CN110484065B - Preparation method of fluorinated silica particle-based super-amphiphobic coating suitable for various soft and hard substrates - Google Patents
Preparation method of fluorinated silica particle-based super-amphiphobic coating suitable for various soft and hard substrates Download PDFInfo
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- CN110484065B CN110484065B CN201910706226.6A CN201910706226A CN110484065B CN 110484065 B CN110484065 B CN 110484065B CN 201910706226 A CN201910706226 A CN 201910706226A CN 110484065 B CN110484065 B CN 110484065B
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 90
- 238000000576 coating method Methods 0.000 claims abstract description 47
- 239000000758 substrate Substances 0.000 claims abstract description 46
- 239000011248 coating agent Substances 0.000 claims abstract description 43
- 238000002360 preparation method Methods 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 239000011259 mixed solution Substances 0.000 claims description 32
- 235000012239 silicon dioxide Nutrition 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 239000000377 silicon dioxide Substances 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 15
- 238000003760 magnetic stirring Methods 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 239000004744 fabric Substances 0.000 claims description 11
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 10
- 238000003618 dip coating Methods 0.000 claims description 10
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 8
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 8
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 7
- 239000003607 modifier Substances 0.000 claims description 7
- 239000007921 spray Substances 0.000 claims description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- -1 1-ethyl-(3-dimethylaminopropyl) Chemical group 0.000 claims 2
- 150000001718 carbodiimides Chemical class 0.000 claims 2
- 229910021487 silica fume Inorganic materials 0.000 claims 2
- 238000005119 centrifugation Methods 0.000 claims 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims 1
- 229920000131 polyvinylidene Polymers 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 10
- 238000005507 spraying Methods 0.000 abstract description 9
- 230000003373 anti-fouling effect Effects 0.000 abstract description 4
- 230000003075 superhydrophobic effect Effects 0.000 abstract description 4
- 238000004140 cleaning Methods 0.000 abstract description 3
- 238000005096 rolling process Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000007598 dipping method Methods 0.000 abstract 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 18
- 239000006196 drop Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000005543 nano-size silicon particle Substances 0.000 description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229940078552 o-xylene Drugs 0.000 description 9
- 239000000123 paper Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 239000010779 crude oil Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- MARCAKLHFUYDJE-UHFFFAOYSA-N 1,2-xylene;hydrate Chemical compound O.CC1=CC=CC=C1C MARCAKLHFUYDJE-UHFFFAOYSA-N 0.000 description 1
- 239000011165 3D composite Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/008—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character comprising a mixture of materials covered by two or more of the groups C03C17/02, C03C17/06, C03C17/22 and C03C17/28
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
- C08J9/42—Impregnation with macromolecular compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating 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
- C09D127/02—Coating 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
- C09D127/12—Coating 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
- C09D127/16—Homopolymers or copolymers of vinylidene fluoride
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/77—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof
- D06M11/79—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with silicon or compounds thereof with silicon dioxide, silicic acids or their salts
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
- D06M15/256—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing fluorine
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
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- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H19/00—Coated paper; Coating material
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- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
- D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- 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
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Abstract
本发明涉及一种基于氟化二氧化硅颗粒的适用于各种软硬质基底的超双疏涂层的制备方法，基于溶胶‑凝胶法以氟化的微纳米二氧化硅构筑三维复合多级结构具有超疏水且超疏油特性的有机涂层。由于无基底依赖性，该涂层可以通过喷涂或浸涂的方式涂覆在各种软质和硬质基底上并表现出良好的超疏液性能。表面能低至28.7mN/m的有机液体在涂覆有该图层的表面上亦能维持球状并且接触角维持于150°以上。当动态液滴以一定速度撞击平放表面时，液滴以饼状形式在表面弹跳直至动能耗尽，在倾斜表面上液滴亦可以小于10°的滚动角在表面滚动或以弹跳的方式离开表面。即使经高温、酸碱等苛刻条件处理后，涂覆的表面仍表现出良好的自清洁和抗污功能。
The invention relates to a preparation method of a super-amphiphobic coating suitable for various soft and hard substrates based on fluorinated silica particles. Organic coatings with superhydrophobic and superoleophobic properties in hierarchical structure. With no substrate dependence, the coating can be applied on various soft and hard substrates by spraying or dipping and exhibits good superlyophobic properties. The organic liquid with a surface energy as low as 28.7 mN/m can also maintain spherical shape on the surface coated with the layer and the contact angle is maintained above 150°. When a dynamic droplet hits a flat surface at a certain speed, the droplet bounces on the surface in the form of a cake until the kinetic energy is exhausted. On an inclined surface, the droplet can also roll on the surface with a rolling angle of less than 10° or leave in a bouncing manner. surface. Even after being treated with harsh conditions such as high temperature, acid and alkali, the coated surface still exhibits good self-cleaning and antifouling functions.
Description
Technical Field
The invention belongs to the technical field of preparation of durable super-amphiphobic coatings, and particularly relates to a preparation method of a super-amphiphobic coating based on fluorinated silica particles and suitable for various soft and hard substrates.
Background
Because artificial surfaces in natural environment are easily polluted by solid or liquid fluid due to low anti-wettability, and damage to the surfaces caused by various pollution is mostly irreversible and expensive to repair, in recent years, theories and applications of bionic anti-wettability materials inspired by high anti-wettability of various animal and plant surfaces in nature are widely concerned by academia and industry, and various artificial anti-wettability surfaces are successfully prepared. Among them, the super-amphiphobic surface is one of the objects of interest and one of the most promising directions. A super-amphiphobic surface refers to a surface having a contact angle greater than 150 ° and a roll angle less than 10 ° for both a water droplet and a low surface energy oil droplet. Compared with the traditional super-hydrophobic surface, the super-hydrophobic surface has wider application in the aspects of fluid control, self-cleaning anti-fouling, liquid transportation and the like.
Chemical modification by very low surface energy modifiers to reduce the surface energy of the substrate and to finely build a rough structure is a common method of preparing a super-amphiphobic surface. According to the invention, the multistage composite rough structure is constructed by adopting micro-nano silicon dioxide particles with two particle sizes, the surface energy is reduced by assisting with 3-aminopropyl triethoxysilane and perfluorooctanoic acid, the adhesion between the particles and the substrate is enhanced by polyvinylidene fluoride-hexafluoropropylene, and the surface energy is further reduced, so that the stability of the surface structure is ensured, and the surface is easier to resist the wetting of low surface energy liquid. The coating is coated on the surface of the substrate by selecting simple and easy spraying and dip-coating modes, which is convenient for large-scale preparation and production of the super-amphiphobic surface. Based on the method, the durable super-amphiphobic coating prepared by the invention can realize high anti-wettability of water drops and oil drops, and is beneficial to enriching the preparation method of the super-amphiphobic surface and expanding the application of the super-amphiphobic surface in the aspects of fluid control, antifouling and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a super-amphiphobic coating based on fluorinated silica particles and suitable for various soft and hard substrates.
The technical scheme for realizing the purpose of the invention is as follows: a preparation method of a super-amphiphobic coating based on fluorinated silica particles and suitable for various soft and hard substrates is characterized by comprising the following steps:
A. preparation of silica sol: mixing nano silicon dioxide and micron silicon dioxide according to a certain proportion, dispersing the mixture into a certain amount of ethanol solution, magnetically stirring the mixture for a period of time, adding a certain amount of 3-aminopropyltriethoxysilane into the mixed solution, magnetically stirring the mixture at normal temperature for a period of time, and finally respectively adding a certain amount of perfluorooctanoic acid and 1-ethyl- (3-dimethylaminopropyl) carbodiimide into the mixed solution, and reacting the mixture at a certain temperature for a period of time to obtain particle sol;
B. preparation of solid fluorinated particles: cooling the obtained sol to normal temperature, centrifugally separating out solid particles, washing twice by using ethanol to wash off redundant solvent and unreacted modifier, and drying at a certain temperature;
C. preparing a super-amphiphobic coating: dissolving a certain amount of polyvinylidene fluoride-hexafluoropropylene in a certain amount of N, N-dimethylformamide by magnetic stirring, adding a certain amount of N-octylamine into the N, N-dimethylformamide, adding a certain amount of fluorinated silica particles into the solution, and stirring for a period of time by magnetic stirring to obtain a light yellow mixed solution;
D. preparing a super-amphiphobic surface: soaking the substrate material in mixed solution of ethanol and acetone, ultrasonic treating for certain time, drying, adding proper amount of mixed solution in light yellow color into a spray gun, spraying onto hard substrate, and dip coating to form coating on soft substrate.
Further, in the step A, the raw materials are in parts by weight as follows: the ratio of the silicon dioxide to the ethanol solution is 20ml to 1g, and the silicon dioxide is the combination of nano silicon dioxide and micron silicon dioxide in different ratios.
Further, in the step A, the selected nano silicon dioxide and the selected micro silicon dioxide are respectively 4:0, 3:1, 2:2 and 1:3 according to the mass ratio.
Further, in the step A, the grain diameters of the nano-silica and the micron-silica are respectively 15-25nm and 0.5-1 μm, the magnetic stirring time of the 3-aminopropyl triethoxysilane is 2-4h, the reaction time of the perfluorooctanoic acid and the 1-ethyl- (3-dimethylaminopropyl) carbodiimide after being added into the mixed solution is 6-10h, and the reaction temperature is 75-90 ℃.
Further, the drying temperature in the step B and the step D is 65 ℃.
Further, in the step C, the mass parts of the polyvinylidene fluoride-hexafluoropropylene, the N, N-dimethylformamide and the N-octylamine are as follows: 1:30:1.
Furthermore, the super-amphiphobic coating is suitable for various soft substrates and hard substrate materials, including cloth, filter paper, PET sheets, sponges and glass.
The invention has the beneficial effects that: compared with the prior art, the invention has the advantages that:
1. the coating has good adhesion with the substrate and stable structure and chemical components.
2. The coating has excellent tolerance and thermal stability.
3. The coating has no substrate dependence and is suitable for various soft and hard substrates.
4. The coating can be coated on the surface of the substrate by adopting a simple method of spin coating or dip coating, and the substrate is endowed with good ultra-lyophobic property.
Drawings
FIG. 1 is a V-shaped bounce test (e-f) of water drops, ethylene glycol and o-xylene on a glass surface coated with a coating, and an adhesion test (e-f) of the water drops and the o-xylene on the surface, wherein the wettabilities (a-b), the water drops (c) and the o-xylene on the surfaces are regulated and controlled by changing the weight ratio of micro-nano particles in example 1 of the invention.
FIG. 2 shows wettability (a) and corresponding contact angle test (b) of droplets having different surface tensions on a glass surface in example 2 of the present invention.
FIG. 3 shows that in example 2 of the present invention, coatings are applied to various substrates, respectively, and the wettability of droplets with various surface tensions on the surfaces is measured (a) PET, (b) stainless steel, (c) paper sheet, (d) sponge, (e) cloth; (f) the o-xylene rolls on the curled cloth surface.
FIG. 4 shows the pie-shaped bounce of water droplets and o-xylene on the surfaces of a flat cloth (a), a paper sheet (b) and a glass (c) and the inelastic bounce of water droplets on an inclined glass surface in example 3 of the present invention.
FIG. 5 shows the change of wettability of water droplets and crude oil on the surface under different treatment conditions in example 4 of the present invention (a) the surface was allowed to stand at normal temperature for 3 to 18 days, (b) the surface was placed in water for 3 to 48 hours, (c) the surface was placed in a solution of pH2 to 14 for 30 minutes, (d) the surface was allowed to stand at 60 to 140 ℃ for 2 hours, (e) the thermogravimetric curve of the coating, and (f-g) the rolling behavior of the water droplets and the crude oil on the surface after the surface was placed in an environment of 140 ℃ for 2 hours, respectively.
Detailed Description
In order to better understand the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples. Various changes or modifications may be effected therein by one skilled in the art and such equivalents are intended to be within the scope of the invention as defined by the claims appended hereto.
Example 1
1. Preparation of silica sol: the surface roughness and the surface wettability can be influenced by different contents of the micro-nano particles, and the surfaces with different oleophobic characteristics are prepared by adjusting the mass ratio of the micro-nano silicon dioxide. Mixing 2g of silicon dioxide with 40ml of ethanol, and then magnetically stirring for 30 minutes at normal temperature, wherein 2g of silicon dioxide is the combination of nano silicon dioxide and micron silicon dioxide in different proportions. The selected nano silicon dioxide and micron silicon dioxide are respectively 4:0, 3:1, 2:2 and 1:3 according to the mass ratio, namely the dosage of the nano silicon dioxide and the micron silicon dioxide is respectively as follows: 2g and 0g, 1.5g and 0.5g, 1g and 1g, 0.5g and 1.5 g; then, 0.5g of 3-aminopropyltriethoxysilane was added to the mixed solution and magnetically stirred at room temperature for 2 hours. Finally, 0.5g of perfluorooctanoic acid and 0.1g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide are respectively added into the mixed solution and react for 6 hours at the temperature of 75 ℃, and then the particle sol is obtained.
2. Preparation of solid fluorinated particles: cooling the obtained sol to normal temperature, centrifugally separating out solid particles, washing twice with ethanol to remove redundant solvent and unreacted modifier, and drying at 65 ℃.
3. Preparing a super-amphiphobic coating: 1g of polyvinylidene fluoride-hexafluoropropylene was dissolved in 30g of N, N-dimethylformamide with magnetic stirring, 1g of N-octylamine was added thereto, 2g of fluorinated silica particles was added to the solution, and magnetic stirring was carried out for 2 hours to obtain a pale yellow mixed solution.
4. Preparing a super-amphiphobic surface: soaking all substrates (cloth, filter paper, PET sheets, sponges and glass) in a mixed solution of ethanol and acetone for ultrasonic treatment for 20 minutes, drying for later use, adding a proper amount of light yellow mixed solution into a spray gun, spraying the mixture onto a hard substrate, and coating a coating on the soft substrate by adopting a dip-coating mode.
5. Regulating and controlling surface wettability by micro-nano mass ratio, namely a liquid drop adhesion test, wherein water drops, ethylene glycol and o-xylene are in mass ratio of nano SiO2: micron SiO2The 3:1 surface exhibits the best anti-wetting properties with the largest contact angle and the lowest roll angle on the surface, and when a drop of water and o-xylene are both rapidly injected obliquely onto the surface, the drop can splash from the surface without sticking to the surface.
Example 2
1. Preparation of silica sol: the surface roughness and the surface wettability can be influenced by different contents of the micro-nano particles, and the surfaces with different oleophobic characteristics are prepared by adjusting the mass ratio of the micro-nano silicon dioxide. Mixing 4g of silicon dioxide with 80ml of ethanol, then magnetically stirring for 30 minutes at normal temperature, wherein the proportion of the nano silicon dioxide to the micron silicon dioxide is respectively 4g to 0g, 3g to 1g, 2g to 2g, 1g to 3g, and then adding 1g of 3-aminopropyltriethoxysilane into the mixed solution, and magnetically stirring for 3 hours at normal temperature. Finally, 1g of perfluorooctanoic acid and 0.2g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide are respectively added into the mixed solution and react for 6 hours at the temperature of 75 ℃, and then the particle sol is obtained.
2. Preparation of solid fluorinated particles: cooling the obtained sol to normal temperature, centrifugally separating out solid particles, washing twice with ethanol to remove redundant solvent and unreacted modifier, and drying at 65 ℃.
3. Preparing a super-amphiphobic coating: a1 g amount of polyvinylidene fluoride-hexafluoropropylene was dissolved in 30g of N, N-dimethylformamide with magnetic stirring and 1g of N-octylamine was added thereto, 2g of fluorinated silica particles was added to the solution, and magnetic stirring was carried out for 2 hours to obtain a pale yellow mixed solution.
4. Preparing a super-amphiphobic surface: soaking all substrates (cloth, filter paper, PET sheets, sponges and glass) in a mixed solution of ethanol and acetone for ultrasonic treatment for 20 minutes, drying for later use, adding a proper amount of light yellow mixed solution into a spray gun, spraying the mixture onto a hard substrate, and coating a coating on the soft substrate by adopting a dip-coating mode.
5. Wettability of droplets of various surface tensions on super-amphiphobic surfaces and substrate-independent testing of coatings: water drops, glycerol, ethylene glycol, crude oil, o-xylene all have contact angles greater than 150 ° on the coated glass surface, and the coated PET plate, stainless steel, paper sheet, cloth, sponge surfaces all have good resistance to wetting by water and oil compared to the substrate without the coating.
Example 3
1. Preparation of silica sol: the surface roughness and the surface wettability can be influenced by different contents of the micro-nano particles, and the surfaces with different oleophobic characteristics are prepared by adjusting the mass ratio of the micro-nano silicon dioxide. 2g of silicon dioxide and 40ml of ethanol are mixed and then are magnetically stirred for 30 minutes at normal temperature, wherein the nano-silicon dioxide and the micro-silicon dioxide are respectively 2g and 0g, 1.5g and 0.5g, 1g and 1g, 0.5g and 1.5g according to the proportion, and then 0.5g of 3-aminopropyltriethoxysilane is added into the mixed solution and is magnetically stirred for 3 hours at normal temperature. Finally, 0.5g of perfluorooctanoic acid and 0.1g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide are respectively added into the mixed solution and react for 8 hours at the temperature of 85 ℃, and then the particle sol is obtained.
2. Preparation of solid fluorinated particles: cooling the obtained sol to normal temperature, centrifugally separating out solid particles, washing twice with ethanol to remove redundant solvent and unreacted modifier, and drying at 65 ℃.
3. Preparing a super-amphiphobic coating: a1 g amount of polyvinylidene fluoride-hexafluoropropylene was dissolved in 30g of N, N-dimethylformamide with magnetic stirring and 1g of N-octylamine was added thereto, 2g of fluorinated silica particles was added to the solution, and magnetic stirring was carried out for 2 hours to obtain a pale yellow mixed solution.
4. Preparing a super-amphiphobic surface: soaking all substrates (cloth, filter paper, PET sheets, sponges and glass) in a mixed solution of ethanol and acetone for ultrasonic treatment for 20 minutes, drying for later use, adding a proper amount of light yellow mixed solution into a spray gun, spraying the mixture onto a hard substrate, and coating a coating on the soft substrate by adopting a dip-coating mode.
5. The liquid drop bounces on the super-amphiphobic surface in a cake manner: after the water drop and the o-xylene drop at a height of 5 cm and collide with the glass, paper and cloth substrate coated with the coating, the water drop is at rest after multiple inelastic collisions occur on the surface, and bounces off the surface in a cake shape during bouncing.
Example 4
1. Preparation of silica sol: the surface roughness and the surface wettability can be influenced by different contents of the micro-nano particles, and the surfaces with different oleophobic characteristics are prepared by adjusting the mass ratio of the micro-nano silicon dioxide. Mixing 4g of silicon dioxide with 80ml of ethanol, then magnetically stirring for 30 minutes at normal temperature, wherein the proportion of the nano silicon dioxide to the micron silicon dioxide is respectively 4g to 0g, 3g to 1g, 2g to 2g, 1g to 3g, and then adding 1g of 3-aminopropyltriethoxysilane into the mixed solution, and magnetically stirring for 4 hours at normal temperature. Finally, 1g of perfluorooctanoic acid and 0.2g of 1-ethyl- (3-dimethylaminopropyl) carbodiimide are respectively added into the mixed solution and react for 10 hours at the temperature of 95 ℃, and then the particle sol is obtained.
2. Preparation of solid fluorinated particles: cooling the obtained sol to normal temperature, centrifugally separating out solid particles, washing twice with ethanol to remove redundant solvent and unreacted modifier, and drying at 65 ℃.
3. Preparing a super-amphiphobic coating: a1 g amount of polyvinylidene fluoride-hexafluoropropylene was dissolved in 30g of N, N-dimethylformamide with magnetic stirring and 1g of N-octylamine was added thereto, 2g of fluorinated silica particles was added to the solution, and magnetic stirring was carried out for 2 hours to obtain a pale yellow mixed solution.
4. Preparing a super-amphiphobic surface: soaking all substrates (cloth, filter paper, PET sheets, sponges and glass) in a mixed solution of ethanol and acetone for ultrasonic treatment for 20 minutes, drying for later use, adding a proper amount of light yellow mixed solution into a spray gun, spraying the mixture onto a hard substrate, and coating a coating on the soft substrate by adopting a dip-coating mode.
5. Testing the durability of the super-amphiphobic surface: the contact angle of the water drop and the crude oil measured after the glass coated with the coating is respectively kept still for 18 days at room temperature, is soaked in water for 48 hours, is soaked in solutions with different pH values for 30 minutes and is kept still for 2 hours under different temperature environments is maintained to be more than 150 degrees, and the stable structure and chemical composition and the durable property of the surface are proved.
The invention successfully prepares the organic coating with super-hydrophobic and super-oleophobic characteristics by constructing a three-dimensional composite multilevel structure by fluorinated micro-nano silicon dioxide based on a sol-gel method and adopting a spraying or dip-coating mode. Due to no substrate dependence, the coating can be coated on various soft and hard substrates by means of spraying or dip coating and shows good ultralyophobic performance. Organic liquids with surface energies as low as 28.7mN/m can also maintain a spherical shape and contact angles above 150 ° on the surface coated with the coating. When the dynamic liquid drop impacts a flat surface at a certain speed, the liquid drop bounces on the surface in a cake-shaped mode until the kinetic energy is exhausted, and the liquid drop can roll on the surface or leave the surface in a bouncing mode at a rolling angle smaller than 10 degrees on an inclined surface. In view of excellent lyophobic property and structural stability, the coated surface still shows good self-cleaning and anti-fouling functions even after being treated under severe conditions of high temperature, acid and alkali and the like.
Finally, it should be noted that the above-mentioned contents are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, and that the simple modifications or equivalent substitutions of the technical solutions of the present invention by those of ordinary skill in the art can be made without departing from the spirit and scope of the technical solutions of the present invention.
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