CN110982308A - Graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating - Google Patents

Graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating Download PDF

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CN110982308A
CN110982308A CN201911300196.5A CN201911300196A CN110982308A CN 110982308 A CN110982308 A CN 110982308A CN 201911300196 A CN201911300196 A CN 201911300196A CN 110982308 A CN110982308 A CN 110982308A
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graphene
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胡宏武
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Anhui Cloud Digital Push Network Technology Co Ltd
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    • 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
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract

The invention provides a graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating, which relates to the technical field of coatings, and comprises the following raw materials in parts by weight: 50-65 parts of nano alumina sol, 0.5-3 parts of graphene, 1-5 parts of modified tetrapod-like zinc oxide whiskers, 5-8 parts of polyester modified organic silicon resin, 3-7 parts of zirconium diboride ceramic closed-pore hollow microspheres, 2-5 parts of polycrystalline mullite fibers, 2-4.5 parts of silane coupling agent, 2-3.5 parts of aluminum dihydrogen phosphate, 3-5 parts of ethylene glycol, 0.3-0.8 part of dispersing agent and 0.2-0.4 part of flatting agent. According to the invention, the nano alumina sol is used as a main body, and the components such as graphene and tetrapod-like zinc oxide whiskers are added, so that the prepared rice ceramic coating is beautiful and compact in coating, high-temperature resistant, strong in corrosion resistance and excellent in adhesive force even when a small amount of polyester modified organic silicon resin is added.

Description

Graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating
Technical Field
The invention relates to the technical field of coatings, and particularly relates to a graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating.
Background
With the rapid development of modern science and technology, the innovation level and manufacturing technology of industrial equipment are continuously improved, and the demand for some special coatings with high temperature resistance and the like is increased. And part of exhaust equipment used in high-temperature environment and a chimney. The protection of the external surfaces of smelting furnaces, heaters, high-temperature reaction kettles, vehicle exhaust pipes, engines and the like is increasingly important. After high-temperature-resistant paint is coated on some high-temperature facilities, the high-temperature-resistant paint cannot be immediately put into operation; the high-temperature resistant coating coated on other equipment such as parts of vehicle exhaust pipes, engines and the like is treated for a long time in an alternative state of normal temperature, high temperature and water cooling scouring, so that the requirement on the comprehensive performance of the high-temperature resistant coating is very strict. Therefore, in the study of high temperature coatings, the mechanical properties, heat resistance, and performance requirements such as corrosion resistance before and after high temperature of the coatings need to be considered.
At present, the main high-temperature resistant coating mainly used is mainly an organic silicon coating. However, with the increase of the working temperature, at 800 ℃ of 700-.
With the progress of science and technology, new materials are emerging continuously, people utilize nano ceramic materials developed by nano technology to enhance and improve the functionality of the materials, such as heat insulation, heat preservation, high temperature resistance, insulativity, self-cleaning property, corrosion resistance and the like, the strength, toughness and superplasticity of the materials are greatly improved, a plurality of defects of the traditional ceramics are overcome, and important influences are generated on the mechanical, electrical, thermal, magnetic, optical, energy-saving and protective properties of the materials. The nano material is represented by nano ceramic paint, the nano ceramic paint is one of organic/inorganic hybrid paints, has excellent film forming property and flexibility, but is different from common organic/inorganic hybrid materials in that the main component of a film forming material is inorganic nano ions, and the inorganic component is as high as 70-80%.
Chinese patent with application number CN201610149378.7 discloses an energy-storage luminescent ceramic coating, which is prepared from three groups of components in parts by weight as follows: the component A comprises: 30-90 parts of nano silica sol, 10-30 parts of nano alumina sol, 0-20 parts of filler, 0.2-5 parts of catalyst and 1-60 parts of water; and B component: 30-70 parts of organic silicon resin, 10-30 parts of organic solvent, 5-20 parts of binder and 2-10 parts of auxiliary agent; 50-90 parts of energy storage luminescent powder and 0-50 parts of solvent. Wherein the weight ratio of A to B is 1:0.5-1: 3; the weight ratio of (A + B) to C is 1:0.1-1: 0.8. The coating disclosed by the invention has the functions of high temperature resistance, environmental protection, self-cleaning property and the like of ceramic coatings, and also has the characteristic of self-luminescence, so that the application field is very wide. But still contains more organic silicon resin, easily produces poisonous and harmful gas, and comprehensive properties is not strong, is not suitable for long-term protection under high temperature.
Disclosure of Invention
The invention aims to provide a graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating, which is prepared by taking nano alumina sol as a main body and adding components such as graphene, tetrapod-like zinc oxide whisker and the like, and has the advantages of attractive and compact coating, high temperature resistance, strong corrosion resistance and excellent adhesion even when a small amount of polyester modified organic silicon resin is added.
In order to achieve the purpose, the invention is realized by the following technical scheme:
the graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating comprises the following raw materials in parts by weight: 50-65 parts of nano alumina sol, 0.5-3 parts of graphene, 1-5 parts of modified tetrapod-like zinc oxide whiskers, 5-8 parts of polyester modified organic silicon resin, 3-7 parts of zirconium diboride ceramic closed-pore hollow microspheres, 2-5 parts of polycrystalline mullite fibers, 2-4.5 parts of silane coupling agent, 2-3.5 parts of aluminum dihydrogen phosphate, 3-5 parts of ethylene glycol, 0.3-0.8 part of dispersing agent and 0.2-0.4 part of flatting agent.
Preferably, the particle size of the nano alumina in the nano alumina sol is 10-20 nm.
Preferably, the preparation method of the graphene comprises the following steps: preparing graphene oxide by using natural crystalline flake graphite as a raw material by using a Hummers method, and reducing the graphene oxide to prepare graphene; the diameter of the graphene is 0.5-1 mu m, and the thickness of the graphene is 0.5-3 nm.
Preferably, the preparation method of the modified tetrapod-like zinc oxide whisker comprises the following steps: dropwise adding hydrochloric acid into water to adjust the pH value to 4.5-5, then adding tetrapod-like zinc oxide whiskers, and stirring at the temperature of 70-80 ℃ for 3-4 h; then carrying out suction filtration, washing and drying to obtain the modified tetrapod-like zinc oxide whisker; the length of the needle body of the tetrapod-like zinc oxide whisker used by the modified tetrapod-like zinc oxide whisker is 15-30 mu m, and the diameter of the root of the needle body is 1-3 mu m.
Preferably, the particle size of the zirconium diboride ceramic closed-cell hollow microspheres is 5-15 μm.
Preferably, the diameter of the polycrystalline mullite fiber is 1-20 mu m, and the length-diameter ratio is more than or equal to 8.
Preferably, the silane coupling agent is one or more of gamma-glycidoxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, and N- β - (aminoethyl) -gamma-aminopropylmethyldimethoxysilane.
Preferably, the dispersant is one of BYK-187, BYK-190 and BYK-191.
Preferably, the leveling agent is one of BYK-310, BYK-354 and BYK-358.
The preparation method of the graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating comprises the following steps:
(1) dissolving a silane coupling agent in acetone, adding graphene, modified tetrapod-like zinc oxide whiskers, zirconium diboride ceramic closed-pore hollow microspheres and polycrystalline mullite fibers, stirring at normal temperature for 60-90min, then vacuum-drying at 60-70 ℃ for 60-90min, and then placing at 120-135 ℃ for 60-90min to obtain a pretreatment mixture;
(2) and (2) placing the polyester modified organic silicon resin and the aluminum dihydrogen phosphate into a stirring tank, sequentially adding the dispersing agent, the pretreated mixture and the ethylene glycol at the rotating speed of 400r/min through 300-.
The invention has the beneficial effects that:
according to the invention, the graphene is added into the nano alumina sol, and as the alumina nano particles in the sol attract the graphene and the modified tetrapod-like zinc oxide whiskers to be combined with the graphene and the modified tetrapod-like zinc oxide whiskers, and the graphene and the modified tetrapod-like zinc oxide whiskers have strong physical binding force, the combination can reduce the generation of coating cracks and can effectively increase the corrosion resistance of the coating. The graphene can also effectively improve the toughness of the coating and reduce the generation of defects such as cracks in the coating, and the coating still has good adhesive force at high temperature and is not easy to peel off at high temperature. The added modified tetrapod-like zinc oxide whiskers can effectively improve the strength and the cracking resistance of the coating, have a strong reinforcing effect on the heat resistance of the coating, and the acid-modified tetrapod-like zinc oxide whiskers have enhanced surface roughness, so that the bonding force between the acid-modified tetrapod-like zinc oxide whiskers and other components is stronger. On the basis, a small amount of polyester modified organic silicon resin is added to form a three-dimensional network structure, the network structure is inserted among the nano particles, so that the coating is smoother, the storage stability can be improved, and the adhesion of the coating is greatly improved by matching with aluminum dihydrogen phosphate. The zirconium boride ceramic closed-cell hollow microspheres added in the invention can enhance the heat resistance of the coating, and the polycrystalline mullite fiber has a certain enhancement effect on the coating and greatly improves the heat resistance of the coating.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but 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:
the graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating comprises the following raw materials in parts by weight: 60 parts of nano alumina sol, 2 parts of graphene, 3 parts of modified tetrapod-like zinc oxide whiskers, 7 parts of polyester modified organic silicon resin, 5 parts of zirconium diboride ceramic closed-pore hollow microspheres, 3 parts of polycrystalline mullite fiber, 3.5 parts of gamma-glycidyl ether oxypropyl trimethoxysilane, 3 parts of aluminum dihydrogen phosphate, 4 parts of ethylene glycol, BYK-1870.5 parts of a dispersing agent and BYK-3100.3 parts of a flatting agent.
The grain diameter of the nano alumina in the nano alumina sol is 10-20 nm. The diameter of the graphene is 0.5-1 μm, and the thickness of the graphene is 0.5-3 nm. The particle size of the zirconium diboride ceramic closed-cell hollow microspheres is 5-15 μm. The diameter of the polycrystalline mullite fiber is 1-20 μm, and the length-diameter ratio is more than or equal to 8.
The preparation method of the modified tetrapod-like zinc oxide whisker comprises the following steps: dropwise adding hydrochloric acid into water to adjust the pH value to 4.5-5, then adding tetrapod-like zinc oxide whiskers, and stirring at the temperature of 70-80 ℃ for 3-4 h; then carrying out suction filtration, washing and drying to obtain the modified tetrapod-like zinc oxide whisker; the length of the needle body of the tetrapod-like zinc oxide whisker used by the modified tetrapod-like zinc oxide whisker is 15-30 mu m, and the diameter of the root of the needle body is 1-3 mu m.
The preparation method of the graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating comprises the following steps:
(1) dissolving gamma-glycidyl ether oxypropyltrimethoxysilane in acetone, adding graphene, modified tetrapod-like zinc oxide whiskers, zirconium diboride ceramic closed-pore hollow microspheres and polycrystalline mullite fibers, stirring at normal temperature for 80min, drying at 65 ℃ for 80min in vacuum, and standing at 125 ℃ for 70min to obtain a pretreatment mixture;
(2) and (2) placing the polyester modified organic silicon resin and the aluminum dihydrogen phosphate into a stirring tank, sequentially adding a dispersing agent BYK-187, the pretreated mixture and the ethylene glycol at the rotating speed of 400r/min, uniformly stirring, adding the nano alumina sol and the flatting agent BYK-310, stirring at the rotating speed of 1000r/min for 25min, and uniformly dispersing to obtain the high-temperature-resistant nano ceramic coating.
Example 2:
the graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating comprises the following raw materials in parts by weight: 585 parts of nano alumina sol, 2 parts of graphene, 3 parts of modified tetrapod-like zinc oxide whiskers, 7 parts of polyester modified organic silicon resin, 6 parts of zirconium diboride ceramic closed-cell hollow microspheres, 4 parts of polycrystalline mullite fiber, 2.5 parts of gamma- (methacryloyloxy) propyl trimethoxy silane, 2.5 parts of aluminum dihydrogen phosphate, 5 parts of ethylene glycol, BYK-1900.5 parts of a dispersing agent and BYK-3580.35 parts of a flatting agent.
The grain diameter of the nano alumina in the nano alumina sol is 10-20 nm. The diameter of the graphene is 0.5-1 μm, and the thickness of the graphene is 0.5-3 nm. The particle size of the zirconium diboride ceramic closed-cell hollow microspheres is 5-15 μm. The diameter of the polycrystalline mullite fiber is 1-20 μm, and the length-diameter ratio is more than or equal to 8.
The preparation method of the modified tetrapod-like zinc oxide whisker comprises the following steps: dropwise adding hydrochloric acid into water to adjust the pH value to 4.5, then adding tetrapod-like zinc oxide whiskers, and stirring at the temperature of 70 ℃ for 3.5 hours; then carrying out suction filtration, washing and drying to obtain the modified tetrapod-like zinc oxide whisker; the length of the needle body of the tetrapod-like zinc oxide whisker used by the modified tetrapod-like zinc oxide whisker is 15-30 mu m, and the diameter of the root of the needle body is 1-3 mu m.
The preparation method of the graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating comprises the following steps:
(1) dissolving gamma- (methacryloyloxy) propyl trimethoxy silane in acetone, adding graphene, modified tetrapod-like zinc oxide whiskers, zirconium diboride ceramic closed-pore hollow microspheres and polycrystalline mullite fibers, stirring at normal temperature for 70min, vacuum-drying at 70 ℃ for 80min, and standing at 130 ℃ for 80min to obtain a pretreatment mixture;
(2) and (2) placing the polyester modified organic silicon resin and aluminum dihydrogen phosphate into a stirring tank, sequentially adding a dispersing agent BYK-190, a pretreated mixture and ethylene glycol at the rotating speed of 300r/min, uniformly stirring, adding nano alumina sol and a flatting agent BYK-358, stirring at the rotating speed of 800r/min for 30min, and uniformly dispersing to obtain the high-temperature-resistant nano ceramic coating.
Example 3:
the graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating comprises the following raw materials, by weight, 65 parts of nano alumina sol, 0.5 part of graphene, 3 parts of modified tetrapod-like zinc oxide whisker, 8 parts of polyester modified organic silicon resin, 5 parts of zirconium diboride ceramic closed-pore hollow microspheres, 5 parts of polycrystalline mullite fiber, 2 parts of N- β - (aminoethyl) -gamma-aminopropyl methyl dimethoxysilane, 3 parts of aluminum dihydrogen phosphate, 5 parts of ethylene glycol, BYK-1900.3 parts of a dispersing agent and BYK-3100.3 parts of a flatting agent.
The grain diameter of the nano alumina in the nano alumina sol is 10-20 nm. The diameter of the graphene is 0.5-1 μm, and the thickness of the graphene is 0.5-3 nm. The particle size of the zirconium diboride ceramic closed-cell hollow microspheres is 5-15 μm. The diameter of the polycrystalline mullite fiber is 1-20 μm, and the length-diameter ratio is more than or equal to 8.
The preparation method of the modified tetrapod-like zinc oxide whisker comprises the following steps: dropwise adding hydrochloric acid into water to adjust the pH value to 5, then adding tetrapod-like zinc oxide whiskers, and stirring for 4 hours at the temperature of 70 ℃; then carrying out suction filtration, washing and drying to obtain the modified tetrapod-like zinc oxide whisker; the length of the needle body of the tetrapod-like zinc oxide whisker used by the modified tetrapod-like zinc oxide whisker is 15-30 mu m, and the diameter of the root of the needle body is 1-3 mu m.
The preparation method of the graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating comprises the following steps:
(1) dissolving N- β - (aminoethyl) -gamma-aminopropylmethyldimethoxysilane in acetone, adding graphene, modified tetrapod-like zinc oxide whiskers, zirconium diboride ceramic closed-pore hollow microspheres and polycrystalline mullite fibers, stirring at normal temperature for 90min, vacuum drying at 65 ℃ for 70min, and standing at 135 ℃ for 60min to obtain a pretreatment mixture;
(2) and (2) placing the polyester modified organic silicon resin and aluminum dihydrogen phosphate into a stirring tank, sequentially adding a dispersing agent BYK-190, a pretreated mixture and ethylene glycol at the rotating speed of 400r/min, uniformly stirring, adding a nano alumina sol and a flatting agent BYK-310, stirring at the rotating speed of 800r/min for 30min, and uniformly dispersing to obtain the high-temperature-resistant nano ceramic coating.
Example 4:
the graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating comprises the following raw materials in parts by weight: 55 parts of nano alumina sol, 2 parts of graphene, 1 part of modified tetrapod-like zinc oxide whisker, 6 parts of polyester modified organic silicon resin, 7 parts of zirconium diboride ceramic closed-cell hollow microspheres, 3 parts of polycrystalline mullite fiber, 4.5 parts of gamma- (methacryloyloxy) propyl trimethoxy silane, 2 parts of aluminum dihydrogen phosphate, 3 parts of ethylene glycol, BYK-1870.6 parts of a dispersing agent and BYK-3580.2 parts of a flatting agent.
The grain diameter of the nano alumina in the nano alumina sol is 10-20 nm. The diameter of the graphene is 0.5-1 μm, and the thickness of the graphene is 0.5-3 nm. The particle size of the zirconium diboride ceramic closed-cell hollow microspheres is 5-15 μm. The diameter of the polycrystalline mullite fiber is 1-20 μm, and the length-diameter ratio is more than or equal to 8.
The preparation method of the modified tetrapod-like zinc oxide whisker comprises the following steps: dropwise adding hydrochloric acid into water to adjust the pH value to 4.5, then adding tetrapod-like zinc oxide whiskers, and stirring for 3 hours at the temperature of 80 ℃; then carrying out suction filtration, washing and drying to obtain the modified tetrapod-like zinc oxide whisker; the length of the needle body of the tetrapod-like zinc oxide whisker used by the modified tetrapod-like zinc oxide whisker is 15-30 mu m, and the diameter of the root of the needle body is 1-3 mu m.
The preparation method of the graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating comprises the following steps:
(1) dissolving gamma- (methacryloyloxy) propyl trimethoxy silane in acetone, adding graphene, modified tetrapod-like zinc oxide whiskers, zirconium diboride ceramic closed-pore hollow microspheres and polycrystalline mullite fibers, stirring at normal temperature for 60min, vacuum-drying at 60 ℃ for 90min, and standing at 130 ℃ for 80min to obtain a pretreatment mixture;
(2) and (2) placing the polyester modified organic silicon resin and the aluminum dihydrogen phosphate into a stirring tank, sequentially adding a dispersing agent BYK-187, the pretreated mixture and the ethylene glycol at the rotating speed of 400r/min, uniformly stirring, adding the nano alumina sol and the flatting agent BYK-358, stirring at the rotating speed of 900r/min for 30min, and uniformly dispersing to obtain the high-temperature-resistant nano ceramic coating.
Example 5:
the graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating comprises the following raw materials in parts by weight: 62 parts of nano alumina sol, 3 parts of graphene, 5 parts of modified tetrapod-like zinc oxide whiskers, 5 parts of polyester modified organic silicon resin, 3 parts of zirconium diboride ceramic closed-pore hollow microspheres, 2 parts of polycrystalline mullite fiber, 3 parts of gamma-glycidyl ether oxypropyl trimethoxy silane, 3.5 parts of aluminum dihydrogen phosphate, 4 parts of ethylene glycol, BYK-1910.8 parts of a dispersing agent and BYK-3540.4 parts of a flatting agent.
The grain diameter of the nano alumina in the nano alumina sol is 10-20 nm. The diameter of the graphene is 0.5-1 μm, and the thickness of the graphene is 0.5-3 nm. The particle size of the zirconium diboride ceramic closed-cell hollow microspheres is 5-15 μm. The diameter of the polycrystalline mullite fiber is 1-20 μm, and the length-diameter ratio is more than or equal to 8.
The preparation method of the modified tetrapod-like zinc oxide whisker comprises the following steps: dropwise adding hydrochloric acid into water to adjust the pH value to 5, then adding tetrapod-like zinc oxide whiskers, and stirring at the temperature of 75 ℃ for 3.5 hours; then carrying out suction filtration, washing and drying to obtain the modified tetrapod-like zinc oxide whisker; the length of the needle body of the tetrapod-like zinc oxide whisker used by the modified tetrapod-like zinc oxide whisker is 15-30 mu m, and the diameter of the root of the needle body is 1-3 mu m.
The preparation method of the graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating comprises the following steps:
(1) dissolving a silane coupling agent in acetone, adding graphene, modified tetrapod-like zinc oxide whiskers, zirconium diboride ceramic closed-pore hollow microspheres and polycrystalline mullite fibers, stirring at normal temperature for 70min, drying at 70 ℃ in vacuum for 60min, and then placing at 120 ℃ for 60min to obtain a pretreatment mixture;
(2) and (2) placing the polyester modified organic silicon resin and the aluminum dihydrogen phosphate into a stirring tank, sequentially adding the dispersant BYK-191, the pretreated mixture and the ethylene glycol at the rotating speed of 400r/min for 300-.
Example 6:
the graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating comprises the following raw materials in parts by weight: 53 parts of nano alumina sol, 2 parts of graphene, 3 parts of modified tetrapod-like zinc oxide whiskers, 6 parts of polyester modified organic silicon resin, 6 parts of zirconium diboride ceramic closed-cell hollow microspheres, 2 parts of polycrystalline mullite fibers, 4 parts of a silane coupling agent, 3 parts of aluminum dihydrogen phosphate, 4 parts of ethylene glycol, a dispersing agent, BYK-1900.5 parts and a flatting agent BYK-3580.25 parts.
The grain diameter of the nano alumina in the nano alumina sol is 10-20 nm. The diameter of the graphene is 0.5-1 μm, and the thickness of the graphene is 0.5-3 nm. The particle size of the zirconium diboride ceramic closed-cell hollow microspheres is 5-15 μm. The diameter of the polycrystalline mullite fiber is 1-20 μm, and the length-diameter ratio is more than or equal to 8.
The silane coupling agent is gamma-glycidoxypropyltrimethoxysilane or gamma- (methacryloyloxy) propyltrimethoxysilane in a mass ratio of 1: 1.
The preparation method of the modified tetrapod-like zinc oxide whisker is the same as that of example 1.
The preparation method of the graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating is the same as that in example 1.
Example 7:
the graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating comprises the following raw materials in parts by weight: 62 parts of nano alumina sol, 2 parts of graphene, 3 parts of modified tetrapod-like zinc oxide whiskers, 5 parts of polyester modified organic silicon resin, 5 parts of zirconium diboride ceramic closed-cell hollow microspheres, 3 parts of polycrystalline mullite fibers, 3.5 parts of a silane coupling agent, 3 parts of aluminum dihydrogen phosphate, 4 parts of ethylene glycol, BYK-1900.5 parts of a dispersing agent and BYK-3100.2 parts of a flatting agent.
The grain diameter of the nano alumina in the nano alumina sol is 10-20 nm. The diameter of the graphene is 0.5-1 μm, and the thickness of the graphene is 0.5-3 nm. The particle size of the zirconium diboride ceramic closed-cell hollow microspheres is 5-15 μm. The diameter of the polycrystalline mullite fiber is 1-20 μm, and the length-diameter ratio is more than or equal to 8.
The silane coupling agent is gamma-glycidoxypropyltrimethoxysilane or gamma- (methacryloyloxy) propyltrimethoxysilane in a mass ratio of 3: 1.
The preparation method of the modified tetrapod-like zinc oxide whisker is the same as that of example 2.
The preparation method of the graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating is the same as that in example 2.
Example 8:
the graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating comprises the following raw materials in parts by weight: 55 parts of nano alumina sol, 2.5 parts of graphene, 3.5 parts of modified tetrapod-like zinc oxide whiskers, 7 parts of polyester modified organic silicon resin, 6 parts of zirconium diboride ceramic closed-pore hollow microspheres, 4 parts of polycrystalline mullite fibers, 3 parts of a silane coupling agent, 2.5 parts of aluminum dihydrogen phosphate, 3.5 parts of ethylene glycol, BYK-1910.4 parts of a dispersing agent and BYK-3100.4 parts of a flatting agent.
The grain diameter of the nano alumina in the nano alumina sol is 10-20 nm. The diameter of the graphene is 0.5-1 μm, and the thickness of the graphene is 0.5-3 nm. The particle size of the zirconium diboride ceramic closed-cell hollow microspheres is 5-15 μm. The diameter of the polycrystalline mullite fiber is 1-20 μm, and the length-diameter ratio is more than or equal to 8.
The silane coupling agent is gamma-glycidoxypropyltrimethoxysilane or gamma- (methacryloyloxy) propyltrimethoxysilane in a mass ratio of 3: 1.
The preparation method of the modified tetrapod-like zinc oxide whisker is the same as that of example 2.
The preparation method of the graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating is the same as that in example 2.
And (3) performance testing:
the adhesion, drying time, and storage stability of the high temperature resistant nanoceramic coatings of examples 1-8 were tested. Specific test results are shown in table 1.
Table 1:
Figure BDA0002320178890000111
as can be seen from Table 1, the high-temperature nano ceramic coating disclosed by the invention can be self-dried at normal temperature, and is strong in adhesive force, attractive in coating appearance and strong in storage stability.
The high temperature resistant nanoceramic coatings of examples 1-8 were tested for corrosion resistance, heat resistance, and quench resistance, with the following specific conditions: acid resistance (5% H)2SO4500h), alkali resistance (5% NaOH, 500h), salt spray resistance (800h), post heat resistance salt spray (1000 ℃, 300h), heat resistance (1000 ℃, 10 h). Specific test results are shown in table 2.
Table 2:
Figure BDA0002320178890000121
as is clear from Table 2, the high temperature resistant nano-ceramic coatings of examples 1 to 8 are excellent in corrosion resistance, high temperature heat resistance, and very good.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. The graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating is characterized by comprising the following raw materials in parts by weight: 50-65 parts of nano alumina sol, 0.5-3 parts of graphene, 1-5 parts of modified tetrapod-like zinc oxide whiskers, 5-8 parts of polyester modified organic silicon resin, 3-7 parts of zirconium diboride ceramic closed-pore hollow microspheres, 2-5 parts of polycrystalline mullite fibers, 2-4.5 parts of silane coupling agent, 2-3.5 parts of aluminum dihydrogen phosphate, 3-5 parts of ethylene glycol, 0.3-0.8 part of dispersing agent and 0.2-0.4 part of flatting agent.
2. The graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nanoceramic coating according to claim 1, wherein the particle size of nano alumina in the nano alumina sol is 10-20 nm.
3. The graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nanoceramic coating according to claim 1, wherein the preparation method of the graphene comprises the following steps: preparing graphene oxide by using natural crystalline flake graphite as a raw material by using a Hummers method, and reducing the graphene oxide to prepare graphene; the diameter of the graphene is 0.5-1 mu m, and the thickness of the graphene is 0.5-3 nm.
4. The graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nanoceramic coating according to claim 1, wherein the preparation method of the modified tetrapod-like zinc oxide whisker comprises the following steps: dropwise adding hydrochloric acid into water to adjust the pH value to 4.5-5, then adding tetrapod-like zinc oxide whiskers, and stirring at the temperature of 70-80 ℃ for 3-4 h; then carrying out suction filtration, washing and drying to obtain the modified tetrapod-like zinc oxide whisker; the length of the needle body of the tetrapod-like zinc oxide whisker used by the modified tetrapod-like zinc oxide whisker is 15-30 mu m, and the diameter of the root of the needle body is 1-3 mu m.
5. The graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nanoceramic coating according to claim 1, wherein the particle size of the zirconium diboride ceramic closed-cell cenospheres is 5-15 μm.
6. The graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating according to claim 1, wherein the diameter of the polycrystalline mullite fiber is 1-20 μm, and the length-diameter ratio is not less than 8.
7. The graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nanoceramic coating according to claim 1, wherein the silane coupling agent is one or more of gamma-glycidoxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, and N- β - (aminoethyl) -gamma-aminopropylmethyldimethoxysilane.
8. The graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nanoceramic coating as claimed in claim 1, wherein the dispersant is one of BYK-187, BYK-190 and BYK-191.
9. The graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nano ceramic coating as claimed in claim 1, wherein the leveling agent is one of BYK-310, BYK-354 and BYK-358.
10. The graphene/tetrapod-like zinc oxide whisker high-temperature-resistant nanoceramic coating according to any one of claims 1-9, wherein the preparation method comprises the following steps:
(1) dissolving a silane coupling agent in acetone, adding graphene, modified tetrapod-like zinc oxide whiskers, zirconium diboride ceramic closed-pore hollow microspheres and polycrystalline mullite fibers, stirring at normal temperature for 60-90min, then vacuum-drying at 60-70 ℃ for 60-90min, and then placing at 120-135 ℃ for 60-90min to obtain a pretreatment mixture;
(2) and (2) placing the polyester modified organic silicon resin and the aluminum dihydrogen phosphate into a stirring tank, sequentially adding the dispersing agent, the pretreated mixture and the ethylene glycol at the rotating speed of 400r/min through 300-.
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* Cited by examiner, † Cited by third party
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CN114644843A (en) * 2020-12-18 2022-06-21 深圳优易材料科技有限公司 Anticorrosive and anti-sticking coating for grate segment of garbage incinerator and preparation method and application thereof
CN115838556A (en) * 2022-12-16 2023-03-24 山东新升实业发展有限责任公司 Metal support anti-corrosion treatment material and production process thereof
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114644843A (en) * 2020-12-18 2022-06-21 深圳优易材料科技有限公司 Anticorrosive and anti-sticking coating for grate segment of garbage incinerator and preparation method and application thereof
CN114644843B (en) * 2020-12-18 2023-10-24 深圳优易材料科技有限公司 Anticorrosive anti-sticking coating for fire grate of garbage incinerator, and preparation method and application thereof
CN115838556A (en) * 2022-12-16 2023-03-24 山东新升实业发展有限责任公司 Metal support anti-corrosion treatment material and production process thereof
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