CN111040582A - Graphene anticorrosive paint special for transformer shell and preparation method thereof - Google Patents
Graphene anticorrosive paint special for transformer shell and preparation method thereof Download PDFInfo
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- CN111040582A CN111040582A CN201911409012.9A CN201911409012A CN111040582A CN 111040582 A CN111040582 A CN 111040582A CN 201911409012 A CN201911409012 A CN 201911409012A CN 111040582 A CN111040582 A CN 111040582A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/04—Epoxynovolacs
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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
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0893—Zinc
Abstract
The invention relates to a graphene anticorrosive paint special for a transformer shell. A graphene anticorrosive paint special for a transformer shell is composed of a component A and a component B according to a mass ratio of 5-20: 1; the component A comprises the following raw materials in percentage by weight: 5-20% of epoxy resin, 1-5% of coupling agent, 2-15% of rheological additive, 1-15% of graphene resin slurry, 10-55% of zinc powder, 15-32% of filler and 5-25% of mixed solvent; the component B comprises the following raw materials in percentage by weight: 25-40% of curing agent and 60-75% of mixed solvent; the graphene resin slurry is composed of 30-50% of epoxy resin, 1-5% of rheological additive, 35-45% of mixed solvent, 1-15% of graphene and 5-10% of dispersant. The graphene anticorrosive paint special for the transformer shell has the advantages of high strength, good toughness, strong adhesion capability, low zinc content, neutral salt spray resistance testing time of more than 6000h, good corrosion resistance and capability of prolonging the service life of a transformer.
Description
Technical Field
The invention belongs to the technical field of anticorrosive coatings, and particularly relates to a graphene anticorrosive coating special for a transformer shell and a preparation method thereof.
Background
The transformer is an important device of a power system, is mostly installed in an outdoor and open environment, has a severe operation environment, is easily subjected to wind, sunshine, severe cold, high temperature, erosion of atmospheric acid rain or salt fog substances all the year round, is easy to age, corrode and damage, easily causes power equipment faults, brings great influence to normal production and life of people, and also causes great loss to power departments. In order to overcome the above problems, various measures have been developed to prevent and suppress the corrosion phenomenon of the transformer, and among them, the application of anticorrosive paint on the surface of the transformer case is the most economical and effective protection means.
At present, the common anticorrosive coatings at home and abroad mainly comprise epoxy coatings, polyurethane coatings, zinc-rich coatings and the like. The epoxy anticorrosive paint has good film-forming property and higher adhesive force, but the epoxy anticorrosive paint is not ageing-resistant, is easy to pulverize and has poor medium energy for bearing strong corrosion at high temperature; the polyurethane coating has excellent adhesive force, good mechanical property and good chemical corrosion resistance, but has poor construction performance and storage stability, and a paint film is easy to foam; the zinc-rich coating has the functions of shielding, electrochemical protection, self-repairing and passivation of a coating, but the corrosion resistance of the zinc-rich coating (the zinc content is usually more than 70 percent) is at the cost of sacrificing zinc powder, and a large amount of zinc oxide mist is generated during welding, so that the life health of operators is damaged.
In view of the above problems, there is a need for an environment-friendly anticorrosive coating with good corrosion resistance, good storage stability, convenient construction, low zinc content for coating protection of transformer housings.
Graphene is a novel carbonaceous material with a two-dimensional lamellar structure and formed by tightly stacking single-layer carbon atoms, has the characteristics of excellent rigidity, dimensional stability, toughness and the like, can remarkably improve the mechanical property of the coating when used as a modifier of the anticorrosive coating resin, and can overcome the defects of large mixing amount of common inorganic fillers, low modification efficiency and the like. In addition, the unique lamellar structure of the graphene can form a labyrinth physical barrier in the coating to isolate corrosion factors, long-acting protection is provided for metal, and meanwhile, an electric conduction and heat conduction channel can be constructed.
The prior art CN108727940A relates to a high-performance anticorrosive paint for a transformer, which comprises the following raw materials in parts by weight: 34-38 parts of phenolic resin, 27-31 parts of ferrocene modified polyphenylene sulfone resin, 16-22 parts of modified microcline feldspar, 5-9 parts of silicon carbide, 4-8 parts of expanded graphite, 3-5 parts of polyvinylpyrrolidone, 1-3 parts of pine juice, 2-4 parts of fumed silica and 6-10 parts of nano pearl powder. The modified microcline feldspar and the silicon carbide are used as main anticorrosive raw materials, so that the acid and alkali resistance of the coating is enhanced; the expanded graphite and the nano pearl powder improve the compactness of the material and further improve the comprehensive performance of the coating, and although the high-temperature-resistant anticorrosive coating (without graphene) for the transformer is provided, the high-temperature-resistant anticorrosive coating has more fillers and influences the mechanical property of the material.
The prior art CN105131679A discloses a graphene anticorrosive paint and a preparation method thereof, wherein the graphene anticorrosive paint takes graphene, zinc silicate, talcum powder, hexafluorobutyl methacrylate-acrylate copolymer emulsion, organosilicon modified fluorocarbon resin, hydroxyethyl cellulose, acrylic acid, 2,4, 6-tris (dimethylaminomethyl) phenol, dibutyltin dilaurate, styrene-acrylic emulsion, sodium tripolyphosphate, gas phase aluminum oxide, aluminum silicate fiber, triisopropyl phenyl phosphate, ammonium carbonate, titanium dioxide, a toughening agent, a coagulant, a diluent, iron powder and silica sol as raw materials, and is prepared by a step-by-step mixing method, so that the graphene anticorrosive paint with corrosion resistance, wear resistance and heat absorption is suitable for outdoor equipment of power grids. According to the invention, graphene is added into an organic silicon modified fluorocarbon resin system to prepare the anticorrosive coating, and the anticorrosive coating is coated on power grid outdoor equipment and subjected to a salt spray test and a scratch performance test, but the invention does not relate to the research of an epoxy resin system.
The prior art CN108395785A discloses an anticorrosive coating for a surface layer of power equipment and a preparation method thereof, relating to the field of anticorrosive coatings and comprising raw materials of 25-35 parts of epoxy resin, 15-25 parts of polyurethane resin, 30-40 parts of polyacrylic resin, 5-10 parts of polydimethylsiloxane, 4-8 parts of dibutyl phthalate, 6-10 parts of mica, 3-6 parts of red earth, 510 parts of bentonite, 4-8 parts of talcum powder, 4-8 parts of graphene, 3-6 parts of zinc powder, 3-6 parts of zinc oxide, 3-6 parts of aluminum oxide, 4-8 parts of glass fiber, 3-6 parts of nano titanium dioxide, 3-6 parts of nano silicon carbide, 2-4 parts of microcrystalline paraffin, 2-4 parts of butyl stearate, 10-15 parts of acetone and the like by weight; the coating of the invention has excellent heat resistance and aging resistance, and the coating is not easy to chap and is easy to operate. According to the invention, the graphene is added into the epoxy resin coating, so that the permeability resistance, the thermal stability and the chemical stability of the coating are improved after the graphene is added, but the invention does not mention the research on the anticorrosion performance of the coating, the anticorrosion effect and the like.
In view of the above, the invention provides a graphene anticorrosive paint special for a transformer shell and a preparation method thereof.
Disclosure of Invention
The invention aims to provide the special graphene anticorrosive paint for the transformer shell, which has the advantages of high strength, good toughness, strong adhesion capacity, low zinc content, good corrosion resistance and capability of prolonging the service life of a transformer, and the neutral salt spray resistance test time exceeds 6000 h.
In order to realize the purpose, the adopted technical scheme is as follows:
a graphene anticorrosive paint special for a transformer shell is composed of a component A and a component B according to a mass ratio of 5-20: 1;
the component A comprises the following raw materials in percentage by weight: 5-20% of epoxy resin, 1-5% of coupling agent, 2-15% of rheological additive, 1-15% of graphene resin slurry, 10-55% of zinc powder, 15-32% of filler and 5-25% of mixed solvent;
the graphene resin slurry is prepared from the following raw materials in percentage by weight: 30-50% of epoxy resin, 1-5% of rheological additive, 35-45% of mixed solvent, 1-15% of graphene and 5-10% of dispersant;
the component B comprises the following raw materials in percentage by weight: 25-40% of curing agent and 60-75% of mixed solvent.
Furthermore, the coupling agent is selected from one or more of gamma-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane.
Furthermore, the rheological additive is selected from one or more of organic bentonite, polyethylene wax and polyamide wax.
Further, the graphene sheet diameter in the graphene resin slurry is 5-50 μm;
the dispersant is one or more of copolymer solution containing acidic functional groups, a composition of polar acidic ester and high molecular alcohol, and high molecular weight copolymer alkyl ammonium salt.
Further, the filler is selected from one or more of mica iron oxide ash, iron calcium powder, phosphorus titanium powder and phosphorus iron powder.
Further, the mixed solvent is selected from at least two of xylene, n-butanol, ethanol, toluene, propylene glycol methyl ether and cyclohexanone.
Further, the curing agent is selected from amine curing agents, including one or more of polyamide curing agents, fatty amine curing agents and phenolic amine curing agents.
Further, the epoxy resin is selected from any one of a low molecular weight bisphenol a type epoxy resin, a medium molecular weight bisphenol a type epoxy resin, a high molecular weight bisphenol a type epoxy resin, and a novolac epoxy resin.
The invention also aims to provide a preparation method of the graphene anticorrosive paint special for the transformer shell, and the preparation method is simple.
In order to realize the purpose, the adopted technical scheme is as follows:
the preparation method of the graphene anticorrosive paint special for the transformer shell comprises the following steps:
(1) preparing a component A in the coating:
preparing graphene resin slurry:
uniformly mixing the epoxy resin, the rheological additive and the mixed solvent, and then carrying out infiltration treatment on the graphene; after the infiltration treatment is finished, dropwise adding a dispersing agent while stirring, after the dropwise adding is finished, stirring at a high speed for 35min, then ultrasonically dispersing for 20min, and finally grinding by using a three-roller machine to obtain stable graphene resin slurry;
preparing a component A:
mixing epoxy resin, an auxiliary agent, a large amount of mixed solvent, graphene resin slurry and a coupling agent, stirring at a high speed for 30min, then sequentially adding zinc powder, a filler and the rest of the mixed solvent, dispersing, grinding and stirring at a rotation speed of 1500-3000r/min and a temperature of less than or equal to 50 ℃ until the fineness is less than 40 mu m, and filtering to obtain a component A in the coating;
wherein the dosage of the large amount of mixed solvent is not less than 70 percent of the total dosage of the mixed solvent;
(2) preparing a component B in the coating:
dissolving the curing agent with the mixed solvent uniformly at a temperature of not more than 50 ℃, and dispersing for 30min to obtain a component B in the coating;
(3) and (3) blending and stirring the component A and the component B in the coating uniformly according to a predetermined ratio to obtain the graphene anticorrosive coating special for the transformer shell.
Compared with the prior art, the invention has the beneficial effects that:
1. the graphene epoxy anticorrosive paint disclosed by the invention is simple in preparation method, and the graphene epoxy anticorrosive paint prepared by performing infiltration dispersion treatment on graphene and controlling raw material components and proportion has the characteristics of good adhesive force, excellent anticorrosive performance and higher mechanical strength, and meets the long-acting anticorrosive requirement of a transformer shell.
2. Compared with the traditional epoxy zinc-rich anticorrosive coating, when the coating is used as a metal base material for corrosion prevention, the salt spray resistance test performance of the graphene anticorrosive coating provided by the invention can reach more than 6000h at most under the condition of the same zinc content, and the performance of the coating is far superior to that of the traditional epoxy zinc-rich coating (in the existing industry standard HG/T3668-2009, the industry standard of the salt spray resistance time of the organic zinc-rich primer is pointed out, namely the content of metal zinc in nonvolatile components is more than or equal to 80%, the salt spray resistance time is required to be 600h, the content of metal zinc in nonvolatile components is more than or equal to 60%, and the salt spray resistance time is required to be 200 h).
3. The anticorrosive coating of the invention greatly reduces the dosage of zinc powder and reduces the environmental pollution caused by zinc fog and the harm of harmful gas generated in the welding process while improving the anticorrosive effect.
4. The graphene anticorrosive paint special for the transformer shell is less in added raw material variety, wide in source, simple in preparation process and easy for large-scale industrial production.
Drawings
Fig. 1 is a 5000h picture of the graphene anticorrosive coating special for the transformer case prepared in embodiment 2 of the invention after a salt spray test;
FIG. 2 is a 600h picture of a conventional epoxy zinc rich paint containing 84.44% zinc in comparative example 3 after a salt spray test;
FIG. 3 is a picture of the graphene anti-corrosive paint of comparative example 1, which is not within the protection range, after a salt spray test for 200 h;
FIG. 4 is a picture of a coating containing 52.03% zinc and graphene powder added in comparative example 2 after a salt spray test for 300 h;
FIG. 5 is a scanning electron microscope picture (magnification: 20X) of a salt spray test for 600h of the conventional epoxy zinc-rich anticorrosive paint containing 84.44% of zinc in comparative example 3;
FIG. 6 is a 5000h scanning electron microscope picture (magnification: 20X) of the graphene anticorrosive coating special for the transformer case prepared in example 2 of the invention through a salt spray test;
FIG. 7 is a 5000h scanning electron microscope picture (magnification: 1KX) of the graphene anticorrosive coating special for the transformer shell prepared in example 2 of the invention through a salt spray test.
Detailed Description
In order to further illustrate the graphene anticorrosive paint specially used for the transformer housing and the preparation method thereof, and achieve the intended purpose of the invention, the following detailed description is provided with reference to the preferred embodiments for the graphene anticorrosive paint specially used for the transformer housing and the preparation method thereof according to the present invention, and the specific implementation, structure, characteristics and efficacy thereof are described in detail. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
The specific embodiment of the graphene anticorrosive coating special for the transformer shell and the preparation method thereof are further described in detail below:
the graphene anticorrosive coatings prepared in examples 1-2 and comparative example 1 were prepared as follows.
A: preparing a component A in the coating:
(1) preparing graphene resin slurry:
uniformly mixing the epoxy resin, the rheological additive and the mixed solvent according to a ratio, and performing infiltration treatment on the graphene to obtain the graphene after the infiltration treatment; and after the soaking treatment, dropwise adding a dispersing agent (solvent-free high molecular weight copolymer alkyl ammonium salt) into the mixed solution after the soaking treatment while stirring, after dropwise adding, stirring at a high speed for 35min, performing ultrasonic dispersion for 20min, and finally grinding by using a three-roller machine to obtain the stable graphene resin slurry.
The graphene resin slurry is prepared from the following raw materials in percentage by weight: 30-50% of epoxy resin, 1-5% of rheological additive, 35-45% of mixed solvent, 1-15% of graphene and 5-10% of dispersant. The graphene sheet diameter in the graphene resin slurry is 5-50 μm.
Adopting an infiltration dispersion method to perform infiltration treatment on graphene in a solvent and resin (EP), and preparing a composite intermediate with the advantages of the graphene and the EP through a graphene/EP synergistic effect: the graphene after infiltration and dispersion is adsorbed by the epoxy groups of EP, so that the graphene can be uniformly dispersed in an EP matrix, and various excellent properties of the graphene are fully exerted; in addition, by utilizing the characteristics of excellent rigidity, dimensional stability, toughness and the like of the graphene as the modifier of EP, the mechanical property of the coating can be obviously improved, and the defects of large mixing amount of common inorganic filler, low modification efficiency and the like can be overcome.
(2) Preparation:
adding epoxy resin, rheological additive, a large amount of mixed solvent, graphene resin slurry and coupling agent in the component A formula into a stirring tank, mixing for 30min at high speed, sequentially adding zinc powder, filler and the rest of mixed solvent, performing dispersion, grinding and stirring treatment at the rotation speed of 1500-3000r/min and the temperature of less than or equal to 50 ℃, sampling and testing, wherein the fineness is less than 40 mu m, and filtering by using a filter screen to obtain the component A in the coating;
wherein the component A comprises the following raw materials in percentage by weight: 5-20% of epoxy resin, 1-5% of coupling agent, 2-15% of rheological additive, 1-15% of graphene resin slurry, 10-55% of zinc powder, 15-32% of filler and 5-25% of mixed solvent.
The epoxy resin, the rheological additive and the mixed solvent in the graphene resin slurry are the same as those in the component A.
The dosage of the large amount of mixed solvent is not less than 70 percent of the total dosage of the mixed solvent.
B: preparing a component B in the coating:
according to the formula amount of the component B, the amine curing agent and the mixed solvent are uniformly dissolved and dispersed at low speed for 30min, and the temperature is controlled to be less than or equal to 50 ℃, so that the component B in the coating is obtained; the component B comprises the following raw materials in percentage by weight: 25-40% of curing agent and 60-75% of mixed solvent.
And mixing the component A and the component B in the coating according to the mass ratio of (5-20) to 1, and uniformly stirring to obtain the graphene anticorrosive coating.
Example 3.
The procedure of example 3 was the same as that of examples 1-2, except for the specific ingredients and amounts thereof.
The graphene anticorrosive paint special for the transformer shell prepared in the embodiment 3 is composed of a component A and a component B according to a mass ratio of 15: 1;
the component A comprises the following raw materials in percentage by weight: 5% of epoxy resin (novolac epoxy resin), 2% of coupling agent (3-aminopropyltriethoxysilane), 3% of rheological additive (polyethylene wax), 14% of graphene resin slurry, 55% of zinc powder, 15% of filler (iron calcium powder) and 6% of mixed solvent (ethanol and toluene);
the graphene resin slurry is prepared from the following raw materials in percentage by weight: 44% of novolac epoxy resin, 2% of rheological additive, 45% of mixed solvent, 4% of graphene and 5% of dispersant (copolymer solution containing acidic functional groups);
the component B comprises the following raw materials in percentage by weight: 35% of curing agent (fatty amine curing agent) and 65% of mixed solvent (ethanol and toluene).
Example 4.
The procedure of example 4 was the same as that of examples 1-2, except for the specific ingredients and amounts thereof.
The graphene anticorrosive paint special for the transformer shell prepared in the embodiment 4 consists of a component A and a component B according to a mass ratio of 12: 1;
the component A comprises the following raw materials in percentage by weight: 12% of epoxy resin (novolac epoxy resin), 5% of coupling agent (gamma- (methacryloyloxy) propyl trimethoxy silane), 4% of rheological additive (polyamide wax), 12% of graphene resin slurry, 25% of zinc powder, 32% of filler (phosphorus iron powder) and 10% of mixed solvent (toluene and propylene glycol methyl ether);
the graphene resin slurry is prepared from the following raw materials in percentage by weight: 35% of novolac epoxy resin, 5% of rheological additive, 40% of mixed solvent, 10% of graphene and 10% of dispersing agent (high molecular alcohol);
the component B comprises the following raw materials in percentage by weight: 40% of curing agent (phenolic aldehyde amine curing agent) and 60% of mixed solvent (toluene and propylene glycol methyl ether).
Example 5.
The procedure of example 5 was the same as that of examples 1-2, except for the specific ingredients and amounts thereof.
The graphene anticorrosive paint special for the transformer shell prepared in the embodiment 5 consists of a component A and a component B according to a mass ratio of 8: 1;
the component A comprises the following raw materials in percentage by weight: 10% of epoxy resin (novolac epoxy resin), 1% of coupling agent (gamma-glycidyl ether oxypropyltrimethoxysilane), 5% of rheological additive (polyethylene wax and polyamide wax), 10% of graphene resin slurry, 40% of zinc powder, 27% of filler (ferrophosphorus powder) and 7% of mixed solvent (cyclohexanone and toluene);
the graphene resin slurry is prepared from the following raw materials in percentage by weight: 50% of novolac epoxy resin, 2% of rheological additive, 35% of mixed solvent, 7% of graphene and 6% of dispersing agent (polar acid ester and high molecular alcohol);
the component B comprises the following raw materials in percentage by weight: 30% of curing agent (polyamide curing agent and phenolic amine curing agent) and 70% of mixed solvent (cyclohexanone and toluene).
Comparative examples 2 to 3 the method of preparing the anticorrosive coatings was as follows.
A: preparing a component A in the coating:
adding epoxy resin, rheological additive, a large amount of mixed solvent, graphene powder (graphene is not added in a comparative example 3) and coupling agent in the component A formula into a stirring tank for mixing, stirring at high speed for 30min, then sequentially adding zinc powder, filler and the rest of mixed solvent, performing dispersion, grinding and stirring treatment under the conditions that the rotating speed is 1500-3000r/min and the temperature is less than or equal to 50 ℃, sampling and testing, wherein the fineness is less than 40 mu m, and filtering by using a filter screen to obtain the component A in the coating;
wherein the dosage of the large amount of mixed solvent is not less than 70 percent of the total dosage of the mixed solvent.
B: preparing a component B in the coating:
according to the formula amount of the component B, the amine curing agent and the mixed solvent are uniformly dissolved and dispersed at low speed for 30min, and the temperature is controlled to be less than or equal to 50 ℃, so that the component B in the coating is obtained;
and (3) mixing the component A and the component B in the paint according to the mass ratio of (5-20) to 1, and uniformly stirring to obtain the anticorrosive paint.
Embodiment 1-2 is the graphene anticorrosive paint special for the transformer housing of the invention; comparative example 1 is a graphene anticorrosive coating with the component dosage not within the protection range; comparative example 2 is a paint to which graphene powder is added, comparative example 3 is a conventional epoxy zinc-rich paint (84.44% zinc content), and the components and the amounts thereof in the examples and comparative examples are shown in table 1.
TABLE 1
The anticorrosive coatings prepared in the examples 1-2 and the comparative examples 1-3 are subjected to performance tests, the appearance and the color of the coating are observed by visual observation, the impact strength, the hardness and the adhesion are tested, the salt spray resistance is tested by GB/T1771-2007, and the coating after salt spray corrosion is subjected to scanning electron microscope analysis, and the test results are shown in Table 2 and figures 1-7.
TABLE 2 comparison of the properties of the examples and comparative examples
As can be seen from the above table, the graphene anticorrosive coating special for the transformer case prepared in example 1-2 has a smooth and flat appearance, the physical and mechanical properties of pencil hardness of more than 5H, adhesion of not less than 1 grade, and impact resistance of 50 cm. While comparative examples 1 and 2 have relatively poor hardness and adhesion properties. Namely, the physical and mechanical properties of the graphene anticorrosive paint special for the transformer shell prepared by the invention reach the test and detection standards of the traditional epoxy zinc-rich anticorrosive paint. However, compared with the traditional epoxy zinc-rich paint, the graphene anticorrosive paint special for the transformer shell, prepared by the invention, has the advantages that the zinc powder content is only 10-55%, and the salt spray resistance is superior to that of the traditional epoxy zinc-rich paint under the condition of low zinc content.
In the transformer shell special-purpose graphene anticorrosive paint in fig. 1, the content of metal zinc is 50.59%, and the salt spray test time is 5000 h; FIG. 2 shows comparative example 3 (a conventional epoxy zinc-rich paint with a zinc content of 84.44%) with a salt spray test time of 600 h. FIG. 3 shows comparative example 1 (graphene anticorrosive paint with the amount of components out of the protection range), with a salt spray test time of 200 h; fig. 4 shows comparative example 2 (coating with added graphene powder) with a salt spray test time of 300 h. The macro phenomenon of the salt spray test is a test board of the anticorrosive paint which is not sprayed with graphene, the surface of a paint film of the test board foams, and a large amount of white zinc salt corrosive is generated; the graphene anticorrosive paint special for the transformer shell, which is prepared according to the formula dosage, has the advantages that the sprayed test board has a complete surface except a slight corrosion phenomenon at a scratch position of 1mm, and the surface of the coating is hardly corroded (HG/T3668-2009 indicates that the unidirectional expansion corrosion at the scratch position is less than or equal to 2mm, and the phenomena of bubbling, rusting, cracking, peeling and the like do not exist in a scratch area, so that a salt spray resistance experiment is passed). And after the comparative examples 1 and 2 are respectively tested by 200h and 300h salt spray experiments, the unidirectional corrosion expansion at the surface scratches of the test board is more than or equal to 2 mm. By analyzing and comparing Scanning Electron Microscope (SEM) images 5, 6 and 7, the fact that a layer of 'thin yarn' exists on the surface of the coating of the graphene anticorrosive coating special for the transformer shell and prepared according to the formula dosage, zinc balls are completely coated, and the yarn layer achieves the synergistic effect on the shielding performance and the cathode protection performance of the coating, namely the compactness of a zinc-rich epoxy coating film can be obviously improved by adding the graphene, molecules such as water, oxygen and the like are effectively prevented from permeating into the surface of a matrix, the corrosion degree of the coating is reduced, and therefore the corrosion of a metal base material is reduced.
After the technical scheme of the invention is implemented in a large amount, the salt spray testing time is more than 6000h at most.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (9)
1. The graphene anticorrosive paint special for the transformer shell is characterized by comprising a component A and a component B according to the mass ratio of 5-20: 1;
the component A comprises the following raw materials in percentage by weight: 5-20% of epoxy resin, 1-5% of coupling agent, 2-15% of rheological additive, 1-15% of graphene resin slurry, 10-55% of zinc powder, 15-32% of filler and 5-25% of mixed solvent;
the graphene resin slurry is prepared from the following raw materials in percentage by weight: 30-50% of epoxy resin, 1-5% of rheological additive, 35-45% of mixed solvent, 1-15% of graphene and 5-10% of dispersant;
the component B comprises the following raw materials in percentage by weight: 25-40% of curing agent and 60-75% of mixed solvent.
2. The graphene anticorrosive paint special for transformer housings as claimed in claim 1, wherein the coupling agent is one or more selected from gamma-glycidoxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane and gamma- (methacryloyloxy) propyltrimethoxysilane.
3. The graphene anticorrosive paint special for transformer housings of claim 1, wherein the rheological additive is one or more selected from organic bentonite, polyethylene wax and polyamide wax.
4. The graphene anticorrosive paint special for transformer housings as claimed in claim 1, wherein the graphene sheet diameter in the graphene resin slurry is 5-50 μm;
the dispersant is one or more of copolymer solution containing acidic functional groups, a composition of polar acidic ester and high molecular alcohol, and high molecular weight copolymer alkyl ammonium salt.
5. The graphene anticorrosive paint special for transformer housings as claimed in claim 1, wherein the filler is selected from one or more of mica iron oxide ash, iron calcium powder, phosphorus titanium powder and phosphorus iron powder.
6. The graphene anticorrosive paint special for transformer housings of claim 1, wherein the mixed solvent is at least two selected from xylene, n-butanol, ethanol, toluene, propylene glycol methyl ether and cyclohexanone.
7. The graphene anticorrosive paint special for transformer housings as claimed in claim 1, wherein the curing agent is selected from amine curing agents including one or more of polyamide curing agents, aliphatic amine curing agents and phenolic amine curing agents.
8. The graphene anticorrosive paint special for transformer housings according to claim 1, wherein the epoxy resin is selected from any one of low molecular weight bisphenol A epoxy resin, medium molecular weight bisphenol A epoxy resin, high molecular weight bisphenol A epoxy resin, and novolac epoxy resin.
9. The preparation method of the graphene anticorrosive paint special for the transformer housing, disclosed by claim 1, is characterized by comprising the following steps of:
(1) preparing a component A in the coating:
preparing graphene resin slurry:
uniformly mixing the epoxy resin, the rheological additive and the mixed solvent, and then carrying out infiltration treatment on the graphene; after the infiltration treatment is finished, dropwise adding a dispersing agent while stirring, after the dropwise adding is finished, stirring at a high speed for 35min, then ultrasonically dispersing for 20min, and finally grinding by using a three-roller machine to obtain stable graphene resin slurry;
preparing a component A:
mixing epoxy resin, an auxiliary agent, a large amount of mixed solvent, graphene resin slurry and a coupling agent, stirring at a high speed for 30min, then sequentially adding zinc powder, a filler and the rest of the mixed solvent, dispersing, grinding and stirring at a rotation speed of 1500-3000r/min and a temperature of less than or equal to 50 ℃ until the fineness is less than 40 mu m, and filtering to obtain a component A in the coating;
wherein the dosage of the large amount of mixed solvent is not less than 70 percent of the total dosage of the mixed solvent;
(2) preparing a component B in the coating:
dissolving the curing agent with the mixed solvent uniformly at a temperature of not more than 50 ℃, and dispersing for 30min to obtain a component B in the coating;
(3) and (3) blending and stirring the component A and the component B in the coating uniformly according to a predetermined ratio to obtain the graphene anticorrosive coating special for the transformer shell.
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Application publication date: 20200421 |