CN107384055B - Durable super-hydrophobic coating and preparation method thereof - Google Patents

Durable super-hydrophobic coating and preparation method thereof Download PDF

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CN107384055B
CN107384055B CN201710592813.8A CN201710592813A CN107384055B CN 107384055 B CN107384055 B CN 107384055B CN 201710592813 A CN201710592813 A CN 201710592813A CN 107384055 B CN107384055 B CN 107384055B
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coating
hydrophobic
curing
super
semi
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CN107384055A (en
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张友法
张丽清
肖振
余新泉
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Southeast University
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D127/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment 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
    • B05D3/04Pretreatment 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 gases
    • B05D3/0406Pretreatment 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 gases the gas being air
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment 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
    • B05D3/10Pretreatment 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
    • B05D3/107Post-treatment of applied coatings
    • B05D3/108Curing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
    • B05D5/083Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface involving the use of fluoropolymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/14Paints containing biocides, e.g. fungicides, insecticides or pesticides
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    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16Antifouling paints; Underwater paints
    • C09D5/1606Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612Non-macromolecular compounds
    • C09D5/1618Non-macromolecular compounds inorganic
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    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2506/00Halogenated polymers
    • B05D2506/10Fluorinated polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2518/00Other type of polymers
    • B05D2518/10Silicon-containing polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2601/00Inorganic fillers
    • B05D2601/20Inorganic fillers used for non-pigmentation effect
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    • B05D2601/00Inorganic fillers
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    • B05D2601/22Silica
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2601/00Inorganic fillers
    • B05D2601/20Inorganic fillers used for non-pigmentation effect
    • B05D2601/24Titanium dioxide, e.g. rutile
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • C08K2003/2241Titanium dioxide
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    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/36Silica
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/22Expanded, porous or hollow particles
    • C08K7/24Expanded, porous or hollow particles inorganic

Abstract

A durable super-hydrophobic coating and a preparation method thereof, the preparation steps are that the hybrid coating is prepared: under the condition of low-speed mechanical stirring, sequentially adding hydrophobic micro-nano particles, hydrophobic resin and a curing agent into a volatile organic solvent, then stirring at a high speed, and performing ultrasonic dispersion to obtain a hybrid coating; semi-curing the coating: coating the hybrid coating on the surface of a base material and semi-curing; and (3) complete curing: and soaking the semi-cured coating in a mixed soaking solution of a curing agent and a volatile organic solvent, taking out and drying to obtain the durable super-hydrophobic coating with good wear resistance. The preparation method has no special requirements on the base material and the shape thereof, is suitable for the surfaces of various common base materials such as metal, glass, wood, concrete and the like, has simple equipment, easy operation and low cost, can be constructed in a large area, and has great application value in the super-hydrophobic fields of self-cleaning, corrosion and mildew prevention, ice and frost prevention, oil-water separation and the like.

Description

Durable super-hydrophobic coating and preparation method thereof
Technical Field
The invention belongs to the technical field of preparation and application of coatings, and particularly relates to a durable super-hydrophobic coating and a preparation method thereof.
Background
The super-hydrophobic surface refers to a surface with a contact angle of more than 150 degrees and a rolling angle of less than 10 degrees with a water drop. Since the discovery of the lotus leaf effect, the super-hydrophobic surface has wide application in the fields of self-cleaning, corrosion and mildew prevention, ice and frost prevention, oil-water separation and the like. The traditional super-hydrophobic surface preparation method is mainly characterized in that a micro-nano rough structure is constructed on the surface of a substrate by a bionic means and is modified by a low-surface-energy substance, or the rough structure is directly constructed on the surface of a low-surface-energy material. The methods have high requirements on substrate materials, complex process equipment and difficult realization of large-scale production. Therefore, if the method is simplified, the super-hydrophobic coating containing the micro-nano particles is prepared and coated on the surface of the required substrate, so that the method has no excessive requirements on the substrate, is easy to realize and is easy for large-scale production.
With the intensive research on the super-hydrophobic coating, the super-hydrophobicity and the abrasion resistance are found to be contradictory to some extent. The coating with good super-hydrophobic performance generally has low resin content and high particle content, and particles are easy to fall off under the action of external force, so that the wear resistance of the coating is poor. If the resin content is increased, the particles are easily covered by the resin, the roughness of the coating is reduced, and the super-hydrophobic property is poor. Therefore, how to solve the contradiction and ensure the super-hydrophobic property of the coating and improve the wear resistance of the coating becomes a research hotspot. In recent years, the main methods proposed include enhancing the bonding force between the coating and the substrate, and preventing the particles from partially or completely falling off under mechanical force, thereby reducing the surface roughness, and this method has limited improvement in abrasion resistance, and if good results are achieved, it is usually necessary to add an additional primer layer between the coating and the substrate, which makes the process complicated and the materials expensive.
Based on the method, the invention provides a novel method for preparing the durable super-hydrophobic coating, and the technical problem that the super-hydrophobicity and the wear resistance are mutually inconsistent is effectively solved. The method does not need to additionally prepare primer, has simple equipment and process, is easy to operate, is suitable for large-scale preparation and production, has good wear resistance of the obtained coating, is not easy to damage the super-hydrophobic property, is suitable for various common substrate materials, and can be widely applied to the super-hydrophobic field.
Disclosure of Invention
The technical problem to be solved is as follows: in order to solve the technical problem that the super-hydrophobic surface is not wear-resistant, the invention provides a durable super-hydrophobic coating and a preparation method thereof. The equipment and the process are simple, the operation is easy, and the method is suitable for large-scale preparation and production.
The technical scheme is as follows: a preparation method of a durable super-hydrophobic coating comprises the following preparation steps: preparing a hybrid coating: sequentially adding hydrophobic micro-nano particles, hydrophobic resin and a curing agent into a volatile organic solvent under the condition of 100 plus 500rpm low-speed mechanical stirring, then stirring at the high speed of 1000 plus 2000rpm for 5-15min, and then performing ultrasonic dispersion for 5-10min to obtain a hybrid coating; semi-curing the coating: coating the hybrid coating on the surface of a base material and semi-curing; and (3) complete curing: and soaking the semi-cured coating in a mixed soaking solution of a curing agent and a volatile organic solvent for 5-60min, taking out and drying to obtain the durable super-hydrophobic coating with good wear resistance.
Preferably, the hydrophobic micro-nano particles are at least one of hydrophobic silicon dioxide, carborundum, titanium dioxide, carbon nano tubes, carbon black or graphite with the particle size of 10nm-50 μm, the hydrophobic resin is fluorocarbon resin or organic silicon resin capable of being cured at room temperature, and the curing agent is isocyanate.
Preferably, the hybrid coating comprises the following components in parts by mass: 10-25 parts of volatile organic solvent, 0.6-2.2 parts of hydrophobic micro-nano particles, 3-7.5 parts of hydrophobic resin, no more than 1 part of curing agent, wherein the mass ratio of the hydrophobic micro-nano particles to the hydrophobic resin is (2-3):10, and the dosage of the curing agent is 30-80wt.% of the dosage when the curing agent is completely cured.
Preferably, the semi-curing refers to that the coating is not completely cured after being placed at room temperature for 8-20 hours after being coated; the curing agent and volatile organic solvent mixed soaking solution used in the complete curing is the same as the curing agent and volatile organic solvent used in the hybrid coating in type, and comprises no more than 1 part by mass of the curing agent and 20 parts by mass of the volatile organic solvent.
Preferably, the coating is brush coating, spray coating, roller coating or dip coating.
Preferably, the substrate is metal, glass, wood or concrete.
Preferably, the volatile organic solvent is at least one of ketones, alcohols, and esters.
The durable super-hydrophobic coating prepared by the method.
Has the advantages that: (1) the hydrophobic micro-nano particles are firstly dispersed in a volatile organic solvent, so that the uniformity of subsequent particles dispersed in resin is improved, and the occurrence of particle agglomeration is effectively avoided. (2) The mass ratio of the hydrophobic micro-nano particles to the hydrophobic resin is controlled within the range of (2-3):10, so that on one hand, enough particle number is ensured, the particles cannot be completely covered by the resin, and on the other hand, the content of the resin is high, the adhesion to the particles is good, and the bonding force between the particles and a substrate is good. (3) The hybrid coating is semi-cured to promote the bonding of the particles and the resin, but the bonding between the particles and the resin is not too tight due to incomplete curing, which is beneficial to the exposure of the particles in the subsequent soaking process, thereby achieving an ideal coarse structure. (4) By using the simple process of soaking, on one hand, the resin is promoted to be dissolved, the surface layer particles are continuously exposed, the roughness is improved, and the super-hydrophobicity is better; on the other hand, the curing is promoted, the bonding degree between the particles and the resin is improved, the particles with weak surface bonding are removed, the transparency of the coating is enhanced, and the wear resistance of the coating is comprehensively improved. (5) The preparation method has no special requirements on the base material and the shape thereof, is suitable for the surfaces of various common base materials such as metal, glass, wood, concrete and the like, has simple equipment, easy operation and low cost, can be constructed in a large area, and has great application value in the super-hydrophobic fields of self-cleaning, corrosion and mildew prevention, ice and frost prevention, oil-water separation and the like.
Drawings
FIG. 1 is an optical photograph of the contact angle of a water droplet of a coating without immersion treatment.
FIG. 2 scanning electron micrograph of coating without immersion treatment.
Fig. 3 optical photograph of contact angle of water drop of super-hydrophobic coating obtained after soaking.
Fig. 4 scanning electron microscope photograph of the superhydrophobic coating obtained after soaking.
FIG. 5 is a scanning electron microscope photograph of the surface of the superhydrophobic coating obtained after soaking after sanding for 80 cycles.
Detailed Description
The following examples are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Example 1
Under the condition of low-speed stirring at 400rpm, 0.6 part of hydrophobic micro-nano titanium dioxide particles, 3 parts of FEVE resin and 0.7 part of hexamethylene diisocyanate trimer curing agent are sequentially added into 10 parts of butyl acetate solution, the mixture is stirred at 1500rpm for 10min, ultrasonic dispersion is carried out for 5min, the obtained coating is coated on the surface of a glass sheet in a brush mode, curing is carried out at room temperature for 24h, the water contact angle is 146.5 degrees, and the rolling angle is 23.1 degrees. Fig. 1 is an optical photograph of a contact angle of a water droplet of the resultant coating, and fig. 2 is a scanning electron microscope photograph of the coating.
Example 2
Under the condition of low-speed stirring at 500rpm, adding 1.5 parts of hydrophobic micro-nano fumed silica particles, 6 parts of FEVE resin and 1 part of hexamethylene diisocyanate trimer curing agent into 20 parts of butyl acetate solution in sequence, stirring at 1500rpm for 15min, then performing ultrasonic dispersion for 10min, and brushing the obtained coating on the surface of a glass sheet to obtain a plurality of samples. Taking out a part of the sample, directly drying the sample at room temperature for 24 hours without soaking, and completely curing the sample. And (5) taking the residual sample, drying for 16h at room temperature to reach a semi-solidified state. Adding 1 part of hexamethylene diisocyanate trimer curing agent into 20 parts of butyl acetate solution, and performing ultrasonic dispersion for 10min to uniformly mix to prepare a soaking solution. And immersing the semi-cured coating in the soaking solution for 30min, taking out, and drying at room temperature for 24h for complete curing. The water contact angle of the coating without soaking treatment is 147.4 degrees, and the rolling angle is 15.0 degrees; the water contact angle of the soaked coating is 157.6 degrees, and the rolling angle is 1.0 degrees. Fig. 3 is an optical photograph showing a contact angle of a water droplet of the coating layer subjected to the immersion treatment, and fig. 4 is a scanning electron microscope photograph thereof.
Example 3
Under the condition of low-speed stirring at 500rpm, 1 part of hydrophobic carbon nanotube particles, 4 parts of FEVE resin and 0.8 part of hexamethylene diisocyanate trimer curing agent are sequentially added into 15 parts of butyl acetate solution, the mixture is stirred at 1800rpm at high speed for 10min, ultrasonic dispersion is carried out for 10min, the obtained coating is brushed on the surface of a glass sheet, and the glass sheet is dried at room temperature for 20h to be semi-cured. 0.5 part of hexamethylene diisocyanate trimer curing agent is added into 20 parts of butyl acetate solution, and the mixture is evenly mixed by ultrasonic dispersion for 15min to prepare soaking liquid. And immersing the semi-cured coating in the soaking solution for 60min, taking out, drying at room temperature for 24h, and completely curing, wherein the water contact angle of the obtained coating is 159.4 degrees, and the rolling angle is 1.0 degrees.
Example 4
Under the condition of low-speed stirring at 500rpm, adding 2.2 parts of hydrophobic micro-nano chain silica particles and 7.5 parts of 41082 type fluorocarbon resin into 25 parts of acetone solution in sequence, stirring at 1500rpm for 15min, then ultrasonically dispersing for 5min, spraying the obtained coating on the surface of a glass sheet, drying at room temperature for 8h to semi-solidify the coating, then immersing the coating in the acetone solution for 5min, taking out the coating, and solidifying at 80 ℃ for 24h, wherein the water contact angle of the obtained coating is 152.2 degrees, and the rolling angle is 9.0 degrees.
Example 5
The non-soaked and soaked coatings from example 2 were removed and rubbed against 1200 grit sandpaper under a weight of 100g until the roll angle was greater than 20. Each rubbing cycle is 10cm in the transverse direction and the longitudinal direction. After the coating which is not soaked is rubbed for 5 periods, the water contact angle is 146.8 degrees, and the rolling angle is 45.6 degrees. After the coating subjected to soaking treatment is rubbed for 80 cycles, the water contact angle is 148.2 degrees, and the rolling angle is 20.6 degrees. FIG. 5 is a scanning electron micrograph of the surface of the dip-treated coating after 80 cycles of rubbing.
Example 6
The non-immersion treated coating and the immersion treated coating obtained in example 2 were taken out several times and their average light transmittance was measured. In the wavelength range of 400-800nm, the average light transmittance of the coating without soaking treatment is 60 percent; the average light transmittance of the coating after soaking treatment was 82%.

Claims (1)

1. A preparation method of a durable super-hydrophobic coating is characterized by comprising the following preparation steps: under the condition of low-speed stirring at 500rpm, sequentially adding 1.5 parts of hydrophobic micro-nano gas-phase silica particles, 6 parts of FEVE resin and 1 part of hexamethylene diisocyanate trimer curing agent into 20 parts of butyl acetate solution, stirring at 1500rpm for 15min, then performing ultrasonic dispersion for 10min, and brushing the obtained coating on the surface of a glass sheet; drying at room temperature for 16h to reach semi-curing state; adding 1 part of hexamethylene diisocyanate trimer curing agent into 20 parts of butyl acetate solution, and performing ultrasonic dispersion for 10min to uniformly mix the solution and prepare a soaking solution; and immersing the semi-cured coating in the soaking solution for 30min, taking out, drying at room temperature for 24h, and completely curing to obtain the durable super-hydrophobic coating.
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CN116063687A (en) * 2021-11-01 2023-05-05 中国石油化工股份有限公司 Hydrophobic quartz sand and preparation method and application thereof
CN114085590B (en) * 2021-11-15 2022-06-07 中北大学 Method for forming organic-inorganic hybrid super-hydrophobic anticorrosive coating on surface of carbon steel
CN115477885B (en) * 2022-09-19 2023-08-25 中科融志国际科技(北京)有限公司 Multifunctional anti-icing coating and fan blade
CN115340822B (en) * 2022-09-24 2023-11-07 中京新材料科技(河北)有限公司 Super-smooth self-cleaning coating and preparation method thereof
CN115521670A (en) * 2022-10-24 2022-12-27 江苏理工学院 Normal-temperature cured super-hydrophobic fluorocarbon resin coating and preparation method thereof

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