CN112175482B - Durable super-hydrophobic composite material coating and preparation method thereof - Google Patents

Durable super-hydrophobic composite material coating and preparation method thereof Download PDF

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CN112175482B
CN112175482B CN202011068347.1A CN202011068347A CN112175482B CN 112175482 B CN112175482 B CN 112175482B CN 202011068347 A CN202011068347 A CN 202011068347A CN 112175482 B CN112175482 B CN 112175482B
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coating
acntb
sio
coupling agent
epoxy resin
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CN112175482A (en
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袁莉
王泽浩
顾嫒娟
梁国正
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Suzhou University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/08—Processes 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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Abstract

The invention discloses a durable super-hydrophobic composite material coating and a preparation method thereof2Coating of the coupling agent suspension on ACNTB-SiO2A coupling agent, epoxy resin, diglycidyl ether terminated polydimethylsiloxane and an amino-terminated hyperbranched polysiloxane mixture, and then curing to obtain the durable super-hydrophobic composite coating. The super-hydrophobic coating disclosed by the invention has the characteristics of simplicity and convenience in operation, durability and good hydrophobicity, and the prepared coating has excellent mechanical property and wear resistance. In particular, the present invention relates to a hydrophobic nanoparticleSiO rice2The particles are stored in the pores of the ACNTB, and when the coating structure is destroyed, the adhesive is decomposed by pyrolysis, and the SiO is promoted by the gas product formed2The nano-structure can be transferred to the surface of the coating to construct a new nano-structure surface with the exposed CNT, and the super-hydrophobic property of the coating can be restored.

Description

Durable super-hydrophobic composite material coating and preparation method thereof
Technical Field
The invention relates to a durable super-hydrophobic composite coating and a preparation method thereof, in particular to a super-hydrophobic composite coating with a micro/nano structure surface and excellent impact resistance, friction resistance and self-repairing functions and a preparation method thereof.
Background
The material with super-hydrophobic property has very wide application prospect in different fields of self-cleaning, anti-icing, anti-fogging, anti-corrosion, oil-water separation and the like. Research shows that the super-hydrophobic performance of the material surface can be realized by designing a complex micron/nanometer multilevel structure and introducing a low-surface-energy substance. Currently, hydrophobic inorganic nanoparticles (SiO)2、ZnO、TiO2、CNT、Al2O3Graphene, etc.) are commonly used for constructing a micron/nanometer multilevel surface structure to realize the hydrophobicity of the material, but due to weak van der waals force interaction among inorganic nano-particles, the surface of the super-hydrophobic coating shows weak mechanical properties and tolerance, the super-hydrophobicity of the material is seriously influenced, and the application of the super-hydrophobic material in actual life is greatly limited. Therefore, it is a challenging task to prepare superhydrophobic coating materials with good mechanical properties and stability and durability.
In summary, aiming at the problems and development trends of the existing super-hydrophobic coating materials, the improvement of the functions of the coating components and the endowment of the self-repairing function of the coating have positive significance for constructing the durable environment-friendly super-hydrophobic material with a stable structure and expanding the application of the durable environment-friendly super-hydrophobic material.
Disclosure of Invention
Needle of the inventionFor the problem of poor durability of the super-hydrophobic coating caused by weak interaction between inorganic particles, weak particle/binder interface and the like, the composite super-hydrophobic coating with the micro/nano surface structure is prepared by combining the micron-sized particles which have strong interaction particle interaction and are formed by combining and hybridizing multi-stage nano particles with an epoxy system adhesive. The super-hydrophobic coating disclosed by the invention has the characteristics of simplicity and convenience in operation, durability and good hydrophobicity, and the prepared coating has excellent mechanical property and wear resistance. In particular, the hydrophobic nano SiO of the invention2The particles are stored in the pores of the ACNTB, and when the coating structure is destroyed, the adhesive is decomposed by pyrolysis, and the SiO is promoted by the gas product formed2The nano-structure can be transferred to the surface of the coating to construct a new nano-structure surface with the exposed CNT, and the super-hydrophobic property of the coating can be restored.
In order to achieve the purpose, the invention adopts the technical scheme that:
a durable super-hydrophobic composite material coating is prepared through preparing ACNTB-SiO2Coating of the coupling agent suspension on ACNTB-SiO2-a gel surface of a mixture of a coupling agent, epoxy resin, diglycidyl ether-terminated polydimethylsiloxane, and amino-terminated hyperbranched polysiloxane, followed by curing to obtain a durable superhydrophobic composite coating; or mixing ACNTB-SiO2Coating the coupling agent suspension on the surface of the gel of the epoxy resin and amino-terminated hyperbranched polysiloxane mixture, and curing to obtain a durable super-hydrophobic composite coating; or mixing ACNTB-SiO2Coating the coupling agent suspension on the surface of a gel of a mixture of epoxy resin, diglycidyl ether-terminated polydimethylsiloxane and amino-terminated hyperbranched polysiloxane, and curing to obtain a durable super-hydrophobic composite coating; or mixing ACNTB-SiO2Coating of the coupling agent suspension on ACNTB-SiO2-a gel surface of a mixture of a coupling agent, epoxy resin and amino-terminated hyperbranched polysiloxane, and then curing to obtain a durable superhydrophobic composite coating.
In the invention, multi-wall carbon oriented carbon nanotube bundle, alkali, solvent and tetra-silicic acidAfter the ethyl ester is mixed and reacted, adding a silane coupling agent, and continuing the reaction to obtain the ACNTB-SiO2-a coupling agent.
Furthermore, the weight ratio of the multi-walled carbon oriented carbon nanotube bundle to tetraethyl orthosilicate to the silane coupling agent to the alkali to the solvent is (1-2) to (9-14) to (2-5) to (9-12) to (100-200); wherein, the bundle diameter of the multi-wall carbon oriented carbon nano tube bundle (ACNTB) is 10-25 μm, the length is 30-100 μm, the multi-wall carbon oriented carbon nano tube bundle has rich pore structures, all CNTs are oriented along a certain direction, and obvious physical entanglement exists among the CNTs; the silane coupling agent is gamma-methacryloxypropyl trimethoxysilane, hexamethyl silazane, dodecyl trimethoxysilane, vinyl trimethoxysilane, phenyl trimethoxysilane or hexadecyl trimethoxysilane; the alkali is ammonia water or triethanolamine; the solvent is water, ethanol, ethyl acetate or their mixture. ACNTB-SiO2The preparation method of the coupling agent comprises the steps of adding the ACNTB particles into an alkali solvent at room temperature, stirring, adding a mixed solution of TEOS and the solvent, reacting at 30-60 ℃ for 18-36h, adding the silane coupling agent, continuing stirring for 6h, finishing the reaction, naturally cooling to room temperature, washing the obtained suspension with ethanol for 2-5 times, centrifuging for three times, and drying in a vacuum oven at 60 ℃ for 12h to obtain black micron-sized ACNTB-coupling agent modified SiO2Nanometer hybrid particle (ACNTB-SiO)2Coupling agents) in which SiO is present2Assembled in the pore structure of the ACNTB and on the CNT surface.
In the present invention, in the mixture, ACNTB-SiO2The weight portions of the coupling agent, the epoxy resin, the diglycidyl ether terminated polydimethylsiloxane and the amino-terminated hyperbranched polysiloxane are respectively 0-1 portion, 70-100 portions, 0-70 portions and 30-60 portions, wherein, the weight portions of the ACNTB-SiO are2The coupling agent may be used in an amount of 0 or else different from 0; the dosage of the diglycidyl ether end-capped polydimethylsiloxane can be 0 or not; in suspension, ACNTB-SiO24.0 to 20 parts by weight of a coupling agent. In the present invention, ACNTB-SiO24.0-20 parts of total coupling agent, including ACNTB-SiO, possibly added in a gel system2Coupling agent and ACNTB-SiO in suspension2-amount of coupling agent.
In the invention, the epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, hydrogenated bisphenol A epoxy resin, novolac epoxy resin, multifunctional glycidyl ether resin, glycidyl ester epoxy resin and halogen epoxy resin; the diglycidyl ether-terminated polydimethylsiloxane (DGETPDMS) is a colorless transparent liquid, has a viscosity (25 ℃) of 50 to 10000 mPa.s and a specific gravity (25 ℃) of 1.05 to 1.10.
In the invention, the curing process is (50-70 ℃)/1 h + (80-150 ℃)/1-2 h.
The invention discloses application of the durable super-hydrophobic composite material coating in preparation of a wear-resistant hydrophobic coating; the abrasion-resistant hydrophobic coating has a multi-level micro/nano structured surface.
The preparation method of the durable super-hydrophobic composite coating comprises the following steps: epoxy resin and ACNTB-SiO are mixed at 30-150 DEG C2Uniformly mixing a coupling agent (0-1 part), DGETPDMS (0-70 parts) and HBPSi, maintaining for 10-20min to obtain a resin adhesive prepolymer tiled gel, and adding a solution containing ACNTB-SiO when the prepolymer reaches a gel state2Dripping toluene suspension of a coupling agent on the surface of the gel, and curing for 50-70 ℃/1h + (80-150 ℃)/1-2 h to obtain the durable super-hydrophobic epoxy/ACNTB-SiO with the micro/nano structure surface after the solvent is volatilized2-a coupling agent composite coating; ACNTB-SiO2The weight ratio of the coupling agent to the toluene is 1: 25-50.
In the technical scheme, the ACNTB-SiO2The coupling agent particles have a stable structure, SiO2The nano particles assembled in the pores of the micron-sized ACNTB particles can effectively transfer the load borne by the CNT in the ACNTB and limit the relative slippage of the CNT, and conversely, the SiO is used for2The nanoparticles are assembled in a pore structure in the ACNTB, SiO2The nanoparticles are immobilized by the CNTs. Micron-sized ACNTB-SiO2CNT and SiO in coupling agent particles2The particle confinement and constrained interaction relationship is such that CNT and SiO2The interaction is enhanced, thereby leading the micron-sized ACNTB-SiO2The coupling agent particles being stableAnd (5) structure.
In the technical scheme, the amine value of the amino-terminated hyperbranched polysiloxane HBPSi is 0.5-0.65 mol/100g, such as 0.59 mol/100 g; the synthesis process of HBPSi can be as follows: mixing 3-aminopropyltriethoxysilane (KH550), deionized water and absolute ethyl alcohol at 60 ℃, stirring for 4h under the protection of nitrogen, cooling the reaction system to room temperature to obtain transparent liquid, and reducing the pressure of the reaction system by using a vacuum pressure reducing device to obtain HBPSi with an amine value of 0.59 mol/100g, wherein the mass ratio of KH550 to deionized water to absolute ethyl alcohol is 22:100: 16.
The super-hydrophobic coating prepared by the invention has a multi-stage micro/nano structure surface, the water Contact Angle (CA) of the surface of the super-hydrophobic coating can reach 155-. Particularly, the super-hydrophobic coating has excellent anti-friction performance and mechanical performance, and the super-hydrophobic performance of the coating can be still maintained after the coating is abraded by 800-mesh sand paper under the action of 100g of load for nearly 300 cycles (one-cycle friction stroke is 10 cm) and after the coating is impacted by 1188KPa water pressure for 120 s. Due to ACNTB-SiO2Presence of coupling agent particles, partial decomposition of the resin by heat treatment of the damaged coating, and nano-SiO2The nano-carbon nano-tube can easily migrate to the surface of the coating under the action of heat and airflow of decomposed products, and the nano-carbon nano-tube and the CNT can construct a new nano-structure surface, so that the super-hydrophobic property of the coating can be restored.
An aligned carbon nanotube bundle (ACNTB) is an aggregate (generally micron-sized bundle diameter) formed by a plurality of CNTs arranged in a certain direction and bound by van der waals force, and the carbon nanotubes are physically entangled, and because a single carbon tube is relatively long, the physically entangled carbon nanotubes are not easily dissociated, but the ACNTB has a rich pore structure, so that the ACNTB is unstable in structure, and under the action of external force, the CNTs in the ACNTB are easy to slip, and the CNTs are poor in interaction and cannot be effectively supported. Adding the ACNTB particles into an alkali solvent at room temperature, stirring, adding a mixed solution of TEOS and the solvent, adding a silane coupling agent after reaction, continuing stirring, finishing the reaction, naturally cooling to room temperature, washing the obtained suspension with ethanol, centrifuging and drying to obtain black micron-sized ACNTB-coupling agent modified SiO2Nanometer hybrid particle (ACNTB-SiO)2Coupling agents) in which SiO is present2Assembled in the porous structure of ACNTB and on the surface of CNT, can enhance the function between CNTs, effectively transfer the acting force between CNT tubes, increase the stability of ACNTB structure, and SiO2As a hydrophobic particle, the hydrophobic particle is easily obtained by hydrolyzing and modifying Tetramethylsilane (TEOS), and the abundant pore structure of ACNTB is reserved super-hydrophobic SiO2The particles are prepared to a sufficient condition, SiO2The particles stored in the pores of the ACNTB can not only improve the function among CNTs in the ACNTB and enhance the structural stability of the ACNTB, but also help to maintain or improve the superhydrophobicity of the ACNTB.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the super-hydrophobic coating prepared by the invention has outstanding impact resistance, is suitable for most of matrix materials, and has simple preparation process, and the prepared SiO is2The @ ACNTB particles have obvious structural stability and strong interaction among the particles. The composite coating thus formed has outstanding stability of durable superhydrophobic properties. In addition, the damaged coating can be treated at high temperatures to partially decompose the resin and the SiO2The nano-particles are easy to migrate to the surface of the coating under the action of heat and airflow of decomposed products, and the nano-particles and the exposed nano-particles together construct a novel nano-structure surface, so that the super-hydrophobic property of the coating can be restored.
Drawings
FIG. 1 shows ACNTB and ACNTB-SiO in example 12KH570 Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) photographs of (a, a ', c) non-sonicated ACNTB, (c') 5min sonicated ACNTB, (b, b ', d, d') 5min sonicated ACNTB-SiO2-KH570；
FIG. 2 shows ACNTB and ACNTB-SiO in example 12-pore size distribution and particle surface area of KH570 (obtained from specific surface and porosity analyzer);
FIG. 3 is a digital photograph of the water contact angle CA and the rolling angle SA of the coating, a water drop on the surface of the coating, and an SEM photograph of the coating, ACNTB-SiO2-KH570（a, b, g, j），ACNTB（c, d, h, k），SiO2-KH570（e, f, i, l）；
FIG. 4 is ACNTB-SiO2-KH570 and ACNTB-SiO after ACNTB tableting2-KH570 (a), acntb (b) digital and SEM pictures of the coating water droplets on the coating surface;
FIG. 5 shows the superhydrophobic E-51/ACNTB-SiO prepared in example 12-SEM photographs of the water contact angle CA and the rolling angle sa (a) of KH570 composite coating, E-51 coating of example 1-1 and coating of comparative example 1-2, coating example 1-1 (b), coating of example 1(c) and coating of example 1-2 (d);
FIG. 6 shows the superhydrophobic E-51/ACNTB-SiO prepared in example 12CA and SA (a) of the KH570 composite material coating after being impacted by different water flows for 120s, and SEM picture (b) of the surface of the coating after being impacted by water pressure 1329 KPa;
FIG. 7 shows the superhydrophobic E-51/ACNTB-SiO prepared in example 12After the KH570 composite material coating is subjected to different impact energies of sand grains (250 g, the average grain diameter is 251 mu m), the composite coating CA and SA (a) are subjected to single sand grain impact energy of 1.04X 10-7SEM photograph of the coating surface after impact of J/grain (b);
FIG. 8 shows the superhydrophobic E-51/ACNTB-SiO prepared in example 12SEM photographs of KH570 composite coatings after 800 mesh sanding under 100g load after CA and sa (a) and coating rubbing cycles 2 (b), 60 (c), 260(d) and 300 (e) rubbing;
FIG. 9 shows the superhydrophobic E-51/ACNTB-SiO prepared in example 12-water contact angle photographs and SEM photographs of the coating after damage to the KH570 composite coating and tape stripping and after 9h in a 300 ℃ muffle furnace, wherein a, b, d correspond to the coating after heating after damage stripping; c, coating is not heated after peeling corresponding to the damage;
fig. 10 is an SEM photograph of the coatings in example 2 and comparative example 2.
Detailed Description
The raw materials involved in the invention are conventional commercial products, and the specific operation method and the test method involved are conventional conditions except for special instructions; the technical solution of the present invention is further described with reference to the accompanying drawings and examples.
In the examples and comparative examples, the bundle diameter of the multi-walled carbon nanotube bundle (ACNTB) is 10 to 25 μm and the length thereof is 30 to 100 μm.
Synthesis example
Mixing 3-aminopropyltriethoxysilane (KH550), deionized water and absolute ethyl alcohol at 60 ℃, stirring for 4h under the protection of nitrogen, then cooling the reaction system to room temperature to obtain a transparent liquid, and removing the solvent from the reaction system under reduced pressure by using a vacuum pressure reducing device to obtain HBPSi with an amine value of 0.59 mol/100g, wherein the weight ratio of KH550, deionized water and absolute ethyl alcohol is 22:100: 16.
Example 1
Adding 1.0g of ACNTB particles into a mixed solution of 9.1g of ammonia water and 110g of ethanol under the stirring condition, stirring for 10min, dropwise adding a mixed solution of 9.35g of TEOS and 40g of ethanol, heating in a water bath at 60 ℃, conventionally stirring for 18h, adding 2.5g of KH570, continuously stirring for 6h, finishing the reaction, naturally cooling to room temperature, washing and centrifuging the obtained suspension for three times by using ethanol, and collecting ACNTB-SiO2-KH570 granules, then drying in a vacuum oven at 60 deg.C for 12h to obtain black ACNTB-SiO2-KH570 granules.
FIG. 1 shows ACNTB and ACNTB-SiO in example 1 of the present invention2KH570 Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) photographs. As can be seen from fig. 1a, 1a 'and 1c, the CNTs in ACNTB have a certain alignment, there is a significant entanglement between CNTs, and furthermore, ACNTB has a rich pore structure, but as can be seen from fig. 1 c', the structural integrity of ACNTB is significantly destroyed after ultrasonic treatment, and CNTs are easily dissociated; from FIGS. 1b, 1b ', 1d and 1 d' it can be seen that ACNTB-SiO has been sonicated2in-KH 570, nano SiO is adsorbed on the surface of carbon tube2Particles, nano SiO is embedded between the carbon tube and the carbon tube gap2，ACNTB-SiO2-KH570 is integral in its overall structure. It can be seen that the material is composed of nano SiO2ACNTB-SiO constructed by hybridization with ACNTB2the-KH 570 particle structure system is stable in structure and is not easy to break under the action of external force. FIG. 2 shows ACNTB and ACNTB-SiO in example 12Pore size distribution and particle surface area of KH570 from FIG. 2It can be seen that SiO is assembled in the pores due to the ACNTB2，ACNTB-SiO2The pores of the-KH 570 were significantly reduced and the pores became smaller, but ACNTB-SiO2The specific surface area of-KH 570 was larger than that of ACNTB, which indicates that ACNTB-SiO2The KH570 particles have an increased area of interaction with the other components of the coating, which is beneficial to increase the force acting between them.
To evaluate ACNTB-SiO2Superhydrophobicity of-KH 570 particles, prepared from ACNTB-SiO2The KH570 particles and the toluene are prepared into ACNTB-SiO according to the mass ratio of 1:92KH570 solution, and dripping the solution on the surface of the glass slide to form a layer of dense ACNTB-SiO on the surface of the glass slide2Evaporating the solvent in an oven at 60 deg.C to dry, and treating for 1 hr to obtain ACNTB-SiO2-KH570 coating, using the same method to coat ACNTB and SiO2Dripping KH570 particles on the surface of the glass slide to obtain ACNTB and SiO2KH570 coating was used as a comparative sample. FIG. 3 is ACNTB-SiO2-KH570, ACNTB and SiO2The values of water Contact Angle (CA), rolling angle (SA), CA and SA for KH570 coating, ACNTB coating in digital and SEM pictures of coating were 155.7 + -2.5 deg. and 2.5 + -0.5 deg., respectively. SiO 22The CA and SA values of KH570 coatings were 152.7 + -3 deg. and 4 + -0.5 deg., respectively. ACNTB-SiO2The CA and SA values of KH570 coatings were 166.3 + -1 deg. and 1.8 + -0.5 deg., respectively. Apparently, ACNTB-SiO2KH570 coating with a ratio of ACNTB to SiO2Higher CA and lower SA values for KH570 coatings, indicating ACNTB-SiO2the-KH 570 coating has good super-hydrophobic property. For superhydrophobic surfaces, air pockets between the liquid droplets and the solid can form a stable liquid-gas-solid interface, and a solid surface with a complex multilevel structure can increase the gas fraction on the surface and provide more stable air pockets, giving the material better hydrophobicity. ACNTB-SiO2SEM photograph (FIG. 1) of-KH 570 shows that ACNTB-SiO2The KH570 particles are prepared from ACNTB and SiO2-KH570 particles, which have a surface with a complex multilevel nanostructure and can therefore have excellent superhydrophobicity. Wherein, under the condition of stirring, 9.35g of TEOS and 40g of ethanol mixed solution are dropwise added into 9.1g of ammonia water and 110g of ethanol mixed solution, and the mixture is added into 60 ℃ water bathHeating, conventionally stirring for 18h, adding 2.5g KH570, continuously stirring for 6h, reacting, naturally cooling to room temperature, washing the obtained suspension with ethanol, centrifuging for three times, collecting particles, and drying in a vacuum oven at 60 deg.C for 12h to obtain nanometer SiO2-KH570 granules.
FIG. 4 is ACNTB-SiO2-KH570 and ACNTB coating obtained by conventional compression in press2-digital and post-press SEM photographs of CA, water droplets of KH570 and ACNTB flake material on the coating surface. Water in ACNTB-SiO2The CA of KH570 and ACNTB sheet material was 147.4 + -2.5 deg. and 71.7 + -2.5 deg., respectively. Apparently, the compacted ACNTB-SiO2-KH570 sheet material still has hydrophobic properties. As can be seen from the SEM image (FIG. 4 a), the resultant ACNTB-SiO was compressed2-KH570 sheet still leaves much porosity; and the porosity among the CNTs among the compressed ACNTBs is obviously reduced. Due to ACNTB-SiO2-KH570 inter-CNT SiO2The existence of the particles can maintain the spacing between the CNTs and limit the displacement of the CNTs, so that the original structure can be relatively well maintained, which shows that ACNTB-SiO2The KH570 coating has good structural stability.
2g of epoxy resin (E-51), 0.02g of ACNTB-SiO were mixed at 30 ℃2Uniformly mixing KH570, 0.6g of DGETPDMS (colorless transparent liquid with the viscosity of 5000 mPa.s at 25 ℃ and the specific gravity of 1.08 at 25 ℃) and 0.88g of HBPSi for 10min to obtain a resin adhesive prepolymer, uniformly scraping and coating the adhesive prepolymer on the surface of an aluminum plate substrate (the thickness of the adhesive prepolymer layer is 70 mu m), and when the prepolymer reaches a gel state after 15min, adding the prepolymer containing ACNTB-SiO2-KH570 suspension in toluene (ACNTB-SiO)2KH570 and toluene 0.086g and toluene 4.3g respectively) are dripped on the surface of the resin prepolymer, and after standing for 30 minutes, the durable super-hydrophobic E-51/ACNTB-SiO with the micro/nano structure surface is obtained by curing treatment at 60 ℃/1h +100 ℃/1h2-KH570 composite coating, being a durable superhydrophobic composite coating, with a coating thickness of 100 μm.
The following comparative examples 1 to 1, 1 to 2 and 1 to 3 show the unexpected technical effects of the present invention for comparison with examples.
Comparative examples 1 to 1
Uniformly mixing 2g of epoxy resin (E-51), 0.6g of DGETPDMS (colorless transparent liquid with the viscosity (25 ℃) of 5000 mPa.s and the specific gravity (25 ℃) of 1.08) and 0.88g of HBPSi at 30 ℃, maintaining for 10min to obtain a resin adhesive prepolymer, uniformly scraping and coating the adhesive prepolymer on the surface of an aluminum substrate, and curing at 60 ℃/1h +100 ℃/1h to obtain an E-51 coating when the prepolymer reaches a gel state, wherein the thickness of the coating is 100 mu m.
Comparative examples 1 to 2
2g of epoxy resin (E-51), 0.02g of ACNTB-SiO were mixed at 30 ℃2-KH570, 0.6g DGETPDMS (colorless transparent liquid, viscosity (25 deg.C) 5000 mPa.s, specific gravity (25 deg.C) 1.08), 0.88g HBPSi, mixing well, maintaining for 10min to obtain resin adhesive prepolymer, mixing with ACNTB-SiO2-KH570 toluene suspension (ACNTB-SiO)2-KH 570: toluene =0.086g:4.3g), then blade-coating on the surface of the base material, curing at 60 ℃/1h +100 ℃/1h when the prepolymer reaches the gel state to obtain E-51/ACNTB-SiO2KH570-blend coating, thickness of 100 μm.
FIG. 5 shows a drop of superhydrophobic E-51/ACNTB-SiO prepared in example 12-KH570 composite coating, E-51 coating of comparative example 1-1 and E-51/ACNTB-SiO of comparative example 1-22-KH 570-SEM photograph of water contact angle CA and sliding angle SA values on the blend coating, surface of the coating. The CA and SA of the coating in example 1 were respectively: 159 ° and 2.5 °. It can be seen that E-51/ACNTB-SiO in example 1 is present in comparison with the coatings of comparative examples 1-1 and 1-22-KH570 composite coatings have excellent superhydrophobicity. As can be seen from the SEM photograph of FIG. 5c, E-51/ACNTB-SiO2KH570 composite coating with micrometer protrusions, and nano CNT and SiO were clearly observed on the coating surface2Presence of particles, E-51/ACNTB-SiO2The micro/nano-structured surface of the KH570 composite material coating is favorable for adsorbing a large amount of air molecules, reducing the contact of water drops with the surface of the coating, and enabling the coating to show excellent super-hydrophobicity; while the coatings of comparative examples 1-1 and 1-2 had low CA and high SA values.
FIG. 6 shows the superhydrophobic E-51/ACNTB-SiO prepared in example 1 after different water stream impact (120 s)2SEM images of the surface of the coating after impact of CA and SA and water pressure 1329KPa of KH570 composite coating. From FIG. 6a, it can be seen that EP/ACNTB-SiO occurs after different water pressure shocks2The CA of the KH570 coating is slightly reduced, the SA value is gradually increased, but after 1188KPa water pressure scouring for 120s, the EP/ACNTB-SiO2KH570 coating has CA value of 151.4 + -1.5 deg., and SA value is maintained at 7.1 + -1.5 deg.. After the coating is impacted by the water pressure of 1329KPa, CA is reduced to 147.7 +/-1.5 degrees, SA is increased to 14.3 +/-3 degrees from 2.5 +/-0.5 degrees, and the super-hydrophobicity of the coating can disappear but the coating still has high hydrophobicity. As can be seen from fig. 6b, after the pressure impact of 1329KPa, the naked CNTs can be clearly observed on the surface of the coating, and the hydrophobicity of the coating can be effectively guaranteed by a large number of naked particles.
FIG. 7 is the superhydrophobic E-51/ACNTB-SiO prepared in example 12-KH570 composite coating CA and SA after different impact energy of sand grains (average grain size 251 μm) and composite coating CA and SA after 1.04X 10-7SEM photograph of the coating surface after energy impact of J/grain. As the impact energy of the quartz sand increases, the CA and SA values of the composite coating after impact slowly decrease and increase, respectively. When the impact energy is 1.04X 10-7At J/grain, the coating CA is 151.3 +/-1.6 degrees and the SA is 11.5 +/-1.9 degrees, which shows that the coating also shows good impact resistance to sand impact. After undergoing 1.04X 10-7After the J/grain sand impact, the damaged area of the composite material coating still can keep a good rough surface structure, and protruding nano particles can be observed on the surface, which plays a positive role in maintaining the super-hydrophobic property. When the impact energy reaches 1.3X 10-7At J/grain, the CA and SA of the coating are respectively 125.7 +/-2 degrees and 45.2 +/-2.9 degrees, and the super-hydrophobic property is lost.
The water impact test (fig. 6) and the sand drop test (fig. 7) show that the composite coating in example 1 has excellent impact resistance and excellent strength and toughness, and strong interaction among particles can effectively resist external force, thereby playing a positive role in prolonging the service life of the coating.
FIG. 8 shows the superhydrophobic E-51/ACNTB-SiO prepared in example 12-change in CA and SA after 800 mesh sanding of a KH570 composite coating under a 100g load and SEM pictures of the coating surface. As can be seen from the figure, when the coating was subjected to 2 rubbing cycles, the CA of the coating increased and the SA slightly decreased; as can be seen from fig. 8b, the coating surface has significantly protruding CNTs, and this surface structure can increase the amount of air molecules adsorbed on the coating surface and reduce the contact of water droplets with the coating surface. In particular, when the rubbing cycle reached 260 times, the CA and SA of the coating remained above 150 ° and below 10 °, indicating that the coating still had superhydrophobicity, at which time the coating surface still had abundant nanoparticles. The invention E-51/ACNTB-SiO2The KH570 composite material coating can withstand nearly 300 sanding cycles (the friction stroke of the coating on the surface of sandpaper is nearly 30 m), which shows that the coating has excellent wear resistance, and the main reasons are that the coating has excellent mechanical properties and the acting force with the adhesive layer is large, so that the coating can effectively resist the wear caused by external force.
The superhydrophobic E-51/ACNTB-SiO prepared in example 12Compared with the super-hydrophobic coating reported in the prior literature, the KH570 composite coating has the following advantages: (1) the coating does not contain fluorine, and is green and environment-friendly; (3) the super-hydrophobic coating has high impact resistance and friction performance, and the impact pressure of water in the coating reported in the literature at present does not reach 1188KPa, and the impact energy of sand grains reaches 1.04 multiplied by 10-7Coatings that retain superhydrophobicity at J/grain and that have high impact properties while still having superhydrophobic properties after nearly 300 sanding cycles are reported are also not known in the literature.
Super-hydrophobic E-51/ACNTB-SiO prepared in example 12The KH570 composite coating was peeled off (surface particle floating layer removed) with 3M tape after 300 times of 800 mesh sanding under 100g load to obtain a damaged coating; the coating was then placed in a muffle furnace at 300 ℃ for 9h and the water contact angle photographs and SEM photographs of the coating surface before and after heating were measured, see FIG. 9. E-51/ACNTB-SiO2-KH570 composite coating damage and loss of hydrophobicity after tape peeling, CA of coating changed from 123 ° to 160.4 ± 2.5 ° after heating at 300 ℃ for 9h, SA was less than1 deg. As can be seen from SEM pictures, after the damaged coating is heated at 300 ℃, nano particles are gathered on the surface of the coating, and the structure is favorable for recovering the super-hydrophobic property of the coating.
Comparative examples 1 to 3
2g of epoxy resin (E-51), 0.02g of ACNTB-SiO were mixed at 30 ℃2Uniformly mixing-KH 570, 0.6g of DGETPDMS (colorless transparent liquid with the viscosity of 5000 mPa.s at 25 ℃ and the specific gravity of 1.08 at 25 ℃) and 0.88g of 3-aminopropyltriethoxysilane (KH550) for 10min to obtain a resin adhesive prepolymer, uniformly coating the adhesive prepolymer on the surface of an aluminum plate substrate by scraping, and when the prepolymer reaches a gel state after 15min, adding the prepolymer containing ACNTB-SiO2-KH570 suspension in toluene (ACNTB-SiO)2KH570 and toluene 0.086g and 4.3g respectively) are dripped on the surface of the resin prepolymer, and after standing for 30 minutes, E-51/KH550/ACNTB-SiO with micro/nano structure surface is obtained by curing treatment at 60 ℃/1h +100 ℃/1h2-KH570 composite coating, under 1188KPa/120s water pressure, sand impact energy of 1.04X 10-7Neither J/grain nor 50 sandpaper rubbing cycles were superhydrophobic (CA)<130°，SA>15°）。
Comparative examples 1 to 4
2g of epoxy resin (E-51), 0.02g of ACNTB-SiO were mixed at 30 ℃2Uniformly mixing-KH 570, 0.6g of DGETPDMS (colorless transparent liquid with the viscosity of 5000 mPa.s at 25 ℃ and the specific gravity of 1.08 at 25 ℃) and 0.88g of HBPSi for 10min to obtain a resin adhesive prepolymer, uniformly scraping and coating the adhesive prepolymer on the surface of an aluminum plate substrate (the thickness of the adhesive prepolymer layer is 70 mu m), curing the prepolymer at 60 ℃/1h +100 ℃/1h when the prepolymer reaches a gel state after 15min, and dripping the prepolymer containing ACNTB-SiO2-KH570 suspension in toluene (ACNTB-SiO)2KH570 and toluene 0.086g and 4.3g respectively, standing for 30 min, curing at 60 deg.C/1 h +100 deg.C/1 h to obtain coating layer with no hydrophobicity after 1 time of abrasive paper rubbing (CA)<120°，SA>35°）。
In conclusion, the super-hydrophobic ACNTB-SiO formed by utilizing the hybridization of multi-stage nano particles with stable structures2Ultra-hydrophobic made of-KH 570 particlesThe water epoxy composite coating has excellent durability.
Example 2
Adding 1.0g of ACNTB particles into a mixed solution of 9.1g of ammonia water and 110g of ethanol under the stirring condition, stirring for 10min, dropwise adding a mixed solution of 9.35g of TEOS and 40g of ethanol, heating in a water bath at 60 ℃, stirring at a constant speed for 18h, adding 2.5g of KH570, stirring for 6h, finishing the reaction, naturally cooling to room temperature, washing and centrifuging the obtained suspension for three times by using ethanol, and collecting ACNTB-SiO2-KH570 granules, then drying in a vacuum oven at 60 deg.C for 12h to obtain black ACNTB-SiO2-KH570 granules.
2g of epoxy resin (E-51), 0.02g of ACNTB-SiO were mixed at 30 ℃2Uniformly mixing KH570, 0.6g of DGETPDMS (colorless transparent liquid with the viscosity of 5000 mPa.s at 25 ℃ and the specific gravity of 1.08 at 25 ℃) and 0.88g of HBPSi for 10min to obtain a resin adhesive prepolymer, uniformly scraping and coating the adhesive prepolymer on the surface of an aluminum plate substrate (the thickness of the adhesive prepolymer is 70 mu m), and when the prepolymer reaches a gel state after 15min, adding the prepolymer containing ACNTB-SiO2-KH 570-toluene suspension (ACNTB-SiO)2-KH 570: toluene = 0.114g:5.7g) is dripped on the surface of the resin prepolymer, and after the resin prepolymer is placed for 30 minutes, the durable super-hydrophobic E-51/ACNTB-SiO with the micro/nano structure surface is obtained by curing treatment at 60 ℃/1h +100 ℃/1h2-KH570 composite coating with a coating thickness of 100 μm.
Comparative example 2-1
2g of epoxy resin (E-51), 0.02g of ACNTB-SiO were mixed at 30 ℃2-KH570, 0.6g DGETPDMS (colorless transparent liquid, viscosity (25 deg.C) 5000 mPa.s, specific gravity (25 deg.C) 1.08), 0.88g HBPSi, mixing well, maintaining for 10min to obtain resin adhesive prepolymer, mixing with ACNTB-SiO2-KH570 suspension (ACNTB-SiO)2-KH 570: solvent =0.4g:18g), then blade-coating on the surface of a base material, and curing at 60 ℃/1h +100 ℃/1h to obtain E-51/ACNTB-SiO2KH570-blend coating, thickness of 100 μm.
FIG. 10 is an SEM photograph of the coatings of example 2 and comparative example 2-1, and Table 1 shows example 2 and comparative examplePerformance data for the coating in example 2-1; the test method was the same as in example 1. As can be seen from FIG. 10 and Table 1, the present invention employs a small amount of ACNTB-SiO2The KH570 particles can make the coating layer obtain super-hydrophobicity, and the surface of the coating layer has a micro/nano structure surface. The adoption of the blending technology needs to add a large amount of ACNTB-SiO2KH570 particles can make the coating obtain higher CA, but SA is obviously more than 10 degrees, and the coating does not have super-hydrophobicity. As can be seen from Table 1, the coating of example 2 had a water pressure of 1188KPa and a sand impact energy of 1.04X 10-7The super-hydrophobicity of the J/grain and 250 times of abrasive paper after friction cycles is realized, and the super-hydrophobicity can be recovered after the coating is damaged and heated for 9h at 300 ℃.
Figure 180900DEST_PATH_IMAGE001
Comparative examples 2 to 2
Dropwise adding a mixed solution of 9.35g of TEOS and 40g of ethanol into a mixed solution of 9.1g of ammonia water and 110g of ethanol under the stirring condition, heating in a water bath at 60 ℃, uniformly stirring for 18h, adding 2.5g of KH570, continuously stirring for 6h, finishing the reaction, naturally cooling to room temperature, washing and centrifuging the obtained suspension with ethanol for three times, collecting particles, drying in a vacuum oven at 60 ℃ for 12h to obtain SiO2-KH570 granules.
2g of epoxy resin (E-51), 0.02g of SiO were mixed at 30 ℃2Uniformly mixing KH570, 0.6g of DGETPDMS (colorless transparent liquid with the viscosity of 5000 mPa.s at 25 ℃ and the specific gravity of 1.08 at 25 ℃) and 0.88g of HBPSi for 10min to obtain a resin adhesive prepolymer, uniformly scraping and coating the adhesive prepolymer on the surface of an aluminum plate substrate (the thickness of the adhesive prepolymer layer is 70 mu m), and when the prepolymer reaches a gel state after 15min, adding SiO2-KH 570-toluene Suspension (SiO)2-KH 570: toluene = 0.114g:5.7g) is dripped on the surface of the resin prepolymer, and after the resin prepolymer is placed for 30 minutes, the E-51/SiO is obtained by curing treatment at 60 ℃/1h +100 ℃/1h2KH570 composite coating (coating thickness 100 μm), sand impact energy 1.04X 10 under 1188KPa/120s water pressure-7J/grain and 80 times of abrasive paper frictionNone of them has super-hydrophobicity after Circulation (CA)<130°，SA>15°）。
Comparative examples 2 to 3
Dropwise adding 0.2g of KH570 into a mixed solution of 10g of ACNTB particles and 100g of ethanol under the stirring condition at 60 ℃, continuously stirring for 6h, finishing the reaction, naturally cooling to room temperature, washing the obtained suspension with ethanol, centrifuging for three times, collecting particles, and drying in a vacuum oven at 60 ℃ for 12h to obtain the ACNTB-KH570 particles.
2g of epoxy resin (E-51), 0.02g of ACNTB-KH570, 0.6g of DGETPDMS (colorless transparent liquid, viscosity (25 ℃) is 5000 mPa.s, specific gravity (25 ℃) is 1.08) and 0.88g of HBPSi were mixed uniformly at 30 ℃ and maintained for 10min, obtaining resin adhesive prepolymer, then evenly coating the adhesive prepolymer on the surface of an aluminum plate substrate (the thickness of the adhesive prepolymer layer is 70 mu m) by scraping, when the prepolymer reaches a gel state after 15min, then, a suspension containing ACNTB-KH 570-toluene (ACNTB-KH 570: toluene = 0.114g:5.7g) was dropped on the surface of the resin prepolymer, and after standing for 30 minutes, curing at 60 ℃/1h +100 ℃/1h to obtain the E-51/ACNTB-KH570 composite material coating (the coating thickness is 100 mu m), the sand impact energy is 1.04 multiplied by 10 under the water pressure 1188KPa/120 s.-7Neither J/grain nor 30 sandpaper rubbing cycles exhibited superhydrophobicity (CA)<110°，SA>35°）。
In conclusion, the super-hydrophobic ACNTB-SiO formed by utilizing the hybridization of multi-stage nano particles with stable structures2The super-hydrophobic epoxy composite coating prepared from the-KH 570 particles has excellent durability.
Example 3
Adding 2.0g of ACNTB particles into a mixed solution of 12g of ammonia water and 150g of ethanol under the stirring condition, stirring for 10min, dropwise adding a mixed solution of 14g of TEOS and 50g of ethanol, heating in a water bath at 60 ℃, conventionally stirring for 36h, adding 5g of Vinyl Triethoxysilane (VTES), continuously stirring for 6h, finishing the reaction, naturally cooling to room temperature, washing the obtained suspension with ethanol and centrifuging for three times, and collecting ACNTB-SiO2VTES granules, then dried in a vacuum oven at 60 ℃ for 12h to obtain black ACNTB-SiO2VTES particles.
Mixing 2g epoxy resin (E-44) and 0.6g HBPSi uniformly at 80 deg.C, maintaining for 20min to obtain resin adhesive prepolymer, coating the adhesive prepolymer on the surface of aluminum plate substrate (thickness of adhesive prepolymer layer is 70 μm), and adding prepared ACNTB-SiO when the prepolymer reaches gel state2VTES-toluene suspension (ACNTB-SiO)2-VTES: toluene =0.08g:2g) is gradually dripped on the surface of the resin prepolymer, after the solvent is volatilized, the durable super-hydrophobic E-44/ACNTB-SiO with the micro/nano structure surface is obtained by curing treatment at 50 ℃/1h +80 ℃/2h2VTES composite coating, coating thickness 100 μm.
Comparative example 3-1
Mixing 2g epoxy resin (E-44) and 0.6g HBPSi at 80 deg.C, maintaining for 20min to obtain resin adhesive prepolymer, and mixing with ACNTB-SiO2VTES suspension (ACNTB-SiO)2-VTES: solvent =0.08g:2g), then blade-coating the mixture on the surface of a base material, and curing at 50 ℃/1h +80 ℃/2h to obtain E-44/ACNTB-SiO2VTES-blend coating, the thickness of the coating being 100. mu.m.
Table 2 is the performance data for the coatings in example 3 and comparative example 3. As can be seen from Table 2, when the same small amount of ACNTB-SiO is used2When VTES particles are adopted, the composite material coating prepared by the technology can obtain excellent super-hydrophobicity, while the CA of the coating obtained by the blending technology is lower than 150 degrees, the SA is obviously higher than 10 degrees, and the coating does not have super-hydrophobicity. As can be seen from Table 2, the coating of example 3 had a water pressure of 1188KPa/120s and a sand impact energy of 1.04X 10-7The super-hydrophobicity of the J/grain and 300 times of abrasive paper after friction cycles, and the super-hydrophobicity can be recovered after the coating is damaged and heated for 9h at 300 ℃.
Figure 226217DEST_PATH_IMAGE002
Comparative examples 3 to 2
To a mixed solution of 12g of ammonia water and 150g of ethanol, a mixed solution of 14g of TEOS and 50g of ethanol was added dropwise with stirringHeating in 60 deg.C water bath, conventionally stirring for 36 hr, adding 5g Vinyltriethoxysilane (VTES), stirring for 6 hr, reacting, naturally cooling to room temperature, washing the obtained suspension with ethanol, centrifuging for three times, and collecting SiO2VTES granules, then dried in a vacuum oven at 60 ℃ for 12h to give SiO2VTES particles.
Uniformly mixing 2g of epoxy resin (E-44) and 0.6g of HBPSi at 80 ℃, maintaining for 20min to obtain a resin adhesive prepolymer, uniformly coating the adhesive prepolymer on the surface of an aluminum substrate (the thickness of the adhesive prepolymer layer is 70 mu m), and when the prepolymer reaches a gel state, adding a pre-prepared SiO solution2VTES-toluene Suspension (SiO)2-VTES: toluene =0.08g:2g) is gradually dripped on the surface of the resin prepolymer, and after the solvent is volatilized, E-44/SiO is obtained by curing treatment at 50 ℃/1h +80 ℃/2h2VTES composite coating (coating thickness 100 μm) at 1188KPa/120s water pressure, sand impact energy of 1.04X 10-7Neither J/grain nor 70 sandpaper rubbing cycles had superhydrophobicity (CA)<140°，SA>10°）。
In conclusion, the super-hydrophobic ACNTB-SiO formed by utilizing the hybridization of multi-stage nano particles with stable structures2The super-hydrophobic epoxy composite coating prepared by the VTES particles has excellent durability.
Example 4
Adding 1.2g of ACNTB particles into a mixed solution of 9g of ammonia water and 90g of ethanol under the stirring condition, stirring for 10min, dropwise adding a mixed solution of 9.0g of TEOS and 10g of ethanol, heating in a water bath at 60 ℃, stirring at a constant speed for 18h, adding 2g of dodecyl trimethoxy silane (DTMS), stirring for 6h, finishing the reaction, naturally cooling to room temperature, washing and centrifuging the obtained suspension for three times by using ethanol, and collecting ACNTB-SiO2-DTMS granules, then dried in a vacuum oven at 60 ℃ for 12h to obtain black ACNTB-SiO2-DTMS particles.
Uniformly mixing 1.4g of novolac epoxy resin (F51), 1.4g of DGETPDMS and 1.2g of HBPSi at 50 ℃, obtaining a resin adhesive system after 20min, and then uniformly coating the adhesive system on an aluminum plate by scrapingWhen the system reaches the gel state on the surface of the substrate (the thickness of the prepolymer layer of the adhesive is 70 mu m), the prepared ACNTB-SiO is contained2-DTMS-toluene suspension (ACNTB-SiO)2-DTMS: toluene =0.4g: 20g) is gradually dripped on the surface of the resin prepolymer, after the solvent is volatilized, F51/ACNTB-SiO is obtained by curing treatment at 70 ℃/1h +150 ℃/1h2A DTMS composite coating, the thickness of the coating being 100. mu.m.
Comparative example 4-1
Mixing 2g epoxy resin (F51), 1.4g DGETPDMS and 1.2g HBPSi at 50 deg.C, mixing for 20min to obtain resin adhesive prepolymer, and mixing with ACNTB-SiO2-DTMS suspension (ACNTB-SiO)2-DTMS: solvent =0.4g: 20g), then blade coating on the surface of the base material, curing at 70 ℃/1h +150 ℃/1h to obtain F51/ACNTB-SiO2DTMS coating, thickness of 100 μm.
Table 3 shows the coating performance data of example 4 and comparative example 4-1. As can be seen from Table 3, the same amount of ACNTB-SiO was used2DTMS particles, with the technique of the invention, excellent superhydrophobicity of the coating can be obtained; and the CA of the coating obtained by adopting the blending technology is lower than 150 degrees, the SA is obviously larger than 10 degrees, and the coating does not have super-hydrophobicity. As can be seen from Table 3, the coating of example 4 had a water pressure of 1188KPa/120s and a sand impact energy of 1.04X 10-7The super-hydrophobicity of the coating after J/grain and 250 times of abrasive paper friction cycles is realized, and the super-hydrophobicity can be recovered after the coating is damaged and heated for 5 hours at 320 ℃.
Figure 949322DEST_PATH_IMAGE003
Comparative examples 4 to 2
Under the stirring condition, dropwise adding a mixed solution of 9.0g of TEOS and 10g of ethanol into a mixed solution of 9g of ammonia water and 90g of ethanol, heating in a water bath at 60 ℃, uniformly stirring for 18h, adding 2g of dodecyl trimethoxy silane (DTMS), continuously stirring for 6h, finishing the reaction, naturally cooling to room temperature, washing and centrifuging the obtained suspension with ethanol for three times, collecting particles, drying in a vacuum oven at 60 ℃ for 12h to obtain SiO2-DTMS particles.
Adding 10g of ACNTB particles into 90g of ethanol under the stirring condition, stirring for 10min, adding 0.5g of dodecyl trimethoxy silane (DTMS) under the heating of water bath at 60 ℃, continuously stirring for 6h, finishing the reaction, naturally cooling to room temperature, washing and centrifuging the obtained suspension for three times by using ethanol, collecting the particles, and drying in a vacuum oven at 60 ℃ for 12h to obtain the ACNTB-DTMS particles.
Mixing 1.4g of novolac epoxy resin (F51), 1.4g of DGETPDMS and 1.2g of HBPSi uniformly at 50 ℃, obtaining a resin adhesive system after 20min, then uniformly coating the adhesive system on the surface of an aluminum substrate (the thickness of a prepolymer layer of the adhesive is 70 mu m), and when the system reaches a gel state, adding prepared ACNTB-DTMS/SiO2-DTMS/toluene suspension (ACNTB-DTMS, SiO)2Weight of DTMS and toluene is 0.2g, 0.2g and 20g respectively) is gradually dripped on the surface of the resin prepolymer, after the solvent is volatilized, the composite material coating is obtained by curing treatment at 70 ℃/1h +150 ℃/1h, the thickness of the coating is 100 mu m, and the sand impact energy is 1.04 multiplied by 10 under the water pressure of 1188KPa/120s-7Neither J/grain nor 20 sandpaper rubbing cycles were superhydrophobic (CA)<130°，SA>20°）。
In summary, the ACNTB-SiO formed by multi-stage nanoparticle hybridization is utilized2The super-hydrophobic epoxy composite material coating prepared by the DTMS particles has excellent durability.
To ensure SiO2Capable of effectively transferring load, SiO2Must be effectively embedded in the pores of ACNTB. In the present invention, CNT and SiO2Have strong interaction between them, so that SiO2The method can effectively transfer load, thereby effectively enhancing the stability of the structure of the ACNTB and ensuring that the subsequently synthesized coating has stable mechanical property and stability of super-hydrophobic property. Furthermore, the pores in the ACNTB can be used as a micro-reaction container or a mold cavity, which is beneficial to the permeation of TEOS and the in-situ hydrolysis to generate nano SiO2Is embedded in the pores, in this case, SiO2The particles are confined in the pore structure, and when ACNTB is stressed, SiO2Can transfer load between CNT, and improve the bearing force of ACNTB particle. ACNTB-SiO2The nano particles in the system have strong interaction, namely the ACNTB-SiO with a stable structure2The system particles can improve the microscopic stability enhancement of the coating. More interestingly, ACNTB-SiO2The system basically keeps the high long beam diameter ratio of the original ACNTB, is easy to orient along the fluid direction under the driving of a gravitational field and fluid power, and is constructed with a special surface structure coating. Due to SiO2Embedded in the pores of ACNTB to make the unit volume of ACNTB-SiO2The specific surface area of the particles is also much larger than that of the ACNTB particles, and therefore, ACNTB-SiO2The effect of the particles and the adhesive is enhanced, which is beneficial to improving the stability of the super-hydrophobic coating.

Claims (7)

1. The durable super-hydrophobic composite coating is characterized in that the preparation method of the durable super-hydrophobic composite coating comprises the following steps of mixing ACNTB-SiO in parts by weight2Coating of the coupling agent suspension on ACNTB-SiO2-a gel surface of a mixture of a coupling agent, epoxy resin, diglycidyl ether-terminated polydimethylsiloxane, and amino-terminated hyperbranched polysiloxane, followed by curing to obtain a durable superhydrophobic composite coating; or mixing ACNTB-SiO2Coating the coupling agent suspension on the surface of the gel of the epoxy resin and amino-terminated hyperbranched polysiloxane mixture, and curing to obtain a durable super-hydrophobic composite coating; or mixing ACNTB-SiO2Coating the coupling agent suspension on the surface of a gel of a mixture of epoxy resin, diglycidyl ether-terminated polydimethylsiloxane and amino-terminated hyperbranched polysiloxane, and curing to obtain a durable super-hydrophobic composite coating; or mixing ACNTB-SiO2Coating of the coupling agent suspension on ACNTB-SiO2-curing the surface of the gel of the mixture of coupling agent, epoxy resin and amino-terminated hyperbranched polysiloxane to obtain a durable superhydrophobic composite coating; mixing and reacting a multi-walled carbon oriented carbon nanotube bundle, alkali, a solvent and tetraethyl orthosilicate, adding a silane coupling agent, and continuing to react to obtain ACNTB-SiO2-a coupling agent; the diameter of the multi-walled carbon oriented carbon nanotube bundle is 10-25 μm, and the length of the multi-walled carbon oriented carbon nanotube bundle is 30-100 μm; mixing ofIn the compound, ACNTB-SiO2The weight parts of the coupling agent, the epoxy resin, the diglycidyl ether terminated polydimethylsiloxane and the amino-terminated hyperbranched polysiloxane are respectively 0-1 part, 70-100 parts, 0-70 parts and 30-60 parts; ACNTB-SiO2-coupling agent suspension, ACNTB-SiO24.0 to 20 parts by weight of a coupling agent.
2. The durable superhydrophobic composite coating of claim 1, wherein the weight ratio of the multi-walled carbon-oriented carbon nanotube bundles to the tetraethyl orthosilicate is (1-2) to (9-14) to (2-5) to (9-12) to (100-200).
3. The durable superhydrophobic composite coating of claim 1, wherein the silane coupling agent is gamma-methacryloxypropyltrimethoxysilane, hexamethylsilazane, dodecyltrimethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, or hexadecyltrimethoxysilane; the alkali is ammonia water or triethanolamine; the solvent is water, ethanol, ethyl acetate or their mixture.
4. The durable superhydrophobic composite coating of claim 1, wherein the epoxy resin is one or more of bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, hydrogenated bisphenol a epoxy resin, multifunctional glycidyl ether resin, glycidyl ester epoxy resin, halogen epoxy resin; the viscosity of the diglycidyl ether end-capped polydimethylsiloxane is 50-10000 mPa.s/25 ℃, and the specific gravity is 1.05-1.10/25 ℃; the amine value of the amino-terminated hyperbranched polysiloxane is 0.5-0.65 mol/100 g.
5. The method of claim 1, comprising the step of coating ACNTB-SiO with a super-hydrophobic material2Coating of the coupling agent suspension on ACNTB-SiO2Coupling agents, epoxy resins, diglycidyl ether-terminated polydimethylsiloxanes, terminal aminesCuring the gel surface of the hyperbranched polysiloxane mixture to obtain a durable super-hydrophobic composite material coating; or mixing ACNTB-SiO2Coating the coupling agent suspension on the surface of the gel of the epoxy resin and amino-terminated hyperbranched polysiloxane mixture, and curing to obtain a durable super-hydrophobic composite coating; or mixing ACNTB-SiO2Coating the coupling agent suspension on the surface of a gel of a mixture of epoxy resin, diglycidyl ether-terminated polydimethylsiloxane and amino-terminated hyperbranched polysiloxane, and curing to obtain a durable super-hydrophobic composite coating; or mixing ACNTB-SiO2Coating of the coupling agent suspension on ACNTB-SiO2-a gel surface of a mixture of a coupling agent, epoxy resin and amino-terminated hyperbranched polysiloxane, and then curing to obtain a durable superhydrophobic composite coating.
6. Use of the durable superhydrophobic composite coating of claim 1 in the preparation of an abrasion resistant hydrophobic coating.
7. Use according to claim 6, wherein the abrasion resistant hydrophobic coating has a multi-level micro/nano structured surface.
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