 times that of the original solution, adding a certain amount of ammonium acetate, and the molar ratio of tungstic acid to ammonium acetate is 5-7; then transferring the mixed solution into a reaction kettle, and reacting for 11-13 h at 170-190 ℃; repeatedly cleaning the precipitate obtained after the reaction with deionized water, and calcining for 1-3 h at 290-310 ℃ to obtain tungsten trioxide nanoparticles;
C. preparation of aluminum phosphate inorganic binder: adding a certain amount of aluminum hydroxide powder into a certain amount of 60% phosphoric acid solution, wherein the mass ratio of the aluminum hydroxide to the phosphoric acid solution is 0.15-0.16, carrying out heat treatment on the mixed solution, and stirring for a period of time, wherein the reaction temperature and the reaction time of the aluminum hydroxide and the phosphoric acid solution are respectively as follows: obtaining transparent and clean aluminum phosphate solution at 90-110 ℃ for 2-4 h;
D. preparing the ultra-smooth coating: adding a certain amount of the aluminum phosphate inorganic binder obtained in the step C into a certain amount of deionized water, wherein the mass ratio of the inorganic binder to the deionized water is 0.15-0.25, then adding a certain amount of the tungsten trioxide nano particles obtained in the step B into the solution, wherein the mass ratio of the inorganic binder to the tungsten trioxide nano particles is 0.8-1.2, finally adding a certain amount of ethanol, and fully mixing to obtain a spraying solution, wherein the mass ratio of the tungsten trioxide to the ethanol is 0.05-0.1; spraying the mixed solution on a substrate, and respectively curing for 1-3 h and 0.5-1.5 h at 110-130 ℃ and 230-250 ℃ to obtain a sprayed surface; and (3) dropwise adding a certain amount of dimethyl silicone oil to the prepared spraying surface, and irradiating for a certain time under ultraviolet light to realize the grafting of the dimethyl silicone oil, thereby obtaining the super-smooth surface.
2. The method of claim 1 for preparing a tungsten trioxide ultra-slip coating with long-term stability for mist collection, wherein the tungsten trioxide ultra-slip coating comprises the following steps: in the step A, the length and width of the copper sheet are 2cm multiplied by 2 cm.
3. The method of claim 1 for preparing a tungsten trioxide ultra-slip coating with long-term stability for mist collection, wherein the tungsten trioxide ultra-slip coating comprises the following steps: in the step B, the heat treatment temperature and the stirring time of the tungstic acid and hydrogen peroxide mixed solution are respectively as follows: 90-100 ℃ and 2-4 h.
4. The method of claim 1 for preparing a tungsten trioxide ultra-slip coating with long-term stability for mist collection, wherein the tungsten trioxide ultra-slip coating comprises the following steps: in the step D, the ultraviolet illumination time is 0.5 h-1.5 h.
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