WO2020259393A1 - Nanorevêtement super-hydrophobe mécaniquement durable et son procédé de préparation - Google Patents

Nanorevêtement super-hydrophobe mécaniquement durable et son procédé de préparation Download PDF

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WO2020259393A1
WO2020259393A1 PCT/CN2020/096912 CN2020096912W WO2020259393A1 WO 2020259393 A1 WO2020259393 A1 WO 2020259393A1 CN 2020096912 W CN2020096912 W CN 2020096912W WO 2020259393 A1 WO2020259393 A1 WO 2020259393A1
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resin slurry
coating
resin
nano
mechanically durable
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PCT/CN2020/096912
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English (en)
Chinese (zh)
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吴楠
吴彬瑞
彭超义
江大志
杨金水
尹昌平
邢素丽
鞠苏
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国防科技大学
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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
    • 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
    • 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
    • C09D7/65—Additives macromolecular
    • 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
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • 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
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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
    • 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
    • C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
    • C08L2205/16—Fibres; Fibrils

Definitions

  • the invention relates to the technical field of coating preparation, in particular to a mechanically durable superhydrophobic nano coating and a preparation method thereof.
  • the superhydrophobic phenomenon with a contact angle greater than 150° and a rolling angle less than 10° has attracted widespread attention in recent years. It has a strong application background in the fields of self-cleaning, anti-icing, and oil-water separation. Studies have shown that the preparation of superhydrophobic surfaces usually needs to meet two conditions: low surface energy and surface micro-nano secondary structure.
  • the invention provides a mechanically durable super-hydrophobic nano coating and a preparation method thereof, which are used for overcoming defects such as poor mechanical durability of the super-hydrophobic coating in the prior art and realizing excellent mechanical durability of the super-hydrophobic nano coating.
  • the present invention proposes a mechanically durable superhydrophobic nano-coating, the nano-coating uses a nanofiber membrane as a framework reinforcement phase and a resin slurry as a matrix phase;
  • the resin slurry includes resin slurry I and resin slurry II;
  • the resin slurry I is a mixture of hydrophobically modified epoxy resin, nanoparticles, curing agent and diluent;
  • the resin slurry II is a hydrophobic modified Mixture of epoxy resin, curing agent and diluent;
  • the nanofiber membrane is one of polyvinylidene fluoride fiber membrane, polyacrylonitrile fiber membrane, polystyrene fiber membrane, silicon oxycarbon fiber membrane, silicon carbide fiber membrane, alumina fiber membrane and zirconia fiber membrane.
  • the present invention also provides a method for preparing a mechanically durable super-hydrophobic nano-coating, which includes the following steps:
  • the present invention has the following beneficial effects:
  • the mechanically durable super-hydrophobic nano-coating uses nanofiber membrane as the framework reinforcement phase and resin slurry as the matrix phase;
  • the resin slurry includes resin slurry I and resin slurry II;
  • Slurry I is a mixture of hydrophobically modified epoxy resin, nanoparticles, curing agent and diluent;
  • said resin slurry II is a mixture of hydrophobically modified epoxy resin, curing agent and diluent;
  • said nanofiber membrane is One of polyvinylidene fluoride fiber membranes, polyacrylonitrile fiber membranes, polystyrene fiber membranes, silicon-oxycarbon fiber membranes, silicon carbide fiber membranes, alumina fiber membranes, and zirconia fiber membranes.
  • the mechanically durable super-hydrophobic nano-coating uses nano-fiber membranes as the skeleton-reinforcing phase of the super-hydrophobic coating. It uses micro-level holes and nanoparticles between nano-fibers to construct a micro-nano secondary structure, and uses hydrophobic epoxy resin to make nano-fibers
  • the surface of membranes and nanoparticles have low surface energy, which makes their surface super-hydrophobic.
  • the multiphase reinforced nanocomposite similar to the "reinforced concrete" structure formed by the combination of nanofiber membranes, hydrophobic epoxy resins and nanoparticles has excellent mechanical durability, so that the superhydrophobic nano coating has a higher The practical value.
  • the method for preparing the mechanically durable super-hydrophobic nano-coating includes the preparation of resin slurry, the preparation of substrates coated with resin slurry II and the preparation of nanofiber membranes impregnated with resin slurry I.
  • the film is stacked on a substrate coated with resin slurry II, and heated and cured to obtain a mechanically durable super-hydrophobic nano-coating.
  • the preparation method has simple process and low cost, and the prepared product has excellent mechanical durability.
  • Figure 1a is a photo of the surface micro-topography of the superhydrophobic coating obtained in Example 1;
  • Figure 1b is a hydrophobic picture of the surface of the superhydrophobic coating obtained in Example 1;
  • Figure 2a is a photo of the surface micro-topography of the super-hydrophobic coating obtained in Example 1 after being polished 60 times with 600 mesh sandpaper;
  • Figure 2b is a hydrophobic picture of the superhydrophobic coating obtained in Example 1 after being polished 60 times with 600 mesh sandpaper;
  • Figure 3 is a morphology diagram of the silicon carbide fiber used in Example 3;
  • Figure 4a is a photo of the surface micro-topography of the super-hydrophobic coating obtained in Example 3 after being polished 60 times with 600 mesh sandpaper;
  • Figure 4b is a hydrophobic picture of the superhydrophobic coating obtained in Example 3 after being polished 60 times with 600 mesh sandpaper;
  • Figure 5a is a photo of the surface micro-topography of the coated tape in Comparative Example 1 after being stripped five times;
  • Figure 5b is a hydrophobic picture of the coated tape in Comparative Example 1 after being stripped 5 times;
  • Figure 6a is an optical photo of the inside of the coating in Comparative Example 2;
  • Figure 6b is a photo of the surface micro-topography of the coating in Comparative Example 2.
  • the drugs/reagents used are all commercially available.
  • the present invention provides a mechanically durable super-hydrophobic nano-coating, wherein the nano-coating uses a nanofiber membrane as a skeleton reinforcement phase and a resin slurry as a matrix phase;
  • the resin slurry includes resin slurry I and resin slurry II;
  • the resin slurry I is a mixture of hydrophobically modified epoxy resin, nanoparticles, curing agent and diluent;
  • the resin slurry II is a hydrophobic modified Mixture of epoxy resin, curing agent and diluent;
  • the nanofiber membrane is one of polyvinylidene fluoride fiber membrane, polyacrylonitrile fiber membrane, polystyrene fiber membrane, silicon oxycarbon fiber membrane, silicon carbide fiber membrane, alumina fiber membrane and zirconia fiber membrane. Choosing a nanofiber membrane with small fiber diameter, high porosity, and good flexibility is beneficial to improve the hydrophobicity and mechanical durability of the superhydrophobic nano coating.
  • the average thickness of the nanofiber membrane is 10-30 ⁇ m, preferably 10-20 ⁇ m; the average fiber diameter is 200-600 nm, preferably 200-500 nm.
  • the superhydrophobic coating of the present invention uses nanofiber membranes as the skeleton reinforcement phase of the superhydrophobic coating, uses micron-level pores and nanoparticles between nanofibers to jointly construct a micro-nano secondary structure, and uses hydrophobic epoxy resin to make the nanofiber membrane and The surface of the nanoparticles has low surface energy, so that the surface has superhydrophobic properties.
  • the multiphase reinforced nanocomposite with a structure similar to "reinforced concrete" formed by the combination of nanofiber membrane, hydrophobically modified epoxy resin and nanoparticles has excellent mechanical durability.
  • the present invention also provides a method for preparing a mechanically durable superhydrophobic nano coating, which includes the following steps:
  • the hydrophobically modified epoxy resin is one of hydrophobically modified E-51 epoxy resin, E-44 epoxy resin and E-42 epoxy resin. Choosing a suitable resin is conducive to the hydrophobicity of the final product.
  • the nanoparticles are one of silica nanoparticles, titanium dioxide nanoparticles and aluminum oxide nanoparticles. Nanoparticles work together with hydrophobically modified epoxy resin and nanofiber membranes to greatly improve the coating’s Mechanical durability; the curing agent is at least one of diethylenetriamine, diaminodiphenylmethane, polyetheramine D-230 and polyetheramine D-400.
  • a suitable curing agent to form a "reinforced steel "Concrete” has a firm structure; the diluent is at least one of ethyl acetate, ethanol, N,N-dimethylformamide, dimethyl sulfoxide, cyclohexane and acetone, so that the curing agent can be fully dissolved and The hydrophobically modified epoxy resin and/or nanoparticles are uniformly dispersed.
  • the mass ratio of the hydrophobically modified epoxy resin to the nanoparticles is (1.5-3):1; the usage amount of the curing agent is the same as the amine equivalent of the curing agent used and the ring
  • the epoxy value of the oxygen resin is related; the mass ratio of the diluent to the total mass of the hydrophobically modified epoxy resin, nanoparticles and curing agent is (3 ⁇ 5):1, which is beneficial to the hydrophobically modified epoxy resin, nanoparticles and The curing agent is evenly mixed, so that the mechanical durability of the final prepared product is more excellent.
  • the mass ratio of the hydrophobically modified epoxy resin and the curing agent has a corresponding relationship; the mass ratio of the diluent to the total mass of the hydrophobically modified epoxy resin and the curing agent is ( 0.5 ⁇ 1.5):1, which is conducive to the uniform mixing of hydrophobically modified epoxy resin, nanoparticles and curing agent, so that the final prepared product has better mechanical durability.
  • the average particle diameter of the nanoparticles is 20-50 nm.
  • the coating amount for coating the resin slurry II on the substrate is 0.003 to 0.014 g/cm 2 , preferably 0.005 to 0.012 g/cm 2 . If the coating amount is too large, the resin slurry II will completely penetrate the nanofiber membrane and lose its super-hydrophobic performance; if the coating amount is too small, the thickness of the underlying resin reversely infiltrating the nanofiber membrane is small, resulting in poor durability of the nano coating.
  • the immersion time is 3 to 5 minutes, and the temperature is 20 to 30°C, which is beneficial for the nanoparticles and the hydrophobic resin to fully penetrate into the nanofiber membrane without damaging the original mechanical properties of the nanofiber membrane.
  • the volatilization is natural volatilization at room temperature; the number of repeated impregnation and volatilization processes is 3-8 times, preferably 3-5 times, so that the nanoparticles and the hydrophobic resin can fully penetrate the nanofiber membrane.
  • the heating and curing procedure is 70-85° C., 1 to 2 hours in the first stage; 90-100° C., 1 to 2 hours in the second stage. Too low temperature and too short time will lead to incomplete curing; too high temperature and too long time will cause the coating to crack.
  • This embodiment provides a mechanically durable super-hydrophobic nano-coating with a coating thickness of about 0.4mm; the nano-coating uses polyacrylonitrile fiber membrane as the framework reinforcement phase, the average fiber diameter is 200 nm, and the average fiber membrane thickness is 12 ⁇ m; resin slurry as the matrix phase; the resin slurry includes resin slurry I and resin slurry II; the resin slurry I is hydrophobically modified E-51 epoxy resin, aluminum oxide nanoparticles and A mixture of polyetheramine D-230; the resin slurry II is a mixture of hydrophobically modified E-51 epoxy resin and polyetheramine D-230.
  • This embodiment also provides a method for preparing a mechanically durable super-hydrophobic nano-coating, the specific steps are:
  • the surface of the super-hydrophobic nano-coating is uniform nano-particles, as shown in Figure 1a, the water contact angle is 156.8°; after 60 times of sanding with 600 grit sandpaper, the contact angle drops to 147.4°, and the surface of the nanofiber skeleton and nanoparticles are exposed And resin to build a new micro-nano structure, as shown in Figure 2a; after 90 times of sanding with 360 grit sandpaper, the contact angle dropped to 146.6°; after 50 grit impact tests, the contact angle of the superhydrophobic composite material dropped to 142.2 °;
  • the hydrophobic photos of Figures 1b and 2b show that the superhydrophobic nano coating provided by this embodiment has strong hydrophobicity.
  • This embodiment provides a mechanically durable super-hydrophobic nano-coating with a thickness of about 0.4mm; the nano-coating uses a polyvinylidene fluoride fiber membrane as a skeleton, with an average fiber diameter of 400 nm and an average thickness of 25 ⁇ m.
  • the resin slurry is the matrix phase; the resin slurry includes resin slurry I and resin slurry II; the resin slurry I is hydrophobically modified E-51 epoxy resin, titanium dioxide nanoparticles and diethylene triamine The resin slurry II is a mixture of hydrophobically modified E-51 epoxy resin and diethylene triamine.
  • This embodiment also provides a method for preparing a mechanically durable super-hydrophobic nano-coating, the specific steps are:
  • the surface of the super-hydrophobic nano-coating is uniform nanoparticles with an average water contact angle of 155.2°; after 60 times of sanding with 600 grit sandpaper, the contact angle drops to 150.3°, and the surface of the nanofiber skeleton, nanoparticles and resin are exposed; use 360 After 100 times of sandpaper grinding, the surface water contact angle was 148.6°; after 10 times of adhesion with 3M tape, the surface water contact angle was 147.6°; after 50 grit impact tests, the contact angle of the superhydrophobic composite material was 148.2°
  • the above results show that the super-hydrophobic nano-coating using polyvinylidene fluoride nanofiber membrane as the framework can maintain super-hydrophobicity under friction and dynamic impact conditions, indicating that this type of super-hydrophobic nanocomposite has good durability.
  • This embodiment provides a mechanically durable super-hydrophobic nano-coating with a thickness of about 0.4mm; the nano-coating uses a silicon carbide fiber membrane as a skeleton, the average fiber diameter is 500nm, the average fiber membrane thickness is 20 ⁇ m, and the fiber
  • the morphology is shown in Figure 3; the resin slurry is used as the matrix phase; the resin slurry includes resin slurry I and resin slurry II; the resin slurry I is hydrophobically modified E-42 epoxy resin, two A mixture of silicon oxide nanoparticles and polyetheramine D-400; the resin slurry II is a mixture of hydrophobically modified E-42 epoxy resin and polyetheramine D-400.
  • This embodiment also provides a method for preparing a mechanically durable super-hydrophobic nano-coating, the specific steps are:
  • the surface of the super-hydrophobic nano-coating is uniform nanoparticles with an average water contact angle of 158.2°; after 60 times of sanding with 600 grit sandpaper, the contact angle is 151.5°, and the surface of the nanofiber skeleton, silica nanoparticles and epoxy are exposed
  • the enlarged surface structure of the resin is shown in Figure 4a; after 100 times of sanding with 360 grit sandpaper, the surface water contact angle is 147.3°; after 10 times with 3M tape, the surface water contact angle is 148.6°; after 50 grit impacts After the experiment, the contact angle of the superhydrophobic composite material was 150.2°;
  • Figure 4b is a hydrophobic picture of the superhydrophobic coating obtained in this example after being polished 60 times with 600 mesh sandpaper, indicating that the superhydrophobic nano coating obtained in this example has a strong Hydrophobicity.
  • the preparation process of this comparative example is the same as that of Example 1, except that the nanofiber skeleton is not added to the super-hydrophobic coating, and the resin slurry I is directly sprayed on the semi-cured resin slurry II.
  • the resulting coating is ordinary super Hydrophobic coating.
  • the surface morphology of the obtained ordinary superhydrophobic coating is similar to that of Fig. 1a, and the surface is uniformly distributed nanoparticles. But after the tape was peeled off for 5 times, the superhydrophobic coating on the surface fell off and the water contact angle dropped to 110.8°.
  • the morphology of the super-hydrophobic coating after stripping is shown in Figure 5a. It contains only a small amount of nano-particles, and no micro-nano structure is constructed, resulting in the loss of super-hydrophobic performance. This indicates that the nanofiber felt has an effect on resin slurry I and resin slurry II
  • the connection plays an important role in intuitiveness, not only can enhance the role of the resin paste I, but also can play an over-connection role. The two co-authors enhance the mechanical durability of the superhydrophobic coating.
  • Fig. 5b that the ordinary superhydrophobic coating obtained in this comparative example has poor hydrophobic performance after being stripped.
  • step (2) the coating surface density of the resin slurry II is 0.016 g/cm 2 .
  • the internal optical photo of the obtained hydrophobic coating is shown in Figure 6a. Because the surface density of the underlying resin is too large, the fiber coating is completely saturated by the underlying resin. The surface structure and morphology are shown in Figure 6b. The surface micro-nano structure is lost. The water contact angle is only 108°, indicating that the coating surface density of resin slurry II has a greater impact on the superhydrophobic properties of the coating and must be controlled within a reasonable range.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

L'invention concerne un nano-revêtement super-hydrophobe mécaniquement durable et son procédé de préparation, le nano-revêtement utilisant une membrane en nanofibres en tant que phase de renforcement de structure, et une suspension de résine en tant que phase de matrice ; la suspension de résine comprend une suspension de résine I et une suspension de résine II ; la suspension de résine I est un mélange de résine époxy modifiée hydrophobe, de nanoparticules et d'un agent de durcissement ; la suspension de résine II est un mélange de résine époxy modifiée hydrophobe et d'un agent de durcissement ; le procédé de préparation consiste à préparer la suspension de résine, préparer un substrat revêtu de la suspension de résine II, préparer la membrane en nanofibres imprégnée de la suspension de résine I, empiler la membrane en nanofibres imprégnée sur le substrat revêtu de la suspension de résine II, chauffer et faire durcir, pour obtenir le nano-revêtement super-hydrophobe mécaniquement durable. Le procédé de préparation a pour avantages qu'il s'agit d'un procédé simple et peu coûteux, et le nano-revêtement préparé présente une excellente durabilité mécanique.
PCT/CN2020/096912 2019-06-28 2020-06-19 Nanorevêtement super-hydrophobe mécaniquement durable et son procédé de préparation WO2020259393A1 (fr)

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US20230295458A1 (en) * 2020-05-13 2023-09-21 Graphite Innovation And Technologies Inc Composition for a coating, coatings and methods thereof
CN112143399A (zh) * 2020-09-10 2020-12-29 江苏仕邦柔性电子研究院有限公司 一种可阻隔红外光的oled保护膜及其制备方法
CN112251131A (zh) * 2020-11-09 2021-01-22 东阳市聚冉电子科技有限公司 一种高附着力超疏水光固化涂层及其制备方法
CN116355524B (zh) * 2021-12-27 2024-05-17 中国科学院化学研究所 一种柔性超疏液涂层及其制备方法与应用
CN116178007B (zh) * 2022-12-21 2024-02-02 中国建筑材料科学研究总院有限公司 耐高温复合材料聚热环及其制备方法和应用

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CN109825165A (zh) * 2019-01-30 2019-05-31 中国人民解放军国防科技大学 一种耐磨超疏水涂层及其制备方法
CN110172292A (zh) * 2019-06-28 2019-08-27 中国人民解放军国防科技大学 一种机械耐久的超疏水纳米涂层及其制备方法

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