CN113088188A - Hydrophobic nanoparticle-based super-hydrophobic silane membrane and preparation and application thereof - Google Patents

Hydrophobic nanoparticle-based super-hydrophobic silane membrane and preparation and application thereof Download PDF

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CN113088188A
CN113088188A CN202110348129.1A CN202110348129A CN113088188A CN 113088188 A CN113088188 A CN 113088188A CN 202110348129 A CN202110348129 A CN 202110348129A CN 113088188 A CN113088188 A CN 113088188A
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hydrophobic
silane
silane film
solution
stearic acid
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蒋继波
唐佳斌
郭曼利
李雨露
孙冉
黄星
孔玥
姚逸和
周少博
陈晓敏
韩生
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Shanghai Institute of Technology
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    • 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • 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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    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/60—Additives non-macromolecular
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide

Abstract

The invention relates to a super-hydrophobic silane film based on hydrophobic nano particles and preparation and application thereof, wherein the preparation method specifically comprises the following steps: (1) firstly, modifying nanoparticles by using stearic acid to obtain hydrophobic nanoparticles; (2) adding the hydrophobic nano particles obtained in the step (1) into a silane film solution to obtain a hydrophobic nano particle silane film solution; (3) then, preparing the hydrophobic nano particle silane film on the pretreated metal matrix by using the hydrophobic nano particle silane film solution obtained in the step (2); (4) and (4) modifying the hydrophobic nano particle silane film obtained in the step (3) with stearic acid to obtain the super-hydrophobic silane film. Compared with the prior art, the super-hydrophobic silane film obtained by modifying the nano particles and modifying the stearic acid is more feasible and efficient, can effectively reduce the production cost and can ensure the protection effect on the metal substrate.

Description

Hydrophobic nanoparticle-based super-hydrophobic silane membrane and preparation and application thereof
Technical Field
The invention belongs to the field of surface treatment, and particularly relates to a super-hydrophobic silane film based on hydrophobic nanoparticles, and preparation and application thereof.
Background
In recent years, with the increasing demand for quality of life and the increasing awareness of environmental protection and energy conservation, surfaces with self-cleaning functions have been rapidly developed. The self-cleaning surface is a surface on which pollutants or dust on the surface can automatically fall off or be degraded under the action of gravity, rainwater, wind and other external forces.
The surface hydrophobic technology is a basic technology with wide and deep depth and higher practical value, and is widely applied to daily life of people. By designing coatings with different structures, chemical and physical characteristics, new additional functions can be provided for solid materials, particularly the rapidly growing demands of modern industries on hydrophobic coatings, and continuous research power is provided for functionalized hydrophobic coatings. The super-hydrophobic coating is a novel surface technology developed on the basis of the super-hydrophobic coating.
The hydrophobic coating is a low surface energy coating with a static water contact angle theta of a coating film on a smooth surface larger than 90 degrees, while the super-hydrophobic coating is a novel coating with special surface properties, namely a solid coating with a water contact angle larger than 150 degrees and a water contact angle lag smaller than 5 degrees, has the important characteristics of water resistance, fog resistance, snow resistance, pollution resistance, adhesion resistance, oxidation resistance, corrosion resistance, self cleaning, current conduction prevention and the like, and has wide application prospects in fields of scientific research, production, life and the like.
The wetting properties of liquids on solid surfaces are often described by the young's equation. The contact angle between the liquid drop and the solid surface is large, the wettability is poor, and the liquid-phobicity is strong; otherwise, the lyophilic property is strong. The hydrophobicity of a solid surface is closely related to the surface energy of the solid surface. The solid surface energy is low, the static water contact angle is large, and the water contact angle is obvious hydrophobicity when being larger than 90 degrees. The surface energy of the currently known hydrophobic materials organosilicon and organofluorine materials is low, and the surface energy of fluorine-containing groups is in accordance with-CH2－>－CH3>－CF2－>CF2H>－CF3The order of (3) is decreased. -CF3The surface energy of the radical is as little as 6.7m J/m2The water contact angle on a smooth plane is the largest, can be calculated to be 115.2 degrees through a Dupre formula, and the water contact angle of the self-assembled ordered monolayer film with long-chain hydrocarbon groups can reach 112 degrees. While the water contact angles of the organosilicon and the organofluorine polymer which are generally arranged in disorder with low surface energy are respectively 101 degrees and 110 degrees. However, fluorine-based materials are relatively expensive and not suitable for industrial production.
Disclosure of Invention
The invention aims to provide a preparation method of a super-hydrophobic silane film based on hydrophobic nano-particles.
The second purpose of the invention is to provide a super-hydrophobic silane film prepared by the method.
The third purpose of the invention is to provide the application of the super-hydrophobic silane film.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a super-hydrophobic silane film based on hydrophobic nanoparticles comprises the following specific steps:
(1) firstly, modifying nanoparticles by using stearic acid to obtain hydrophobic nanoparticles;
(2) adding the hydrophobic nano particles obtained in the step (1) into a silane film solution to obtain a hydrophobic nano particle silane film solution;
(3) then, preparing the hydrophobic nano particle silane film on the pretreated metal matrix by using the hydrophobic nano particle silane film solution obtained in the step (2);
(4) and (4) modifying the hydrophobic nano particle silane film obtained in the step (3) with stearic acid to obtain the super-hydrophobic silane film. The term "superhydrophobic silane film" in the present invention refers to a film deposited on a metal substrate, and generally, the film is not prepared separately but directly on the metal substrate to be subjected to corrosion protection treatment, so that the film uncovering operation is not required.
In the step (1), the modification process specifically comprises the following steps: and (2) carrying out ultrasonic treatment on the nanoparticles in absolute ethyl alcohol for 1 hour at the room temperature of 25 ℃, adding stearic acid, continuing ultrasonic treatment for 30 minutes, sealing a covering film, stirring for 12 hours in a water bath environment at the temperature of 70 ℃, then stirring for 1 hour at the normal temperature to stabilize the mixed solution, adding absolute ethyl alcohol with the same volume, centrifuging to remove clear liquid, drying a centrifugal product by blowing at the temperature of 120 ℃, and finally grinding the dried product in a planetary ball mill until the particle size is 20-50 nm to finally obtain the hydrophobic nanoparticles.
In the step (1), the weight parts of the nano particles, the ethanol and the stearic acid are (1-5), (30-100), (5-10). Preferably, the weight part ratio of nanoparticles, ethanol and stearic acid is 1 part to 70 parts to 5 parts.
In the step (1), the nanoparticles are selected from one or more of nano silicon dioxide and nano titanium dioxide, and other nanoparticles can be selected according to the situation.
In the step (1), the hydrophobic angle of the hydrophobic nanoparticles is 130-150 degrees. Through experimental modification, nanoparticles with poor hydrophilic or hydrophobic properties can be modified into hydrophobic nanoparticles with a hydrophobic angle of 130-150 degrees.
In the step (2), the preparation process of the hydrophobic nano particle silane film solution comprises the following steps: mixing a silane coupling agent, ethanol and water in sequence at 25 ℃ in a room temperature environment, sealing, laminating, magnetically stirring for 12 hours to obtain a silane membrane solution, adding nanoparticles into the silane membrane solution, and magnetically stirring for 2 hours to obtain the hydrophobic nanoparticle silane membrane solution.
In the step (2), the hydrophobic nanoparticle silane film solution comprises the following components in parts by weight:
Figure BDA0003001393340000031
preferably, the hydrophobic nanoparticle silane film solution comprises the following components in parts by weight:
20 portions of silane coupling agent
70 portions of ethanol
100 portions of deionized water
2 parts of hydrophobic nano particles.
Wherein, the silane coupling agent can be formed by mixing KH-560 and KH-570 in a weight ratio of 1: 1. Ethanol and deionized water were removed during the drying process.
The silane coupling agent is selected from one or more of KH-560, KH-570 or BTSE. These silane coupling agents are relatively common and relatively inexpensive silane coupling agents.
In the step (3), the preparation of the hydrophobic nano particle silane film is selected from one or more of dip coating, spray coating, electrochemical auxiliary deposition or vapor deposition, wherein the spray coating method is to atomize the silane film solution by compressed air for spray coating, and the advantages are that: the spraying conditions can be selected at will, the operation is easy, and the method is suitable for workpieces with the spraying quality being emphasized. Electrochemically assisted deposition is carried out by applying a cathodic potential to a cathode to cause certain components (e.g., O) in solution2、H2O) reduction to OH-Causing the solution near the cathode to be locally alkalized and utilizing OH-Has obvious catalytic action on condensation reaction in the process of silane sol-gel, thereby achieving the aim of promoting the film formation of silaneIn (1). The vapor deposition technology is a technology of vaporizing a material source, namely a liquid surface, into gaseous atoms, molecules or partially ionizing the gaseous atoms into ions by adopting a physical method under a vacuum condition, and depositing a film on the surface of a substrate through a low-pressure gas (or plasma) process.
In the step (3), when a dip coating method is adopted, the preparation process of the hydrophobic nano particle silane film specifically comprises the following steps: and (2) soaking the pretreated metal matrix into the hydrophobic nano particle silane membrane solution for 5 minutes by a dip coating method at the room temperature of 25 ℃, taking out, and drying and curing at the temperature of 80 ℃ for 1 hour to obtain the hydrophobic nano particle silane membrane.
The metal matrix is an iron sheet.
The pretreatment process of the metal matrix comprises the following specific steps: sequentially carrying out degreasing, derusting and washing. The method specifically comprises the following steps: 5% NaOH solution is used as degreasing pretreatment solution, and the degreasing efficiency can be effectively improved in an ultrasonic-assisted environment at 40 ℃ for 3-5 minutes. The rust removal is performed by using an LF-200 environment-friendly neutral rust remover, the rust remover and water are prepared according to the proportion of 1:5 to obtain a solution, a metal matrix is soaked in the solution at 50 ℃, the metal matrix is taken out after the surface of the metal matrix is bright and has no obvious rust mark, the residual rust remover on the surface is washed away by using deionized water, and the metal matrix is dried by nitrogen for later use.
In the step (4), the stearic acid modification specific process is as follows: dissolving stearic acid in absolute ethyl alcohol at the room temperature of 25 ℃ to obtain stearic acid modified solution, soaking the hydrophobic nano particle silane membrane in the stearic acid modified solution for 2 hours, taking out the solution, and drying the solution in an oven at the temperature of 60 ℃ for 1 hour to obtain the super-hydrophobic silane membrane.
The stearic acid modification solution comprises the following components in parts by weight:
stearic acid 5-20 parts
80-160 parts of ethanol.
A superhydrophobic silane film prepared by the preparation method. The super-hydrophobic silane film contains hydrophobic nano particles, a silane coupling agent and stearic acid, the mass ratio of each component is (1-5) to (10-30) to (5-20), and preferably the mass ratio of each component is 2: 20: 5, the thickness of the film is 1-20 μm, and the particle size of the hydrophobic nano particles is 20-50 nm.
The application of the super-hydrophobic silane film in the field of steel corrosion prevention replaces the phosphating and chromizing technologies which are toxic to the environment in a certain aspect. In the preparation process, firstly, the hydrophobicity of the nano particles is improved by a nano particle modification means (the modification principle is that stearic acid is used for wrapping nano silicon dioxide particles, so that a layer of stearic acid is arranged on the surface of the nano silicon dioxide, the hydrophobicity of the nano particles is improved based on the characteristic that the stearic acid is insoluble in water), and further the hydrophobicity and the corrosion resistance of a silane film are improved, then a silane film solution containing the hydrophobic nano particles is used for forming a film on the surface of a metal matrix, silane is hydrolyzed to generate silanol (Si-OH), the silanol can form a hydrogen bond with metal, the silanol can further dehydrate to form a-Si-O-M covalent bond (M represents a metal element) with the metal, and a conversion film is formed on the surface of the metal to improve the affinity of the silane and an inorganic. Meanwhile, silanol molecules can be mutually condensed into Si-O-Si chains, and the Si-O-Si chains are polymerized to form a net-shaped film to cover the metal surface.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the obtained modified hydrophobic nano particles can enhance the corrosion resistance of the material on one hand and can also improve the hydrophobicity of the silane film on the other hand.
2. Compared with expensive fluorine silane, the silane used by the invention has low price and cost and high feasibility.
3. The method is green and environment-friendly, and compared with a phosphating process, the product does not contain phosphorus, is not easy to precipitate slag and does not generate acid mist.
Drawings
FIG. 1 is a hydrophobic angle characterization of the superhydrophobic silane film prepared in example 1;
FIG. 2 is a graph of the impedance of a superhydrophobic silane film soaked in a 3.5 wt.% NaCl solution for one week;
FIG. 3 is a hydrophobic angle characterization of a standard silane film prepared in comparative example 1;
FIG. 4 is an online infrared image of the superhydrophobic silane film made in example 1.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
Raw materials: the silane film solution comprises the following components in parts by weight:
Figure BDA0003001393340000051
the stearic acid modification solution comprises the following components in parts by weight:
stearic acid 5 parts
80 parts of ethanol.
A super-hydrophobic silane film comprises hydrophobic nano particles, a silane coupling agent and stearic acid, wherein the mass ratio of each component is 2: 20: 5, the thickness of the film is 1-20 μm, the particle size of the hydrophobic nano particles is 20-50 nm, the preparation is carried out according to the formula before the preparation, and the preparation method specifically comprises the following steps:
(1) performing ultrasonic treatment on 1 part of nano particles (nano titanium dioxide) in 70 parts of absolute ethyl alcohol for 1 hour at room temperature of 25 ℃, adding 5 parts of stearic acid, continuing performing ultrasonic treatment for 30 minutes, sealing and coating a film, stirring for 12 hours in a water bath environment at 70 ℃, then stirring for 1 hour at normal temperature to stabilize the mixed solution, adding absolute ethyl alcohol with the same volume, centrifuging to remove clear liquid, drying a centrifugal product by blowing at 120 ℃, and finally grinding the dried product in a planetary ball mill until the particle size is 20-50 nm to obtain hydrophobic nano particles;
(2) mixing a silane coupling agent, ethanol and water in proportion at room temperature of 25 ℃ in sequence, sealing, laminating, magnetically stirring for 12 hours to obtain a silane membrane solution, adding 2 parts of the hydrophobic nanoparticles obtained in the step (1) into the silane membrane solution (the specific proportion of the silane membrane solution is as above), and magnetically stirring for 2 hours to obtain a hydrophobic nanoparticle silane membrane solution;
(3) at room temperature of 25 ℃, pre-treated iron sheets (the iron sheets are sequentially degreased, derusted and washed by water, specifically, a 5% NaOH solution is used as a degreasing pre-treatment solution, derusting is carried out by adopting an LF-200 environment-friendly neutral deruster in an ultrasonic auxiliary environment at 40 ℃ for 3-5 minutes, the deruster and water are prepared according to a ratio of 1:5 to obtain a solution, the iron sheets are soaked in the 50 ℃ solution, after the surfaces of the iron sheets are bright and have no obvious rust marks, the iron sheets are taken out, the deruster remained on the surfaces is washed away by deionized water, the nitrogen is used for drying the iron sheets for later use, the same is carried out below), the iron sheets are soaked in the hydrophobic nano particle silane film solution obtained in the step (2) by a dip-coating method, the iron sheets are taken out after 5 minutes, and are dried and cured in an oven at;
(4) dissolving stearic acid in absolute ethyl alcohol at room temperature of 25 ℃ according to a ratio to obtain stearic acid modified solution, soaking the hydrophobic nano particle silane membrane obtained in the step (3) in the stearic acid modified solution, taking out the hydrophobic nano particle silane membrane and drying the hydrophobic nano particle silane membrane in a drying oven at the temperature of 60 ℃ for 1 hour to obtain a super-hydrophobic silane membrane, wherein an online infrared diagram of the membrane is shown in figure 4, and 1217cm is obtained along with the extension of hydrolysis time-1The peaks at the left and right gradually disappeared at 1023cm-1The peaks at the left and right gradually disappeared at 1020cm-1The peaks at the left and right gradually appeared and increased, 910cm-1The peaks at the left and right gradually appeared and increased at 820cm-1The gradual disappearance of the peaks at the left and right indicates the hydrolysis of the superhydrophobic silane film. The hydrophobic angle of the super-hydrophobic silane film is represented as shown in figure 1 through a JC2000C1 type contact angle measuring instrument at room temperature, and the hydrophobic angle degree is 150 degrees through software image analysis. The impedance curve obtained by soaking the superhydrophobic silane film in 3.5 wt.% NaCl solution for one week is shown in fig. 2, and it can be seen that although the superhydrophobic silane film is soaked for a long time, the shape of the alternating current impedance curve of the superhydrophobic silane film is still consistent, and only the curvature radius is gradually reduced, so that it can be concluded that the silane film has strong corrosion resistance in seawater environment and can be used for corrosion protection of steel.
Comparative example 1
Mixing a silane coupling agent, ethanol and water in sequence at room temperature of 25 ℃, sealing, laminating, magnetically stirring for 12 hours to obtain a silane membrane solution, soaking pretreated iron sheets into the solution, taking out after 5 minutes, putting into an oven, and curing for one hour at the environment of 80 ℃ to obtain a standard silane membrane; at room temperature, the hydrophobic angle of the JC2000C1 type contact angle measuring instrument is characterized as shown in figure 3, and the degree of the hydrophobic angle is 100 degrees and the hydrophobic effect is lower than that of the super-hydrophobic silane film prepared in the embodiment 1 of the invention through software image analysis.
Example 2
Raw materials: the silane film solution comprises the following components in parts by weight:
KH-56010 parts of silane coupling agent
30 portions of ethanol
60 parts of deionized water.
The stearic acid modification solution comprises the following components in parts by weight:
stearic acid 6 parts
100 parts of ethanol.
A super-hydrophobic silane film comprises hydrophobic nano particles, a silane coupling agent and stearic acid, wherein the mass ratio of the components is 1: 10: 6, the thickness of the film is 1-20 μm, the particle size of the hydrophobic nano particles is 20-50 nm, the preparation is carried out according to the formula before the preparation, and the preparation method specifically comprises the following steps:
(1) ultrasonically treating 2 parts of nano particles (nano silicon dioxide) in 30 parts of absolute ethyl alcohol for 1 hour at room temperature of 25 ℃, adding 6 parts of stearic acid, continuously performing ultrasonic treatment for 30 minutes, sealing and coating a film, stirring for 12 hours in a water bath environment at 70 ℃, then stirring for 1 hour at normal temperature to stabilize a mixed solution, adding absolute ethyl alcohol with the same volume, centrifuging to remove clear liquid, drying a centrifugal product by blowing at 120 ℃, and finally grinding the dried product in a planetary ball mill until the particle size is 20-50 nm to obtain hydrophobic nano particles;
(2) mixing a silane coupling agent, ethanol and water in proportion at room temperature of 25 ℃ in sequence, sealing, laminating, magnetically stirring for 12 hours to obtain a silane membrane solution, adding 1 part of the hydrophobic nanoparticles obtained in the step (1) into the silane membrane solution (the specific proportion of the silane membrane solution is as above), and magnetically stirring for 2 hours to obtain a hydrophobic nanoparticle silane membrane solution;
(3) spraying the hydrophobic nano particle silane film solution obtained in the step (2) on the iron sheet by a spraying method (namely spraying by using compressed air) at room temperature of 25 ℃, wherein the iron sheet is subjected to pretreatment (the iron sheet is sequentially subjected to degreasing, rust removal and water washing), and then drying and curing in an oven at 80 ℃ for 1 hour to obtain a hydrophobic nano particle silane film;
(4) and (3) dissolving stearic acid in absolute ethyl alcohol at room temperature of 25 ℃ according to a ratio to obtain a stearic acid modified solution, soaking the hydrophobic nano particle silane film obtained in the step (3) in the stearic acid modified solution, taking out the solution and drying the solution in a drying oven at the temperature of 60 ℃ for 1 hour to obtain the super-hydrophobic silane film, wherein the super-hydrophobic silane film has strong corrosion resistance.
Example 3
Raw materials: the silane film solution comprises the following components in parts by weight:
Figure BDA0003001393340000071
the stearic acid modification solution comprises the following components in parts by weight:
stearic acid 20 parts
160 parts of ethanol.
A super-hydrophobic silane film comprises hydrophobic nano particles, a silane coupling agent and stearic acid, wherein the mass ratio of the components is 5: 30: 20, the thickness of the film is 1-20 μm, the particle size of the hydrophobic nano particles is 20-50 nm, the preparation is carried out according to the formula before the preparation, and the preparation method specifically comprises the following steps:
(1) ultrasonic treating 5 parts of nano particles (nano silicon dioxide) in 100 parts of absolute ethyl alcohol for 1 hour at the room temperature of 25 ℃, adding 10 parts of stearic acid, continuing ultrasonic treating for 30 minutes, sealing and coating a film, stirring for 12 hours in a water bath environment at the temperature of 70 ℃, then stirring for 1 hour at the normal temperature to stabilize the mixed solution, adding the absolute ethyl alcohol with the same volume, centrifuging to remove clear liquid, drying a centrifugal product by blowing at the temperature of 120 ℃, and finally grinding the dried product in a planetary ball mill until the particle size is 20-50 nm to obtain hydrophobic nano particles;
(2) mixing a silane coupling agent, ethanol and water in proportion at room temperature of 25 ℃ in sequence, sealing, laminating, magnetically stirring for 12 hours to obtain a silane membrane solution, adding 5 parts of the hydrophobic nanoparticles obtained in the step (1) into the silane membrane solution (the specific proportion of the silane membrane solution is as above), and magnetically stirring for 2 hours to obtain a hydrophobic nanoparticle silane membrane solution;
(3) at room temperature of 25 ℃, performing electrochemical auxiliary deposition on a pretreated iron sheet (the iron sheet is sequentially subjected to degreasing, rust removal and water washing), taking the iron sheet as a cathode electrode, a platinum electrode as an anode electrode, and a calomel electrode as an auxiliary electrode, taking the hydrophobic nano particle silane film solution obtained in the step (2) as an electrolyte, and then drying and curing the electrolyte in an oven at 80 ℃ for 1 hour to obtain a hydrophobic nano particle silane film;
(4) and (3) dissolving stearic acid in absolute ethyl alcohol at room temperature of 25 ℃ according to a ratio to obtain a stearic acid modified solution, soaking the hydrophobic nano particle silane film obtained in the step (3) in the stearic acid modified solution, taking out the solution and drying the solution in a drying oven at the temperature of 60 ℃ for 1 hour to obtain the super-hydrophobic silane film, wherein the super-hydrophobic silane film has strong corrosion resistance.
Example 4
A method for preparing a superhydrophobic silane film, which is the same as that of example 1 except that a vapor deposition technique (physical method is adopted under vacuum condition to vaporize the surface of a material source, namely, a hydrophobic nano particle silane film solution into gaseous atoms, molecules or parts of the gaseous atoms and the molecules into ions, and a thin film is deposited on the surface of a substrate through a low-pressure gas (or plasma) process) is adopted in step (3).
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. A preparation method of a super-hydrophobic silane film based on hydrophobic nanoparticles is characterized by comprising the following steps:
(1) firstly, modifying nanoparticles by using stearic acid to obtain hydrophobic nanoparticles;
(2) adding the hydrophobic nano particles obtained in the step (1) into a silane film solution to obtain a hydrophobic nano particle silane film solution;
(3) then, preparing the hydrophobic nano particle silane film on the pretreated metal matrix by using the hydrophobic nano particle silane film solution obtained in the step (2);
(4) and (4) modifying the hydrophobic nano particle silane film obtained in the step (3) with stearic acid to obtain the super-hydrophobic silane film.
2. The method for preparing the superhydrophobic silane film based on the hydrophobic nanoparticles according to claim 1, wherein in the step (1), the modification process specifically comprises: and (2) carrying out ultrasonic treatment on the nanoparticles in absolute ethyl alcohol for 1 hour at the room temperature of 25 ℃, adding stearic acid, continuing ultrasonic treatment for 30 minutes, sealing a coating film, stirring for 12 hours in a water bath environment at the temperature of 70 ℃, then stirring for 1 hour at the normal temperature to stabilize the mixed solution, adding absolute ethyl alcohol, centrifuging to remove clear liquid, carrying out forced air drying on a centrifugal product at the temperature of 120 ℃, and finally putting the dried product into a planetary ball mill to be ground until the particle size is 20-50 nm, thus obtaining the hydrophobic nanoparticles.
3. The method for preparing the hydrophobic nanoparticle-based superhydrophobic silane film according to claim 2, wherein in the step (1), the weight part ratio of the nanoparticles to the ethanol to the stearic acid is (1-5), (30-100), (5-10);
in the step (1), the nano particles are selected from one or more of nano silicon dioxide or nano titanium dioxide.
4. The method for preparing the hydrophobic nanoparticle-based superhydrophobic silane film according to claim 1, wherein in the step (2), the preparation of the hydrophobic nanoparticle silane film solution comprises the following specific steps: mixing a silane coupling agent, ethanol and water in sequence at 25 ℃ in a room temperature environment, sealing, laminating, magnetically stirring for 12 hours to obtain a silane membrane solution, adding nanoparticles into the silane membrane solution, and magnetically stirring for 2 hours to obtain the hydrophobic nanoparticle silane membrane solution.
5. The method for preparing the hydrophobic nanoparticle-based superhydrophobic silane film according to claim 4, wherein in the step (2), the hydrophobic nanoparticle silane film solution comprises the following components in parts by weight:
Figure FDA0003001393330000021
in the step (2), the silane coupling agent is selected from one or more of KH-560, KH-570 or BTSE.
6. The method for preparing the hydrophobic nanoparticle-based superhydrophobic silane film according to claim 1, wherein in the step (3), the preparation of the hydrophobic nanoparticle silane film is selected from one or more of dip coating, spray coating, electrochemical assisted deposition or vapor deposition.
7. The method for preparing the hydrophobic nanoparticle-based superhydrophobic silane film according to claim 6, wherein in the step (3), when a dip coating method is adopted, the preparation process of the hydrophobic nanoparticle silane film specifically comprises: and (2) soaking the pretreated metal matrix into a hydrophobic nano particle silane film solution by a dip coating method at the room temperature of 25 ℃, taking out, and drying and curing at the temperature of 80 ℃ for 1 hour to obtain the hydrophobic nano particle silane film.
8. The method for preparing the superhydrophobic silane film based on the hydrophobic nanoparticles according to claim 1, wherein in the step (4), the stearic acid modification comprises the following specific steps: dissolving stearic acid in absolute ethyl alcohol at the room temperature of 25 ℃ to obtain stearic acid modified solution, soaking the hydrophobic nano particle silane membrane in the stearic acid modified solution for 2 hours, taking out and drying at the temperature of 60 ℃ for 1 hour to obtain a super-hydrophobic silane membrane;
the stearic acid modification solution comprises the following components in parts by weight:
stearic acid 5-20 parts
80-160 parts of ethanol.
9. A superhydrophobic silane film prepared by the preparation method of any one of claims 1-8.
10. Use of the superhydrophobic silane film of claim 9.
CN202110348129.1A 2021-03-31 2021-03-31 Hydrophobic nanoparticle-based super-hydrophobic silane membrane and preparation and application thereof Pending CN113088188A (en)

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