CN112048202A - Preparation method of steel-based corrosion-resistant super-hydrophobic coating - Google Patents
Preparation method of steel-based corrosion-resistant super-hydrophobic coating Download PDFInfo
- Publication number
- CN112048202A CN112048202A CN202010957590.2A CN202010957590A CN112048202A CN 112048202 A CN112048202 A CN 112048202A CN 202010957590 A CN202010957590 A CN 202010957590A CN 112048202 A CN112048202 A CN 112048202A
- Authority
- CN
- China
- Prior art keywords
- hydrophobic coating
- steel
- cnts
- super
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
- B05D7/16—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
The invention relates to the field of metal surface treatment, in particular to a preparation method of a steel-based corrosion-resistant super-hydrophobic coating. According to the invention, a silanol compound or titanium alcohol is dissolved in absolute ethyl alcohol, citric acid is used as a catalyst, a constant-temperature magnetic stirrer is used for carrying out vigorous stirring, the silanol compound or titanium alcohol compound is completely hydrolyzed to prepare sol, the prepared sol is mixed with the pretreated CNTs dispersion liquid, the mixed solution is sprayed on the surface of steel after impurity removal in a spray drying mode, and then a sample is placed in a tubular furnace for curing reaction and then taken out, so that the corrosion-resistant super-hydrophobic coating can be obtained. The preparation method disclosed by the invention has the advantages of low synthesis temperature, uniform solution dispersion, easiness in reaction, simplicity and convenience in operation, environmental friendliness and no fluorine, the obtained steel-based corrosion-resistant super-hydrophobic coating is excellent in acid-base corrosion resistance, the contact angle can still be kept above 150 degrees after the coating is soaked in an acid-base solution for 12 hours, and the preparation method has important value in the practical application process of steel.
Description
Technical Field
The invention relates to the field of metal surface treatment, in particular to a preparation method of a steel-based corrosion-resistant super-hydrophobic coating.
Background
The steel is an important material indispensable to national construction, has light weight, good toughness and good heat-resisting and sealing performance, and is widely applied to various aspects in life. However, the steel material itself is liable to corrosion, which not only restricts the application of the steel material, but also causes a great economic loss, so that it is necessary to impart corrosion resistance to the steel material. With the gradual deepening of the environmental protection and energy saving concepts, the surface with the self-cleaning function is widely researched, the self-cleaning function can be better realized by coating the super-hydrophobic coating on the surface of the base material, the corrosion of the steel base material can be more effectively prevented by coating the super-hydrophobic coating on the surface of the steel base material, the icing phenomenon generated on the surface of the steel due to water accumulation can be inhibited, and the application range of the steel is greatly expanded.
Chinese invention patent (CN 107740083B) discloses a preparation method of a magnesium alloy surface super-hydrophobic fluorine conversion coating, wherein a micro/nano structure super-hydrophobic fluorine coating is prepared on the surface of a magnesium alloy by adopting a liquid phase growth and hydrothermal treatment combined method, the contact angle of the magnesium alloy prepared by the method is more than 150 degrees, the super-hydrophobic property is better, but the fluorine material has great pollution to the environment, and the fluorine material also has threat to the health of human bodies, and does not accord with the development concept of environmental protection.
Chinese patent application (CN 109749538A) discloses a preparation method of a super-hydrophobic coating, which is prepared by mixing silicon dioxide (SiO)2) Adding the mixture into a mixed solution of a silane coupling agent and isopropanol to react, drying to obtain a solid, performing ball milling and filtering, adding a mixed coating and Polytetrafluoroethylene (PTFE) nano particles, performing magnetic stirring to obtain a spraying liquid A, and spraying the spraying liquid A onto a base material to obtain the super-hydrophobic coating. However, the single fluorine coating has poor wear and corrosion resistance and does not give the substrate permanent corrosion protection.
The mechanical property of a single super-hydrophobic coating is poor, and the steel cannot be protected from corrosion for a long time, so that the performance of the coating needs to be considered, the corrosion-resistant super-hydrophobic coating with good mechanical property is prepared, and the corrosion-resistant super-hydrophobic coating is used for corrosion prevention of the steel, so that the protection time of the steel can be effectively prolonged.
Disclosure of Invention
Aiming at the problems, the invention provides the preparation method of the steel-based corrosion-resistant super-hydrophobic coating, the preparation method is environment-friendly and fluorine-free, the preparation method is simple and convenient, the prepared coating has excellent super-hydrophobic performance and corrosion resistance, and the substrate material coated with the coating can adapt to severe natural environment.
The manufacturing of the micro-nano structure on the surface of the material is a necessary condition for endowing the material with super-hydrophobic performance. Carbon Nanotubes (CNTs) are one typeThe material with excellent performance has wide application, and the carbon atom in the CNTs is SP2It is hybrid and therefore has high modulus and high strength. It has a hardness comparable to that of diamond, but possesses good flexibility, and is called "super fiber". The carbon nano tube is introduced into the super-hydrophobic coating, so that the mechanical property of the coating can be greatly improved, and the coating is endowed with excellent corrosion resistance.
The invention provides a preparation method of a steel-based corrosion-resistant super-hydrophobic coating, which mainly comprises the following steps:
firstly, preprocessing CNTs:
the method comprises the steps of placing CNTs powder in a stainless steel ball milling tank, carrying out ball milling at a certain rotating speed in an Ar protective atmosphere, taking out the CNTs subjected to ball milling, placing the CNTs in a beaker, adding a nitric acid-sulfuric acid mixed acid, carrying out oil bath heating and stirring for a period of time, pouring out a mixed solution, centrifuging, repeatedly washing with distilled water, removing a supernatant to obtain an acid-treated CNTs black liquid, and carrying out freeze drying to obtain an acidified CNTs black powder.
Secondly, preparing the super-hydrophobic coating:
(1) mixing a silanol compound or a titanium alcohol compound with absolute ethyl alcohol, and stirring to form a solution A;
(2) mixing deionized water and absolute ethyl alcohol, dropwise adding citric acid serving as a catalyst, and adjusting the pH value of the solution to 3-4 to form a solution B;
(3) dropwise adding the solution A into the prepared solution B at room temperature, and violently stirring by using a constant-temperature magnetic stirrer to completely hydrolyze the silanol compound or the titanium alcohol compound to prepare sol;
(4) adding the pretreated CNTs into deionized water, and placing the CNTs in an ultrasonic cleaning machine for complete dispersion by ultrasound;
(5) mixing the sol prepared in the step (3) with the CNTs dispersion liquid in the step (4), and placing the mixed solution in an ultrasonic dispersion machine to uniformly disperse the mixed solution;
(6) and (3) spraying the uniformly dispersed mixed solution in the step (5) on the surface of the steel product after impurity removal in a spraying mode, then placing the sample in a tube furnace for curing reaction, and taking out the sample to obtain the corrosion-resistant super-hydrophobic coating.
Further, in the pretreatment process of the CNTs, the rotating speed of the ball mill is 300-500 r/min.
Further, during the pretreatment of the CNTs, the volume fraction of the nitrate is 60%, the volume fraction of the sulfuric acid is 70%, and the volume ratio of the nitric acid to the sulfuric acid is 1: 1; the temperature of the oil bath pot is 40-70 ℃, and the treatment time is 4-8 h.
Further, in the pretreatment process of the CNTs, the freeze drying time is 12-24 h.
Further, the silanol compound in the step (1) comprises one of methyl silanol compound, tetraethyl silicate and tetramethyl ammonium hydroxide silanol compound or a mixture thereof, and the titanium alcohol compound comprises one of titanium trichloride, tetrabutyl titanate and tetraisopropyl titanate or a mixture thereof; the mol ratio of the silanol compound or the titanium alcohol compound to the absolute ethyl alcohol is 1: 1.
Further, the volume ratio of the deionized water to the absolute ethyl alcohol in the step (2) is 1:1
Further, the dropping speed of the solution A into the solution B in the step (3) is 2-5 drops/second; the rotating speed of the constant-temperature magnetic stirrer is 100-150 r/min, and the reaction time is 5-10 h.
Further, the time of ultrasonic dispersion in the step (4) is 2-5 hours.
Further, the power of the ultrasonic dispersion machine in the step (5) is 200-500W, and the ultrasonic treatment time is 10-15 h.
Further, polishing and grinding the steel matrix in the step (6), performing ultrasonic oil removal pretreatment until the surface is smooth, and removing oil stains and oxides on the surface to obtain the steel matrix after impurity removal.
Further, the temperature range of the tube furnace is 300-600 ℃, and the treatment time is 12-24 h.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method used by the invention is environment-friendly and fluorine-free, and is simple and easy to realize.
(2) The invention obtains the silicon and titanium nano particles by the sol-gel method of the silanol compound or the titanium alcohol compound to prepare the super-hydrophobic coating, and has the advantages of low synthesis temperature, uniform solution dispersion and easy reaction.
(3) The CNTs are uniformly dispersed in the sol, so that the coating seed is uniform, and the wear resistance is obviously improved.
(4) The contact angle of the steel-based corrosion-resistant super-hydrophobic coating prepared by the invention is up to more than 158 degrees, and the steel-based corrosion-resistant super-hydrophobic coating has excellent super-hydrophobic property.
(5) The steel-based corrosion-resistant super-hydrophobic coating prepared by the invention has excellent acid and alkali corrosion resistance, and the contact angle can still be kept above 150 degrees after the steel-based corrosion-resistant super-hydrophobic coating is soaked in an acid-base solution for 12 hours, so that the steel-based corrosion-resistant super-hydrophobic coating has important value in the practical application process of steel.
Drawings
FIG. 1 shows the results of the contact angle test of the steel-based corrosion resistant superhydrophobic coatings of examples 1-6.
FIG. 2 is a graph of the soaking time of the steel-based corrosion-resistant superhydrophobic coating in 10 wt% hydrochloric acid solution versus the contact angle in example 1.
FIG. 3 is a graph of the soaking time versus contact angle for the steel-based corrosion resistant superhydrophobic coating of example 1 in a 10 wt% sodium hydroxide solution.
Detailed Description
The technical solutions of the present invention will be described clearly and completely through the following embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a steel-based corrosion-resistant super-hydrophobic coating mainly comprises the following steps:
firstly, preprocessing Carbon Nanotubes (CNTs):
putting 10g of CNTs powder into a ball milling tank filled with stainless steel, carrying out ball milling at the rotating speed of 300r/min in Ar protective atmosphere, taking out the CNTs subjected to ball milling, putting the CNTs subjected to ball milling into a beaker, adding 50mL of a mixed solution of nitric acid with the volume fraction of 60% and sulfuric acid with the volume fraction of 50mL into the CNTs subjected to ball milling, heating and stirring for 5h in an oil bath at 50 ℃, pouring out the mixed solution, centrifuging, repeatedly washing with distilled water, removing the supernatant to obtain an acid-treated CNTs black liquid, and carrying out freeze drying for 15h at-20 to-5 ℃ to obtain an acidified CNTs black powder.
Secondly, preparing the super-hydrophobic coating:
(1) mixing 45.2g tetraethyl silicate with 10.0g absolute ethyl alcohol, and stirring to form a solution A;
(2) mixing 30mL of deionized water with 30mL of absolute ethyl alcohol, and dropwise adding 3mL of citric acid to adjust the pH value of the solution to 3.7 to form a solution B;
(3) dropwise adding the solution A into the solution B at the speed of 2 drops/second at room temperature, and stirring for 8 hours by using a constant-temperature magnetic stirrer with the rotating speed of 120r/min to completely hydrolyze the tetraethyl silicate to prepare sol;
(4) adding the pretreated CNTs into deionized water, and putting the CNTs into an ultrasonic cleaning machine for ultrasonic treatment for 3 hours to completely disperse the CNTs;
(5) mixing the sol prepared in the step (3) with the CNTs dispersion liquid in the step (4), and placing the mixed solution into an ultrasonic dispersion machine with the power of 300W for dispersion for 15 hours;
(6) and (3) spraying the uniformly dispersed mixed solution in the step (5) on the surface of a steel matrix which is polished and pretreated by ultrasonic degreasing to be smooth in surface in a spraying mode, then placing the sample in a 300 ℃ tube furnace for curing for 24 hours, and taking out the sample to obtain the corrosion-resistant super-hydrophobic coating. The static contact angle of the steel-based corrosion-resistant super-hydrophobic coating is tested, the static contact angle is 160.8 degrees, the super-hydrophobic performance is excellent, after the steel-based corrosion-resistant super-hydrophobic coating is soaked in hydrochloric acid and sodium hydroxide solution for 12 hours, the static contact angle can still be kept above 150 degrees, and the super-hydrophobic coating is excellent in acid-base corrosion resistance.
Example 2
A preparation method of a steel-based corrosion-resistant super-hydrophobic coating mainly comprises the following steps:
pretreatment of Carbon Nanotubes (CNTs):
placing 15g of CNTs powder in a ball milling tank filled with stainless steel, carrying out ball milling at the rotating speed of 400r/min in Ar protective atmosphere, taking out the CNTs subjected to ball milling, placing the CNTs in a beaker, adding 60mL of mixed solution of nitric acid and 60mL of sulfuric acid, heating and stirring for 5h in an oil bath at the temperature of 60 ℃, pouring out the mixed solution, centrifuging, repeatedly washing with distilled water, removing the supernatant to obtain acid-treated CNTs black liquid, and carrying out freeze drying for 15h to obtain acidified CNTs black powder.
Preparing a super-hydrophobic coating:
(1) mixing 73.8g of butyl titanate and 10.0g of absolute ethyl alcohol, and stirring to form a solution A;
(2) mixing 40mL of deionized water with 40mL of absolute ethyl alcohol, and dropwise adding 4mL of citric acid to adjust the pH value of the solution to 3.3 to form a solution B;
(3) and dropwise adding the solution A into the solution B at room temperature at the rate of 3 drops/second, and stirring for 8 hours by adopting a constant-temperature magnetic stirrer with the rotating speed of 120r/min to completely hydrolyze the butyl titanate to prepare sol.
(4) Adding the pretreated CNTs into deionized water, and putting the CNTs into an ultrasonic cleaning machine for ultrasonic treatment for 4 hours to completely disperse the CNTs;
(5) mixing the sol prepared in the step (3) with the CNT dispersion liquid in the step (4), and dispersing the mixed solution in an ultrasonic dispersion machine with the power of 70% for 10 hours;
(6) and (3) spraying the uniformly dispersed mixed solution in the step (5) on the surface of a steel matrix which is polished and pretreated by ultrasonic degreasing to be smooth in surface in a spraying mode, then placing the sample in a tube furnace at 250 ℃ for curing for 15h, and taking out the sample to obtain the corrosion-resistant super-hydrophobic coating. Thus obtaining the corrosion-resistant super-hydrophobic coating. The static contact angle of the corrosion-resistant super-hydrophobic coating on the steel base is tested, and the static contact angle is 159.8 degrees, which shows that the coating has excellent super-hydrophobic property.
Example 3
A preparation method of a steel-based corrosion-resistant super-hydrophobic coating mainly comprises the following steps:
pretreatment of Carbon Nanotubes (CNTs):
placing 15g of CNTs powder in a ball milling tank filled with stainless steel, carrying out ball milling at the rotating speed of 350r/min in Ar protective atmosphere, taking out the CNTs subjected to ball milling, placing the CNTs in a beaker, adding 60mL of mixed solution of nitric acid and 60mL of sulfuric acid, heating and stirring for 6h in an oil bath at 65 ℃, pouring out the mixed solution, centrifuging, repeatedly washing with distilled water, removing the supernatant to obtain acid-treated CNTs black liquid, and carrying out freeze drying for 20h to obtain acidified CNTs black powder.
Preparing a super-hydrophobic coating:
(1) mixing 61.7g of tetraisopropyl titanate and 10.0g of absolute ethyl alcohol, and stirring to form a solution A;
(2) mixing 40mL of deionized water with 40mL of absolute ethyl alcohol, and dropwise adding 3.5mL of citric acid to adjust the pH value of the solution to 3.5 to form a solution B;
(3) dropwise adding the solution A into the solution B at the rate of 4 drops/second at room temperature, and stirring for 6 hours by using a constant-temperature magnetic stirrer with the rotating speed of 140r/min to completely hydrolyze the tetraethyl silicate to prepare sol;
(4) adding the pretreated CNTs into deionized water, and putting the CNTs into an ultrasonic cleaning machine for ultrasonic treatment for 4 hours to completely disperse the CNTs;
(5) mixing the sol prepared in the step (3) with the CNT dispersion liquid in the step (4), and placing the mixed solution into an ultrasonic dispersion machine with the power of 68% for dispersing for 13 hours;
(6) and (3) spraying the uniformly dispersed mixed solution in the step (5) on the surface of a steel matrix which is polished and pretreated by ultrasonic degreasing to be smooth in surface in a spraying mode, and then putting the sample in a 400 ℃ tubular furnace for curing for 18h and taking out to obtain the corrosion-resistant super-hydrophobic coating. Thus obtaining the corrosion-resistant super-hydrophobic coating. The static contact angle of the steel-based corrosion-resistant super-hydrophobic coating is tested, and the static contact angle is 160.2 degrees, which shows that the coating has excellent super-hydrophobic property.
Example 4
A preparation method of a steel-based corrosion-resistant super-hydrophobic coating mainly comprises the following steps:
pretreatment of Carbon Nanotubes (CNTs):
placing 20g of CNTs powder in a ball milling tank filled with stainless steel, carrying out ball milling at the rotating speed of 450r/min in Ar protective atmosphere, taking out the CNTs subjected to ball milling, placing the CNTs in a beaker, adding 60mL of mixed solution of nitric acid and 60mL of sulfuric acid, heating and stirring for 5h in an oil bath at 70 ℃, pouring out the mixed solution, centrifuging, repeatedly washing with distilled water, removing the supernatant to obtain acid-treated CNTs black liquid, and carrying out freeze drying for 20h to obtain acidified CNTs black powder.
Preparing a super-hydrophobic coating:
(1) mixing 37.8g of sodium methylsiliconate and 15.0g of absolute ethyl alcohol, and stirring to form a solution A;
(2) mixing 40mL of deionized water with 40mL of absolute ethyl alcohol, and dropwise adding 3.5mL of citric acid to adjust the pH value of the solution to 3.5 to form a solution B;
(3) dropwise adding the solution A into the solution B at the rate of 4 drops/second at room temperature, and stirring for 6 hours by using a constant-temperature magnetic stirrer with the rotating speed of 140r/min to completely hydrolyze the tetraethyl silicate to prepare sol;
(4) adding the pretreated CNTs into deionized water, and putting the CNTs into an ultrasonic cleaning machine for ultrasonic treatment for 5 hours to completely disperse the CNTs;
(5) mixing the sol prepared in the step (3) with the CNT dispersion liquid in the step (4), and dispersing the mixed solution in an ultrasonic dispersing machine with the power of 65% for 12 hours;
(6) and (3) spraying the uniformly dispersed mixed solution in the step (5) on the surface of a steel matrix which is polished and pretreated by ultrasonic degreasing to be smooth in surface in a spraying mode, then placing the sample in a 450 ℃ tube furnace for curing for 16h, and taking out the sample to obtain the corrosion-resistant super-hydrophobic coating. Thus obtaining the corrosion-resistant super-hydrophobic coating. The static contact angle of the steel-based corrosion-resistant super-hydrophobic coating is tested, and the static contact angle is 161.1 degrees, which shows that the coating has excellent super-hydrophobic property.
Example 5
A preparation method of a steel-based corrosion-resistant super-hydrophobic coating mainly comprises the following steps:
pretreatment of Carbon Nanotubes (CNTs):
placing 20g of CNTs powder in a ball milling tank filled with stainless steel, carrying out ball milling at the rotating speed of 450r/min in Ar protective atmosphere, taking out the CNTs subjected to ball milling, placing the CNTs in a beaker, adding 60mL of mixed solution of nitric acid and 60mL of sulfuric acid, heating and stirring for 5h in an oil bath at 70 ℃, pouring out the mixed solution, centrifuging, repeatedly washing with distilled water, removing the supernatant to obtain acid-treated CNTs black liquid, and carrying out freeze drying for 24h to obtain acidified CNTs black powder.
Preparing a super-hydrophobic coating:
(1) mixing 59.0g of tetramethyl ammonium hydroxide silanol compound with 15.0g of absolute ethyl alcohol, and stirring to form a solution A;
(2) mixing 50mL of deionized water with 50mL of absolute ethyl alcohol, and dropwise adding 5.3mL of citric acid to adjust the pH value of the solution to 3.6 to form a solution B;
(3) dropwise adding the solution A into the solution B at the rate of 4 drops/second at room temperature, and stirring for 6 hours by using a constant-temperature magnetic stirrer with the rotating speed of 140r/min to completely hydrolyze the tetraethyl silicate to prepare sol;
(4) adding the pretreated CNTs into deionized water, and placing the mixture in an ultrasonic cleaning machine for 2-5 hours to carry out ultrasonic treatment so as to completely disperse the CNTs;
(5) mixing the sol prepared in the step (3) with the CNT dispersion liquid in the step (4), and dispersing the mixed solution in an ultrasonic dispersing machine with the power of 55% for 15 hours;
(6) and (3) spraying the uniformly dispersed mixed solution in the step (5) on the surface of a steel matrix which is polished and pretreated by ultrasonic degreasing to be smooth in surface in a spraying mode, then placing the sample in a 500 ℃ tube furnace for curing for 20 hours, and taking out the sample to obtain the corrosion-resistant super-hydrophobic coating. The static contact angle of the steel-based corrosion-resistant super-hydrophobic coating is tested, and the static contact angle is 158.2 degrees, which shows that the coating has excellent super-hydrophobic property.
Example 6
A preparation method of a steel-based corrosion-resistant super-hydrophobic coating mainly comprises the following steps:
pretreatment of Carbon Nanotubes (CNTs):
placing 20g of CNTs powder in a ball milling tank filled with stainless steel, carrying out ball milling at the rotating speed of 450r/min in Ar protective atmosphere, taking out the CNTs subjected to ball milling, placing the CNTs in a beaker, adding 60mL of mixed solution of nitric acid and 60mL of sulfuric acid, heating and stirring for 5h in an oil bath at 70 ℃, pouring out the mixed solution, centrifuging, repeatedly washing with distilled water, removing the supernatant to obtain acid-treated CNTs black liquid, and carrying out freeze drying for 24h to obtain acidified CNTs black powder.
Preparing a super-hydrophobic coating:
(1) mixing 50.22g of titanium trichloride and 15.0g of absolute ethyl alcohol, and stirring to form a solution A;
(2) mixing 50mL of deionized water with 50mL of absolute ethyl alcohol, and dropwise adding 5.3mL of citric acid to adjust the pH value of the solution to 3.6 to form a solution B;
(3) dropwise adding the solution A into the solution B at the rate of 4 drops/second at room temperature, and stirring for 6 hours by using a constant-temperature magnetic stirrer with the rotating speed of 140r/min to completely hydrolyze the tetraethyl silicate to prepare sol;
(4) adding the pretreated CNTs into deionized water, and putting the mixture into an ultrasonic cleaning machine for ultrasonic treatment for 4.5 hours to completely disperse the CNTs;
(5) mixing the sol prepared in the step (3) with the CNT dispersion liquid in the step (4), and placing the mixed solution into an ultrasonic dispersion machine with the power of 65% for dispersing for 13 hours;
(6) and (3) spraying the uniformly dispersed mixed solution in the step (5) on the surface of a steel matrix which is polished and pretreated by ultrasonic degreasing to be smooth in surface in a spraying mode, then placing the sample in a 580 ℃ tube furnace for curing for 24 hours, and taking out the sample to obtain the corrosion-resistant super-hydrophobic coating. The static contact angle of the steel-based corrosion-resistant super-hydrophobic coating is tested, and the static contact angle is 160.3 degrees, which shows that the coating has excellent super-hydrophobic property.
And (3) testing chemical corrosion resistance:
the preparation of the corrosion bath solution: respectively preparing a hydrochloric acid solution with the concentration of 10 wt% and a sodium hydroxide solution;
placing the corrosion bath solution into a beaker, placing the beaker into a constant-temperature water bath kettle, keeping the temperature of the water bath kettle at 23 +/-2 ℃, immersing the sample to be tested prepared according to the scheme of the embodiment 1 into the corrosion bath solution, completely immersing the sample into the corrosion bath solution, taking out the sample every 2 hours, washing the surface of the sample by deionized water, sucking water by using filter paper, testing the contact angle of the sample, and observing the corrosion degree of the steel sample.
It was observed that no significant trace of corrosion was observed when the sample was corroded for 12 hours in both the 10 wt% hydrochloric acid solution and the sodium hydroxide solution.
Claims (8)
1. A preparation method of a steel-based corrosion-resistant super-hydrophobic coating is characterized by comprising the following steps: the preparation method comprises the following steps:
firstly, pretreating carbon nano tube CNTs:
placing CNTs powder in a ball milling tank filled with stainless steel balls, carrying out ball milling at a certain rotating speed in an Ar protective atmosphere, taking out the CNTs subjected to ball milling, placing the CNTs in a beaker, adding a nitric acid and sulfuric acid mixed acid, carrying out oil bath heating and stirring for a period of time, pouring out a mixed solution, centrifuging, repeatedly washing with distilled water, removing a supernatant to obtain acid-treated CNTs black liquid, and carrying out freeze drying to obtain acidified CNTs black powder;
secondly, preparing the super-hydrophobic coating:
(1) mixing a silanol compound or a titanium alcohol compound with absolute ethyl alcohol, and stirring to form a solution A;
(2) mixing deionized water and absolute ethyl alcohol, dropwise adding citric acid serving as a catalyst, and adjusting the pH value of the solution to 3-4 to form a solution B;
(3) dropwise adding the solution A into the prepared solution B at room temperature, and violently stirring by using a constant-temperature magnetic stirrer to completely hydrolyze the silanol compound or the titanium alcohol compound to prepare sol;
(4) adding the pretreated CNTs into deionized water, and placing the CNTs in an ultrasonic cleaning machine for complete dispersion by ultrasound;
(5) mixing the sol prepared in the step (3) with the CNTs dispersion liquid obtained in the step (4), and placing the mixed solution in an ultrasonic dispersion machine to uniformly disperse the mixed solution;
(6) and (3) spraying the uniformly dispersed mixed solution in the step (5) on the surface of the steel product after impurity removal in a spraying mode, then placing the sample in a tube furnace for curing reaction, and taking out the sample to obtain the corrosion-resistant super-hydrophobic coating.
2. The preparation method of the steel-based corrosion-resistant super-hydrophobic coating according to claim 1, characterized in that: in the preprocessing process of the CNTs, the rotating speed of the ball mill is 300-500 r/min; the volume fraction of the nitrate is 60%, the volume fraction of the sulfuric acid is 70%, and the volume ratio of the nitrate to the sulfuric acid is 1: 1; the temperature of the oil bath pot is 40-70 ℃, and the treatment time is 4-8 h; the freeze drying time is 12-24 h.
3. The preparation method of the steel-based corrosion-resistant super-hydrophobic coating according to claim 1, characterized in that: in the preparation process of the super-hydrophobic coating, the silanol compound in the step (1) comprises one or a mixture of sodium methyl silanol, tetraethyl silicate and tetramethylammonium hydroxide silanol, and the titanium alcohol compound comprises one or a mixture of titanium trichloride, tetrabutyl titanate and tetraisopropyl titanate; the mol ratio of the silanol compound or the titanium alcohol compound to the absolute ethyl alcohol is 1: 1.
4. The preparation method of the steel-based corrosion-resistant super-hydrophobic coating according to claim 1, characterized in that: in the preparation process of the super-hydrophobic coating, the volume ratio of the deionized water to the absolute ethyl alcohol in the step (2) is 1: 1.
5. The preparation method of the steel-based corrosion-resistant super-hydrophobic coating according to claim 1, characterized in that: in the preparation process of the super-hydrophobic coating, the dropping speed of the solution A into the solution B in the step (3) is 2-5 drops/second; the rotating speed of the constant-temperature magnetic stirrer is 100-150 r/min, and the reaction time is 5-10 h.
6. The preparation method of the steel-based corrosion-resistant super-hydrophobic coating according to claim 1, characterized in that: in the preparation process of the super-hydrophobic coating, the time of ultrasonic dispersion in the step (4) is 2-5 hours.
7. The preparation method of the steel-based corrosion-resistant super-hydrophobic coating according to claim 1, characterized in that: in the preparation process of the super-hydrophobic coating, the power of the ultrasonic dispersion machine in the step (5) is 200W-500W, and the ultrasonic treatment time is 10-15 h.
8. The preparation method of the steel-based corrosion-resistant super-hydrophobic coating according to claim 1, characterized in that: in the preparation process of the super-hydrophobic coating, polishing and grinding the steel matrix in the step (6), performing ultrasonic oil removal pretreatment until the surface is smooth, and removing oil stains and oxides on the surface to obtain a steel matrix after impurity removal; the temperature range of the tubular furnace is 300-600 ℃, and the treatment time is 12-24 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010957590.2A CN112048202A (en) | 2020-09-14 | 2020-09-14 | Preparation method of steel-based corrosion-resistant super-hydrophobic coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010957590.2A CN112048202A (en) | 2020-09-14 | 2020-09-14 | Preparation method of steel-based corrosion-resistant super-hydrophobic coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112048202A true CN112048202A (en) | 2020-12-08 |
Family
ID=73611102
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010957590.2A Withdrawn CN112048202A (en) | 2020-09-14 | 2020-09-14 | Preparation method of steel-based corrosion-resistant super-hydrophobic coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112048202A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115537118A (en) * | 2022-10-12 | 2022-12-30 | 电子科技大学 | Carbon nanotube ceramic coating and application method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289450A (en) * | 2013-04-23 | 2013-09-11 | 宁波墨西科技有限公司 | Carbon nanotube inorganic paint and usage method thereof |
| CN105295457A (en) * | 2015-10-30 | 2016-02-03 | 三棵树涂料股份有限公司 | Preparation method of carbon nano-tube loaded titanium dioxide top facing coating material |
| CN105802446A (en) * | 2016-03-31 | 2016-07-27 | 武汉理工大学 | Wear-resistant and super-hydrophobic coating material and preparation method thereof |
| CN106519744A (en) * | 2016-11-09 | 2017-03-22 | 东南大学 | Preparation method for carbon nanotube super-hydrophobic coating |
| CN107880751A (en) * | 2017-11-22 | 2018-04-06 | 四川凯茨阀门制造有限公司 | A kind of preparation method of metal corrosion-resistant coating |
| JP2020026458A (en) * | 2018-08-09 | 2020-02-20 | Ｋｊ特殊紙株式会社 | Exothermic coating material, planar heating element, and method for producing exothermic coating material |
| CN111218153A (en) * | 2019-11-19 | 2020-06-02 | 李岩康 | Method for producing structure having superhydrophobic surface |
-
2020
- 2020-09-14 CN CN202010957590.2A patent/CN112048202A/en not_active Withdrawn
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103289450A (en) * | 2013-04-23 | 2013-09-11 | 宁波墨西科技有限公司 | Carbon nanotube inorganic paint and usage method thereof |
| CN105295457A (en) * | 2015-10-30 | 2016-02-03 | 三棵树涂料股份有限公司 | Preparation method of carbon nano-tube loaded titanium dioxide top facing coating material |
| CN105802446A (en) * | 2016-03-31 | 2016-07-27 | 武汉理工大学 | Wear-resistant and super-hydrophobic coating material and preparation method thereof |
| CN106519744A (en) * | 2016-11-09 | 2017-03-22 | 东南大学 | Preparation method for carbon nanotube super-hydrophobic coating |
| CN107880751A (en) * | 2017-11-22 | 2018-04-06 | 四川凯茨阀门制造有限公司 | A kind of preparation method of metal corrosion-resistant coating |
| JP2020026458A (en) * | 2018-08-09 | 2020-02-20 | Ｋｊ特殊紙株式会社 | Exothermic coating material, planar heating element, and method for producing exothermic coating material |
| CN111218153A (en) * | 2019-11-19 | 2020-06-02 | 李岩康 | Method for producing structure having superhydrophobic surface |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115537118A (en) * | 2022-10-12 | 2022-12-30 | 电子科技大学 | Carbon nanotube ceramic coating and application method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102390936A (en) | Method for preparing corrosion-resisting and self-cleaning coating | |
| CN110499073B (en) | Method for preparing super-hydrophobic coating by modifying nano-cellulose and nano-particles serving as raw materials in aqueous solution through fluorine-free modifier | |
| CN105504898A (en) | Hydrophilic coating easy to clean and preparing method of hydrophilic coating | |
| CN112048202A (en) | Preparation method of steel-based corrosion-resistant super-hydrophobic coating | |
| CN114702880A (en) | Anti-cracking antioxidant antirust epoxy finish paint and preparation method thereof | |
| CN114276680B (en) | Super-hydrophobic composite material and preparation method and application thereof | |
| CN109179497B (en) | Preparation method of spherical titanium dioxide and application of spherical titanium dioxide in self-cleaning coating | |
| CN113462207B (en) | Photocatalytic self-cleaning composite coating and preparation method thereof | |
| CN115678411B (en) | Method for preparing GO/Ce-MOF@PDA/PU super-hydrophobic self-repairing anti-corrosion coating | |
| CN110564229A (en) | Method for rapidly preparing copper/polytetrafluoroethylene super-amphiphobic coating | |
| CN111020591B (en) | Preparation method of aluminum alloy with polished hydrophobic surface | |
| CN107815218A (en) | A kind of method for preparing polymolecularity graphene anticorrosive paint | |
| CN110643984B (en) | Method for rapidly preparing copper oxide/polytetrafluoroethylene super-amphiphobic coating | |
| JP7513339B1 (en) | Method for producing alkaline red mud coatings to prevent marine biofouling | |
| CN116273795B (en) | Preparation method of super-hydrophobic composite coating for ocean corrosion prevention and coating obtained by preparation method | |
| CN113861828B (en) | Method for preparing KM-SiO2@ PDA @ MoS2 wear-resistant super-hydrophobic coating by utilizing slag | |
| CN113667335A (en) | Super-oleophobic and super-hydrophobic nickel-titanium alloy material and preparation method thereof | |
| CN117210094A (en) | Wear-resistant, heat-conducting and corrosion-resistant super-amphiphobic composite coating and preparation method thereof | |
| CN116516333A (en) | Preparation method of rust conversion waterproof coating | |
| CN114855155A (en) | Aluminum alloy chromium-free treatment liquid and preparation method and application thereof | |
| CN110724957A (en) | Stainless steel surface salting liquid, preparation method and application | |
| CN113481499A (en) | Self-cleaning super-hydrophobic conversion film on metal matrix, preparation method thereof and film forming agent | |
| CN113881933A (en) | Chromium-free passivation solution and preparation method and use method thereof | |
| CN103214960A (en) | Coating technology of anticorrosion coating material | |
| CN103265886A (en) | Anticorrosion process for metal surface |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20201208 |