CN110564229B - Method for rapidly preparing copper/polytetrafluoroethylene super-amphiphobic coating - Google Patents
Method for rapidly preparing copper/polytetrafluoroethylene super-amphiphobic coating Download PDFInfo
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- 239000011248 coating agent Substances 0.000 title claims abstract description 65
- 238000000576 coating method Methods 0.000 title claims abstract description 65
- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 65
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 65
- 239000010949 copper Substances 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 49
- 239000000839 emulsion Substances 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 21
- 238000006073 displacement reaction Methods 0.000 claims abstract description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000002086 nanomaterial Substances 0.000 claims abstract description 14
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000005260 corrosion Methods 0.000 claims abstract description 11
- 230000007797 corrosion Effects 0.000 claims abstract description 10
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- 239000012528 membrane Substances 0.000 claims abstract description 8
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- 239000011159 matrix material Substances 0.000 claims description 16
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 238000007598 dipping method Methods 0.000 claims description 9
- 239000003344 environmental pollutant Substances 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
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- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 5
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- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000000428 dust Substances 0.000 claims description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- 238000013461 design Methods 0.000 claims description 2
- 238000013007 heat curing Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- ZLMJMSJWJFRBEC-OUBTZVSYSA-N potassium-40 Chemical group [40K] ZLMJMSJWJFRBEC-OUBTZVSYSA-N 0.000 claims description 2
- 238000005520 cutting process Methods 0.000 claims 1
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- 239000003513 alkali Substances 0.000 abstract description 3
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- 239000002105 nanoparticle Substances 0.000 description 10
- 230000003075 superhydrophobic effect Effects 0.000 description 8
- 239000007769 metal material Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
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- 229910001431 copper ion Inorganic materials 0.000 description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 2
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- 229920001600 hydrophobic polymer Polymers 0.000 description 2
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- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- PRPAGESBURMWTI-UHFFFAOYSA-N [C].[F] Chemical group [C].[F] PRPAGESBURMWTI-UHFFFAOYSA-N 0.000 description 1
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- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
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- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
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- 239000003440 toxic substance Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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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
- 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
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1668—Vinyl-type polymers
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Abstract
The invention relates to a method for rapidly preparing a copper/polytetrafluoroethylene composite super-amphiphobic coating, which sequentially comprises the following steps: (1) pretreating the surface of the base material (sanding, alkali washing or acid washing, ultrasonic cleaning of acetone, absolute ethyl alcohol and deionized water, and drying); (2) preparing chemical displacement membrane preparation emulsion containing a component A and a component B; (3) depositing a copper/polytetrafluoroethylene composite coating by chemical displacement reaction; (4) and (3) carrying out vacuum thermocuring treatment on the deposited copper/polytetrafluoroethylene composite coating to obtain the copper/polytetrafluoroethylene composite super-amphiphobic coating with the dendritic micro-nano structure. The copper/polytetrafluoroethylene composite super-amphiphobic coating prepared by the invention has the characteristics of super hydrophobicity, super oleophobicity, thermal stability, corrosion resistance and the like. The preparation method is simple and quick, low in cost and environment-friendly, and the prepared super-amphiphobic surface has stable performance and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of coating preparation, special wettability surface and material surface protection. In particular to a method for rapidly preparing a dendritic micro-nano structure copper/polytetrafluoroethylene composite super-amphiphobic (super-hydrophobic and super-oleophobic) coating, which improves the service life and functional application of metal materials such as aluminum materials, magnesium materials, zinc materials, iron and the like by means of the hydrophobic, oleophobic, anti-scaling, self-cleaning and anti-corrosion characteristics of a super-amphiphobic surface.
Background
Aluminum materials, magnesium materials, zinc materials, iron and other metal materials are common engineering materials and play an important role in industrial and social development; however, these metal materials are prone to corrosion, fouling and even damage in the service environment during service, which shortens the service life of the materials and increases the maintenance cost. In recent years, the service life of the metal materials is prolonged by continuously updated antifouling and anticorrosion technologies, and particularly, the surface modification technology for realizing the special wettability of the surface of the material is more and more concerned by people; because the surface with special wettability has the characteristics of super-hydrophobicity or super-lipophobicity, scale prevention, self-cleaning and corrosion prevention, a new idea is provided for the antifouling and corrosion prevention of the matrix.
According to the theory of preparing a particularly wettable surface, two requirements are: firstly, the roughness of the surface of the material is increased, and secondly, the surface energy of the surface of the material is reduced. At present, fluorine-containing polymer (such as polytetrafluoroethylene PTFE) has extremely low intermolecular interaction force of fluorine-carbon chains, extremely low surface energy, low friction and high-temperature corrosion resistance, so that the fluorine-containing polymer is widely applied to the field of hydrophobic non-stick, but the intrinsic hydrophobic contact angle is 90-110 degrees, and the requirement of a super-hydrophobic (static contact angle is more than 150 degrees) surface is not met, so that the special wettability of the surface is realized by combining other technical means.
Chinese patent (publication No. CN109233482A, published as 2019, 1 month, 18 days) discloses a preparation method of a super-amphiphobic durable coating of a water-based system; putting seed emulsion into a container, adding fluorosilane and a surfactant, stirring for 0.5-1h at room temperature, dispersing in water to obtain emulsion, spraying the emulsion on the surface of a substrate, wherein the spraying thickness is 800nm, and heating for 0.5-2h at the temperature of 135 ℃ of 125 ℃ to obtain a super-amphiphobic coating; the invention emphasizes that the industrial emulsion is used for directly preparing the super-amphiphobic coating, compared with the nano particles, the super-amphiphobic coating is simple to operate and better in dispersion, and the prepared super-amphiphobic coating is stable in performance. Chinese patent (application publication No. CN102776548A, application publication date 2012, 11 month 14) discloses a composite electroplating method for preparing a super-hydrophobic film layer on a steel surface; firstly, grinding, polishing and activating steel, then carrying out composite electroplating treatment on the steel in a composite plating solution (comprising a nickel-phosphorus plating solution and nano polytetrafluoroethylene particles), forming a layer of micro-nano structure on the surface of the steel, and finally transferring the steel into a vacuum furnace for heat treatment; the invention emphasizes that the method is suitable for surface treatment of various steel materials and has wide application range. Chinese patent (No. CN104072792B, No. 7/4 in 2017) discloses a preparation method of a super-hydrophobic polytetrafluoroethylene film; firstly, uniformly stirring 15-40 parts of PTFE emulsion, 40-54 parts of ultrapure water, 8-25 parts of zinc acetate and 1-20 parts of sodium chloride or potassium chloride; preparing a membrane on a substrate by adopting a dip coating method, drying, calcining at the temperature of 380 ℃ for 20-40min by 360-fold, and soaking for 30min by using 1mol/L acetic acid solution to obtain the super-hydrophobic polytetrafluoroethylene membrane, wherein the contact angle is 150.5-155.6 degrees, and the rolling angle is less than 30 degrees; adding zinc acetate and chloride salt into PTFE emulsion, obtaining polytetrafluoroethylene with a micro-and nano-structure by utilizing a phase separation principle and a dip coating film making mode, carrying out corrosion treatment on the polytetrafluoroethylene with acetic acid after calcination treatment, and taking down a cross-linked and cured polytetrafluoroethylene film from a substrate to obtain a porous polytetrafluoroethylene film with a micro-nano structure; the technical method is simple, easy for large-scale production, good in surface wear resistance, capable of being repaired and reused, and the reaction principle of the method is mainly that zinc acetate generates zinc oxide at the decomposition temperature to prepare the roughness required by the super-hydrophobic film. Chinese patent (No. CN103992701B, granted on 2016, 9, 7) discloses a preparation method of a super-hydrophobic polymer composite coating containing nano-particles; firstly, mixing a coupling agent, a hydrolysis promoter and deionized water, carrying out normal-temperature hydrolysis, adding nanoparticles, reacting for 0.25-5 h at 50-100 ℃ under magnetic stirring, and carrying out post-treatment to obtain modified nanoparticle powder (aluminum oxide and silicon dioxide); sieving the modified nano particle powder, mixing with fluoropolymer emulsion (polytetrafluoroethylene and fluorinated ethylene propylene), diluting with diluent, stirring, coating on a metal substrate, curing at high temperature, annealing, and cooling to room temperature; the invention emphasizes and provides a simple method for preparing a super-hydrophobic polymer composite coating containing nano particles, the nano particles are modified by a coupling agent, the pH adjusting process in the nano particle hydrophobic treatment process is omitted, the modified nano particles are added into a polymer composite film coating, and the purpose of stabilization is achieved through the interaction of the bonding of the nano particles and the coupling agent and the long chain of the fluorine-containing polymer molecule. Although the above patent technologies can prepare a surface with special wettability and containing PTFE, the technical methods have the disadvantages of high cost, more environmental pollutants, more process steps, complex control conditions of each process, need of support of specific instruments and equipment, poor coating uniformity and substrate binding property and the like, and are not suitable for large-scale industrial application.
The process for preparing the special wettability surface is different from the technical method, and the super-amphiphobic surface with good super-hydrophobicity, super-oleophobicity, thermal stability and corrosion resistance is simply, quickly and efficiently prepared on the aluminum material and other substrates through a two-step method of emulsion chemical replacement and thermosetting film forming. The preparation method and the process are simple, the cost is low, and the prepared copper (Cu)/Polytetrafluoroethylene (PTFE) composite coating with the dendritic micro-nano structure is stable in structure; in addition, the method can be applied to the surfaces of aluminum materials, magnesium, zinc, iron and other metal materials, and is suitable for industrial production.
Disclosure of Invention
The invention aims to develop a method for simply and quickly preparing a super-amphiphobic coating with good super-hydrophobicity, super-oleophobic property, thermal stability, corrosion resistance and other characteristics.
In order to achieve the purpose, the method for rapidly preparing the dendritic micro-nano structure copper/polytetrafluoroethylene composite super-amphiphobic coating sequentially comprises the following steps:
(1) pretreatment of the surface of a substrate
Any one of metal materials such as aluminum, magnesium, zinc, iron and alloys thereof is used as a base material, the base material is cut into required sizes according to use or design requirements, sand paper is used for polishing off dust and rust impurities on the surface of the base material, the polished sample is sequentially placed into acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 5-15min, impurities and pollutants such as dust, rust, oil stain and the like on the surface of the base material are further removed, and then the base material is placed into a constant-temperature blast drying box and dried at 30-100 ℃ for later use; if the impurities and pollutants are not easy to polish, alkali washing in alkaline water washing solution of 3-10% sodium hydroxide for 30s-2min or acid washing in acid washing solution of 20-30% nitric acid for 30s-2min can be used; then sequentially putting into acetone and absolute ethyl alcohol for ultrasonic cleaning for 5-15 min;
(2) preparing chemical displacement membrane-making emulsion by adopting mixed solution method
Taking the following components in parts by mass: 5-40 parts of soluble inorganic salt containing copper ions such as copper sulfate pentahydrate, copper nitrate or copper chloride, 1-3 parts of sodium chloride or potassium chloride and 40-200 parts of deionized water or pure water, and uniformly stirring to prepare a film-making emulsion component A;
taking the following components in parts by mass: 10-50 parts of water-soluble PTFE emulsion as a film-making emulsion component B;
mixing the film-making emulsion component A and the component B, and uniformly stirring to form stable emulsion;
(3) chemical displacement reaction deposition Cu/PTFE composite coating
Dipping the substrate pretreated in the step (1) into the chemical displacement membrane-making emulsion prepared in the step (2), wherein the dipping time is 30s-8min, generating a reddish Cu/PTFE composite coating on the surface of the substrate material, and taking out the substrate for later use; bubbles are generated in the reaction process, when the mass parts of all the components of the chemical displacement membrane preparation emulsion are small, the dipping time is close to the upper limit of a time window for 8min, and when the mass parts of all the components of the chemical displacement membrane preparation emulsion are large, the dipping time is close to the lower limit of the time window for 30 s;
(4) vacuum heat curing film forming process
And (3) putting the matrix sample with the surface covered with the Cu/PTFE composite coating in the step (3) into a vacuum tube furnace or a vacuum heating furnace for thermosetting treatment, ensuring the vacuum condition of the vacuum degree in the furnace being less than-0.1 MPa, properly controlling the heating rate, controlling the heat treatment temperature to be 150-380 ℃, keeping the temperature for 1-5 h, and cooling to room temperature along with the furnace after the thermosetting treatment is finished to obtain the reddish dendritic micro-nano structure Cu/PTFE composite super-amphiphobic coating with super-hydrophobicity, super-lipophobicity, thermal stability and corrosion resistance.
The forming principle of the super-amphiphobic coating is as follows: firstly, carrying out a simple physical or chemical cleaning process on the surface of a base material to obtain a base surface with certain roughness, high cleanliness and multiple active centers on the surface of the base material, so as to improve the bonding property of a deposited coating and the base in the subsequent steps and reduce the influence of impurities and pollutants on the coating; in the prepared chemical displacement membrane preparation emulsion, the reaction mainly takes place that copper ions in a matrix material displacement solution are copper simple substances and are adsorbed on the surface of a matrix material to form a deposited reddish Cu/PTFE composite coating; in the direct thermal curing process, polytetrafluoroethylene deposited in the Cu/PTFE composite coating on the surface of the matrix is cured to form a film under a certain temperature condition, and finally a reddish Cu/PTFE composite super-amphiphobic coating is generated on the surface of the matrix.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method adopts common chemical reagents and materials, quickly prepares the stable and reliable super-amphiphobic surface in a simple and low-cost two-step preparation mode, omits the single operation of low surface energy modification in the conventional preparation of the special wettability surface, and has more direct whole process and higher controllability;
(2) the preparation principle of the invention is simple and direct, the matrix material generates displacement reaction in the chemical displacement membrane-making emulsion, and no pollution and toxic substances are generated, thereby avoiding the harm to human body and environment;
(3) the microstructure of the invention is mainly a dendritic micro-nano structure generated by chemical displacement deposition of a Cu/PTFE composite coating after thermal curing, the structure is stable, and the super hydrophobicity, super oleophobicity and thermal stability of the coating are ensured;
(4) the processing process adopted by the invention has no special requirements on the shape and the size of the sample, increases the popularization and application of the invention, and can be popularized to the surfaces of other metal materials such as magnesium, zinc, iron and the like.
Drawings
FIG. 1 is an SEM image of a Cu/PTFE composite super-amphiphobic coating;
FIG. 2 is a self-cleaning test plot of a Cu/PTFE composite super-amphiphobic coating;
FIG. 3 is a contact angle of a Cu/PTFE composite super-amphiphobic coating to deionized water;
FIG. 4 is a contact angle of a Cu/PTFE composite super-amphiphobic coating to ethylene glycol;
FIG. 5 is a graph of the relationship between the heat preservation time of the Cu/PTFE composite super-amphiphobic coating and the contact angles of water and glycol in the heat preservation process at 260 ℃;
FIG. 6 is a graph of the relationship between the immersion time of the Cu/PTFE composite super-amphiphobic coating in a sodium chloride solution with the mass fraction of 3.5% and the contact angles of water and glycol.
Detailed Description
The invention is described in detail below with reference to the attached drawing figures:
the invention aims to develop a method for simply and quickly preparing a copper/polytetrafluoroethylene composite super-amphiphobic coating with a dendritic micro-nano structure, and the method improves the service life and functional application of a matrix material by virtue of good super-hydrophobicity, super-oleophobic property, thermal stability and corrosion resistance of the surface of the coating.
In order to achieve the purpose, the invention takes pure aluminum and 6061 aluminum alloy as research objects, and prepares the copper/polytetrafluoroethylene composite super-amphiphobic coating on the surface of the matrix.
The first embodiment is as follows:
(1) selecting a 6061 aluminum alloy with the size of 20 multiplied by 40 multiplied by 2mm as a substrate sample, polishing the substrate sample smoothly by using abrasive paper, and sequentially putting the polished sample into acetone and absolute ethyl alcohol for ultrasonic cleaning for 5min to remove grease and pollutants on the surface of the sample;
(2) soaking the cleaned 6061 aluminum alloy sample in chemical replacement film-making emulsion (by mass parts: 10 parts of blue vitriol, 1 part of sodium chloride, 50 parts of deionized water (pure water) and 20 parts of water-soluble PTFE emulsion) by adopting a soaking film-making method for 4min to generate a reddish Cu/PTFE composite coating on the surface of a base material, and taking out the coating for later use;
(3) putting the matrix sample with the surface covered with the Cu/PTFE composite coating in the previous step into a vacuum tube furnace for direct heat treatment, wherein the vacuum degree in the furnace is less than-0.1 MPa, the heating rate is controlled to be 5 ℃/min, the heat treatment temperature is 300 ℃, the heat preservation time is 1.5h, and after the heat treatment is finished, the matrix sample is cooled to room temperature along with the furnace to obtain the dendritic micro-nano structure Cu/PTFE composite super-amphiphobic coating (shown in figure 1) with thermal stability and wear resistance, and performing self-cleaning test on the coating (shown in figure 2); the contact angle of a 3 mul deionized water droplet on the Cu/PTFE composite super amphiphobic coating was about 152.52 ° (as shown in fig. 3), and the contact angle of a 3 mul ethylene glycol droplet on the Cu/PTFE composite super amphiphobic coating was about 151.14 ° (as shown in fig. 4).
(4) Keeping the temperature at 260 ℃ for a period of time, and testing the change conditions of contact angles of deionized water and ethylene glycol droplets to prove that the Cu/PTFE composite super-amphiphobic coating has good thermal stability (as shown in figure 5); the Cu/PTFE composite super-amphiphobic coating is soaked in 3.5 percent (mass fraction) of sodium chloride solution for a period of time, and the change of contact angles of deionized water and ethylene glycol drops is tested, so that the Cu/PTFE composite super-amphiphobic coating is proved to have good corrosion resistance (as shown in figure 6).
The second embodiment is as follows:
(1) selecting a 6061 aluminum alloy with the size of 20 multiplied by 40 multiplied by 2mm as a substrate sample, polishing the substrate sample smoothly by abrasive paper, carrying out alkali washing for 2min in an alkaline washing liquid of 3% sodium hydroxide, and sequentially putting the polished sample into acetone and absolute ethyl alcohol for ultrasonic cleaning for 10min to remove grease and pollutants on the surface of the sample;
(2) soaking the cleaned 6061 aluminum alloy sample in chemical replacement film-making emulsion (the mass parts are 20 parts of blue vitriol, 1.5 parts of sodium chloride, 100 parts of deionized water (pure water) and 30 parts of water-soluble PTFE emulsion) by adopting a soaking film-making method for 3min, generating a reddish Cu/PTFE composite coating on the surface of a base material, and taking out the coating for later use;
(3) and (3) putting the matrix sample with the surface covered with the Cu/PTFE composite coating in the previous step into a muffle furnace for direct heat treatment, wherein the vacuum degree in the furnace is less than-0.1 MPa, the heating rate is controlled to be 6 ℃/min, the heat treatment temperature is 380 ℃, the heat preservation time is 2 hours, and after the heat treatment is finished, the matrix sample is cooled to room temperature along with the furnace, so that the dendritic micro-nano structure Cu/PTFE composite super-amphiphobic coating with the thermal stability and the wear resistance can be prepared.
The third concrete implementation mode:
(1) selecting 6061 pure aluminum with the size of 20 x 40 x 2mm as a substrate sample, polishing the substrate sample smoothly by using abrasive paper, pickling for 2min in pickling solution of 30% nitric acid, and sequentially putting the polished sample into acetone and absolute ethyl alcohol for ultrasonic cleaning for 15min to remove grease and pollutants on the surface of the sample;
(2) soaking the cleaned pure aluminum sample in chemical replacement film-making emulsion (comprising 25 parts by mass of copper sulfate pentahydrate, 2 parts by mass of potassium chloride, 150 parts by mass of deionized water (pure water) and 30 parts by mass of water-soluble PTFE emulsion) for 5min by adopting a dipping and pulling method, generating a reddish Cu/PTFE composite coating on the surface of a base material, and taking out the coating for later use;
(3) and (3) putting the matrix sample with the surface covered with the Cu/PTFE composite coating in the previous step into a muffle furnace for direct heat treatment, wherein the vacuum degree in the furnace is less than-0.1 MPa, the heating rate is controlled to be 5 ℃/min, the heat treatment temperature is 350 ℃, the heat preservation time is 2 hours, and after the heat treatment is finished, the matrix sample is cooled to room temperature along with the furnace, so that the dendritic micro-nano structure Cu/PTFE composite super-amphiphobic coating with the thermal stability and the wear resistance can be prepared.
Claims (1)
1. A method for rapidly preparing a copper/polytetrafluoroethylene composite super-amphiphobic coating sequentially comprises the following steps:
(1) pretreatment of the surface of a substrate
Taking any one of aluminum, magnesium, zinc, iron and alloy materials thereof as a base material, cutting the base material into required sizes according to use or design requirements, polishing away impurities including dust and rust on the surface of the base material by using abrasive paper, sequentially putting the polished sample into acetone, absolute ethyl alcohol and deionized water for ultrasonic cleaning for 5-15min, further removing impurities and pollutants including dust, rust and oil stain on the surface of the base material, then putting the base material into a constant-temperature blast drying box, and drying the base material at 30-100 ℃ for later use; if the impurities and pollutants are not easy to polish, alkaline washing with 3-10% sodium hydroxide alkaline washing solution for 30s-2min, or acid washing with 20-30% nitric acid washing solution for 30s-2 min; then sequentially putting into acetone and absolute ethyl alcohol for ultrasonic cleaning for 5-15 min;
(2) preparing chemical displacement membrane-making emulsion by adopting mixed solution method
Taking the following components in parts by mass: 5-40 parts of copper sulfate pentahydrate or copper nitrate or copper chloride, 1-3 parts of sodium chloride or potassium chloride and 40-200 parts of deionized water or pure water, and uniformly stirring to prepare a film-making emulsion component A;
taking the following components in parts by mass: 10-50 parts of water-soluble PTFE emulsion as a film-making emulsion component B;
mixing the film-making emulsion component A and the component B, and uniformly stirring to form stable emulsion;
(3) chemical displacement reaction deposition Cu/PTFE composite coating
Dipping the substrate pretreated in the step (1) into the chemical displacement membrane-making emulsion prepared in the step (2), wherein the dipping time is 30s-8min, generating a reddish Cu/PTFE composite coating on the surface of the substrate material, and taking out the substrate for later use; bubbles are generated in the reaction process, when the mass parts of all the components of the chemical displacement membrane preparation emulsion are small, the dipping time is close to the upper limit of a time window for 8min, and when the mass parts of all the components of the chemical displacement membrane preparation emulsion are large, the dipping time is close to the lower limit of the time window for 30 s;
(4) vacuum heat curing film forming process
And (3) putting the matrix sample with the surface covered with the Cu/PTFE composite coating in the step (3) into a muffle furnace or a tubular furnace for vacuum thermosetting treatment, ensuring the vacuum condition of the vacuum degree in the furnace being less than-0.1 MPa, properly controlling the heating rate, controlling the heat treatment temperature to be 150-380 ℃, keeping the temperature for 1-5 h, and cooling to room temperature along with the furnace after the thermosetting treatment is finished to obtain the reddish dendritic micro-nano structure Cu/PTFE composite super-amphiphobic coating with super-hydrophobicity, super-lipophobicity, thermal stability and corrosion resistance.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102776548A (en) * | 2012-06-07 | 2012-11-14 | 清华大学 | Method for preparing steel surface super-hydrophobic film |
| CN104072792A (en) * | 2014-07-04 | 2014-10-01 | 无锡市顺业科技有限公司 | Super-hydrophobic polytetrafluoroethylene film |
| CN107267967A (en) * | 2017-07-06 | 2017-10-20 | 中国石油大学(华东) | A kind of method for preparing super-hydrophobic copper coating in aluminum alloy surface |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102776548A (en) * | 2012-06-07 | 2012-11-14 | 清华大学 | Method for preparing steel surface super-hydrophobic film |
| CN104072792A (en) * | 2014-07-04 | 2014-10-01 | 无锡市顺业科技有限公司 | Super-hydrophobic polytetrafluoroethylene film |
| CN107267967A (en) * | 2017-07-06 | 2017-10-20 | 中国石油大学(华东) | A kind of method for preparing super-hydrophobic copper coating in aluminum alloy surface |
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