CN115449278A - Graphene-loaded titanium dioxide composite anticorrosive paint and preparation method thereof - Google Patents

Graphene-loaded titanium dioxide composite anticorrosive paint and preparation method thereof Download PDF

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Publication number
CN115449278A
CN115449278A CN202211284377.5A CN202211284377A CN115449278A CN 115449278 A CN115449278 A CN 115449278A CN 202211284377 A CN202211284377 A CN 202211284377A CN 115449278 A CN115449278 A CN 115449278A
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parts
graphene
weight
vinyl ester
ester resin
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CN202211284377.5A
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Inventor
马国峰
张健
刘瑞
祁蓝钰
张鸿龄
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Shenyang University
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Shenyang University
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D163/00Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C09D163/10Epoxy resins modified by unsaturated compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • C09D7/62Additives non-macromolecular inorganic modified by treatment with other compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2237Oxides; Hydroxides of metals of titanium
    • C08K2003/2241Titanium dioxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives

Abstract

The invention relates to the technical field of anticorrosive coatings, in particular to graphene-loaded TiO 2 Phenolic epoxy vinyl ester resin anticorrosive paint and preparation method thereof, wherein the anticorrosive paint comprises phenolic epoxy vinyl ester resin and graphene loaded TiO 2 Nano-materials, curing agents, initiators, antifoaming agents, leveling agents, anti-settling agents and pigments. The invention adopts an ultraviolet irradiation method to prepare graphene loaded TiO 2 The nano material is used as a filler and is compounded with novolac epoxy vinyl ester resin to prepare the graphene-loaded TiO 2 Phenolic epoxy vinyl ester resin anticorrosive paint. The graphene-supported TiO of the invention 2 The phenolic epoxy vinyl ester resin coating can improve the corrosion resistance and the water resistance of the traditional resin, and the loaded TiO 2 The nano material can shield ultraviolet rayThe ultraviolet resistance of the novolac epoxy vinyl ester resin is improved under the action of a line, the good dispersibility of the novolac epoxy vinyl ester resin improves the dispersibility effect of graphene, the influence of graphene clusters on the isolation performance of the coating is avoided, and the isolation and corrosion resistance of the coating is further improved.

Description

Graphene-loaded titanium dioxide composite anticorrosive paint and preparation method thereof
Technical Field
The invention relates to the technical field of corrosion prevention of power transmission and transformation metal facilities in a heavily polluted environment, in particular to graphene loaded TiO 2 Phenolic epoxy vinyl ester resin anticorrosive paint and a preparation method thereof.
Background
With the development of the industrialized society, the corrosion caused by pollution is increasingly serious, and the atmospheric pollutants discharged by heavy industrial enterprises such as metallurgy, pharmacy, chemical industry and the like particularly contain H 2 S、NH 2 、SO 2 When the acid and alkali substances are used, the O in the air can be generated under the condition of high humidity 2 、CO 2 And their acid, alkali, salts and other elements dissolve in water, causing corrosion of the metal material. In an electric power system, a large amount of corrosion and damage are caused due to erosion of air pollutants, for example, steel-cored aluminum strands, steel structures, breaker mechanism boxes, isolating switch operation boxes and the like in a substation, particularly, steel-cored aluminum strands are obviously fragile and have obviously reduced tensile strength due to the fact that acid ions in the air pollutants corrode and cover the surfaces of wires with pits, and strand breakage and wire breakage are caused in serious cases, so that the service life of the wires is greatly shortened, and the service life of a power grid is greatly influenced by safe and stable operation. Therefore, the performance requirements on the anticorrosive paint are higher and higher, and the anticorrosive paint not only needs to achieve excellent anticorrosive performance, but also needs to have the requirements of easy processing, easy curing, good mechanical properties, environmental protection and the like.
The novolac epoxy vinyl ester resin has excellent heat resistance, mechanical property and chemical property, and also has good processing property of unsaturated polyester resin. Due to the methyl shielding effect outside ester bonds, the water resistance of the resin is improved. Meanwhile, the resin is a high-grade temperature-resistant variety in vinyl ester resin, has high thermal deformation temperature and good acid and alkali corrosion resistance, and has excellent solvent resistance due to high crosslinking density.
The graphene has a stable hybridization mode and a two-dimensional nano structure, has excellent barrier property, shielding property and chemical stability, is widely concerned by people as a high-quality anticorrosion nano filler, and can effectively slow down the permeability of a corrosive medium and improve the corrosion resistance of a material when added to an anticorrosion coating. However, due to the characteristics of high surface energy, large specific surface area, easy aggregation and the like, the dispersion of the coating is very goodA large limitation. Only when the graphite is uniformly distributed in the organic coating, the graphite can effectively fill micropores in the coating, prevent corrosive media from permeating, and has a shielding function. Therefore, the graphene-supported TiO is provided for solving the problems 2 Phenolic epoxy vinyl ester resin anticorrosive paint and a preparation method thereof.
Disclosure of Invention
The invention aims to provide a method for loading TiO on graphene 2 Phenolic epoxy vinyl ester resin anticorrosive paint and preparation method thereof, wherein graphene and TiO are irradiated by ultraviolet 2 Compounding and anti-bonding with novolac epoxy vinyl ester resin are performed to solve the problems set forth in the background art described above.
The purpose of the invention is realized by the following technical scheme:
graphene-loaded TiO 2 The preparation method of the phenolic epoxy vinyl ester resin anticorrosive paint is prepared from the following raw materials: 100 parts of phenolic epoxy vinyl ester resin and 15 to 35 parts of graphene-loaded TiO 2 The paint comprises a nano material, 30-40 parts of a curing agent, 2.3-6.4 parts of an initiator, 5.6-7.4 parts of an antifoaming agent, 2.3-6.4 parts of a leveling agent, 2-4 parts of an anti-settling agent and 5-6 parts of a pigment.
Preferably, the graphene supported TiO 2 The loading of graphene in the nanomaterial was 3%.
Preferably, the curing agent is Cumene Hydroperoxide (CHP).
Preferably, the initiator is tert-butyl perbenzoate (TBPB).
Preferably, the novolac epoxy vinyl ester resin and the graphene-supported TiO are 2 The weight parts of the nano material, the curing agent, the initiator, the defoaming agent, the flatting agent, the anti-settling agent and the pigment are respectively 100 parts by weight of novolac epoxy vinyl ester resin and 15 parts by weight of graphene-loaded TiO 2 The coating comprises a nano material, 30 parts by weight of a curing agent, 2.3 parts by weight of an initiator, 5.6 parts by weight of a defoaming agent, 2.3 parts by weight of a leveling agent, 2 parts by weight of an anti-settling agent and 5 parts by weight of a pigment.
Preferably, the novolac epoxy vinyl ester resin and the graphene-supported TiO are 2 Nano material, curing agent,The weight parts of the initiator, the defoamer, the flatting agent, the anti-settling agent and the pigment are respectively 100 weight parts of novolac epoxy vinyl ester resin and 25 weight parts of graphene-loaded TiO 2 The coating comprises a nano material, 35 parts by weight of a curing agent, 4.5 parts by weight of an initiator, 6.8 parts by weight of a defoaming agent, 4.5 parts by weight of a leveling agent, 3 parts by weight of an anti-settling agent and 6 parts by weight of a pigment.
Preferably, the novolac epoxy vinyl ester resin and the graphene-supported TiO are selected from 2 The weight parts of the nano material, the curing agent, the initiator, the defoaming agent, the flatting agent, the anti-settling agent and the pigment are respectively 100 parts by weight of novolac epoxy vinyl ester resin and 35 parts by weight of graphene-loaded TiO 2 The coating comprises a nano material, 40 parts by weight of a curing agent, 6.4 parts by weight of an initiator, 7.4 parts by weight of a defoaming agent, 6.4 parts by weight of a leveling agent, 4 parts by weight of an anti-settling agent and 6 parts by weight of a pigment.
Preferably, the method comprises the following steps:
(1) graphene/TiO 2 Preparing a nano composite material: firstly, a proper amount of nano TiO is added 2 Uniformly dispersing the graphene into an ethanol solution, mixing the graphene with the ethanol solution, and performing ultrasonic dispersion on the mixture for 40min to obtain a suspension; then, taking nitrogen as the protective atmosphere of the reaction, and reacting for 15h under the condition of ultraviolet irradiation; finally, carrying out suction filtration on the reaction solution, cleaning filter residues and carrying out vacuum drying to finally obtain graphene/TiO 2 A nanocomposite material;
(2) 40 parts by weight of aldehyde epoxy vinyl ester resin is placed in a mixing kettle, and graphene/TiO is added 2 Stirring the nano composite material at the stirring speed of 200r/min for 10 to 20min to obtain a component A;
(3) Adding the remaining aldehyde epoxy vinyl ester resin into a defoaming agent, a curing agent, an initiator, a flatting agent and an anti-settling agent, adjusting the stirring speed to 400/min, continuously stirring for 20 to 40min, and simultaneously carrying out ultrasonic vibration of 15-40KHz in the stirring process to obtain a component B;
(4) Stirring the component A at the rotation speed of 200r/min, adding the component B, adding pigment, stirring for 40min, and filtering to obtain the final product.
The invention has the advantages that:
1. the invention adopts graphene to load TiO 2 The nano material is used as a filler to prepare the graphene-loaded TiO 2 Phenolic epoxy vinyl ester resin anticorrosive paint and preparation method thereof, wherein graphene and TiO are irradiated by ultraviolet 2 The compounding process can overcome the disadvantages of high cost and complex process of the reaction mode. Simultaneous TiO 2 2 The nano material has the advantages of strong ultraviolet shielding effect, good dispersibility, low cost and the like, improves the dispersibility effect of the graphene, avoids the influence of graphene agglomerates on the isolation performance of the coating, and further improves the isolation and corrosion resistance of the coating;
2. the method has the advantages of simple operation, easy control of components, uniform prepared material, laying a foundation for industrial production and good popularization value.
Detailed Description
Example 1
The invention provides a technical scheme that:
graphene-loaded TiO 2 The phenolic epoxy vinyl ester resin anticorrosive paint comprises phenolic epoxy vinyl ester resin and graphene-loaded TiO 2 The coating comprises a nano material, a curing agent, an initiator, a defoaming agent, a flatting agent, an anti-settling agent and a pigment, wherein the nano material comprises 100 parts by weight of phenolic epoxy vinyl ester resin and 100 parts by weight of graphene-loaded TiO 2 15 parts of nano material, 30 parts of curing agent, 2.3 parts of initiator, 5.6 parts of defoaming agent, 2.3 parts of flatting agent, 2 parts of anti-settling agent and 5 parts of pigment. The method comprises the following steps:
(1) graphene/TiO 2 Preparing a nano composite material: firstly, a proper amount of nano TiO is added 2 Uniformly dispersing the mixture into an ethanol solution, mixing the ethanol solution with graphene, and ultrasonically dispersing the mixture for 40min to obtain a suspension; then, taking nitrogen as the protective atmosphere of the reaction, and reacting for 15h under the condition of ultraviolet irradiation; finally, carrying out suction filtration on the reaction solution, cleaning filter residues and carrying out vacuum drying to finally obtain graphene/TiO 2 A nanocomposite material;
(2) 40 parts by weight of aldehyde epoxy vinyl ester resin is placed in a mixing kettle, and graphene/TiO is added 2 Nanocomposite materialsStirring at the stirring speed of 200r/min for 10min to obtain a component A;
(3) Adding the residual aldehyde epoxy vinyl ester resin into a defoaming agent, a curing agent, an initiator, a flatting agent and an anti-settling agent, adjusting the stirring rotating speed to 400/min, continuously stirring for 20min, and simultaneously carrying out 15-40KHz ultrasonic vibration in the stirring process to obtain a component B;
(4) Keeping the rotation speed at 200r/min, stirring the component A, adding the component B, adding the pigment, continuously stirring for 40min, and filtering the mixed solution to obtain a finished product.
Example 2
The invention provides a technical scheme that:
graphene-loaded TiO 2 The anticorrosive paint comprises novolac epoxy vinyl ester resin and graphene-loaded TiO 2 The coating comprises a nano material, a curing agent, an initiator, a defoaming agent, a leveling agent, an anti-settling agent and a pigment, wherein the weight parts of the nano material, the curing agent, the initiator, the defoaming agent, the leveling agent, the anti-settling agent and the pigment are respectively 100 parts of novolac epoxy vinyl ester resin and 100 parts of graphene-loaded TiO 2 25 parts of nano material, 35 parts of curing agent, 4.5 parts of initiator, 6.8 parts of defoaming agent, 4.5 parts of flatting agent, 3 parts of anti-settling agent and 6 parts of pigment. The method comprises the following steps:
(1) graphene/TiO 2 Preparing a nano composite material: firstly, a proper amount of nano TiO is added 2 Uniformly dispersing the mixture into an ethanol solution, mixing the ethanol solution with graphene, and ultrasonically dispersing the mixture for 40min to obtain a suspension; then, taking nitrogen as the protective atmosphere of the reaction, and reacting for 15h under the condition of ultraviolet irradiation; finally, carrying out suction filtration on the reaction liquid, cleaning filter residues and carrying out vacuum drying to finally obtain graphene/TiO 2 A nanocomposite;
(2) Placing 40 parts by weight of aldehyde epoxy vinyl ester resin in a mixing kettle, and adding graphene/TiO 2 Stirring the nano composite material at the stirring speed of 200r/min for 15min to obtain a component A;
(3) Adding the residual aldehyde epoxy vinyl ester resin into a defoaming agent, a curing agent, an initiator, a flatting agent and an anti-settling agent, adjusting the stirring speed to 400/min, continuously stirring for 30min, and simultaneously carrying out 15-40KHz ultrasonic vibration in the stirring process to obtain a component B;
(4) Stirring the component A at the rotation speed of 200r/min, adding the component B, adding pigment, stirring for 40min, and filtering to obtain the final product.
Example 3
The invention provides a technical scheme that:
graphene-loaded TiO 2 The anticorrosive paint comprises novolac epoxy vinyl ester resin and graphene-loaded TiO 2 The coating comprises a nano material, a curing agent, an initiator, a defoaming agent, a flatting agent, an anti-settling agent and a pigment, wherein the nano material comprises 100 parts by weight of phenolic epoxy vinyl ester resin and 100 parts by weight of graphene-loaded TiO 2 35 parts of nano material, 40 parts of curing agent, 6.4 parts of initiator, 7.4 parts of defoaming agent, 6.4 parts of flatting agent, 4 parts of anti-settling agent and 6 parts of pigment. The method comprises the following steps:
(1) graphene/TiO 2 Preparing a nano composite material: firstly, a proper amount of nano TiO is added 2 Uniformly dispersing the mixture into an ethanol solution, mixing the ethanol solution with graphene, and ultrasonically dispersing the mixture for 40min to obtain a suspension; then, taking nitrogen as the protective atmosphere of the reaction, and reacting for 15h under the condition of ultraviolet irradiation; finally, carrying out suction filtration on the reaction liquid, cleaning filter residues and carrying out vacuum drying to finally obtain graphene/TiO 2 A nanocomposite material;
(2) 40 parts by weight of aldehyde epoxy vinyl ester resin is placed in a mixing kettle, and graphene/TiO is added 2 Stirring the nano composite material at the stirring speed of 200r/min for 20min to obtain a component A;
(3) Adding the remaining aldehyde epoxy vinyl ester resin into a defoaming agent, a curing agent, an initiator, a flatting agent and an anti-settling agent, adjusting the stirring speed to 400/min, continuously stirring for 40min, and simultaneously carrying out 15-40KHz ultrasonic vibration in the stirring process to obtain a component B;
(4) Stirring the component A at the rotation speed of 200r/min, adding the component B, adding pigment, stirring for 40min, and filtering to obtain the final product.

Claims (8)

1. Graphene-loaded TiO 2 The preparation method of the phenolic epoxy vinyl ester resin anticorrosive paint is characterized in that the anticorrosive paint is prepared from the following raw materials in parts by weight: 100 parts of phenolic epoxy vinyl ester resin and 15 to 35 parts of graphene-loaded TiO 2 30 to 40 parts of a nano material, 2.3 to 6.4 parts of a curing agent, 5.6 to 7.4 parts of an antifoaming agent, 2.3 to 6.4 parts of a flatting agent, 2 to 4 parts of an anti-settling agent and 5 to 6 parts of a pigment.
2. The graphene-supported TiO of claim 1 2 Phenolic epoxy vinyl ester resin anticorrosive paint, which is characterized in that the graphene loaded TiO 2 The graphene loading in the nanomaterial was 3%.
3. The graphene-supported TiO of claim 1 2 The anticorrosive phenolic epoxy vinyl ester resin paint features that the curing agent is Cumene Hydroperoxide (CHP).
4. The graphene-supported TiO of claim 1 2 The phenolic epoxy vinyl ester resin anticorrosive paint is characterized in that the initiator is tert-butyl perbenzoate (TBPB).
5. The graphene-supported TiO according to claim 1 2 The phenolic epoxy vinyl ester resin anticorrosive paint is characterized in that:
phenolic epoxy vinyl ester resin and graphene loaded TiO 2 The weight parts of the nano material, the curing agent, the initiator, the defoaming agent, the flatting agent, the anti-settling agent and the pigment are respectively 100 parts by weight of phenolic epoxy vinyl ester resin and 15 parts by weight of graphene-loaded TiO 2 Nano material, 30 parts of curing agent, 2.3 parts of initiator, 5.6 parts of defoamer, 2.3 parts of flatting agent, 2 parts of anti-settling agent and 5 parts of pigmentAnd (5) feeding.
6. The graphene-supported TiO of claim 1 2 The phenolic epoxy vinyl ester resin anticorrosive paint is characterized in that:
phenolic epoxy vinyl ester resin and graphene loaded TiO 2 The weight parts of the nano material, the curing agent, the initiator, the defoaming agent, the flatting agent, the anti-settling agent and the pigment are respectively 100 parts by weight of phenolic epoxy vinyl ester resin and 25 parts by weight of graphene-loaded TiO 2 The coating comprises a nano material, 35 parts by weight of a curing agent, 4.5 parts by weight of an initiator, 6.8 parts by weight of a defoaming agent, 4.5 parts by weight of a leveling agent, 3 parts by weight of an anti-settling agent and 6 parts by weight of a pigment.
7. The graphene-supported TiO according to claim 1 2 The phenolic epoxy vinyl ester resin anticorrosive paint is characterized in that:
phenolic epoxy vinyl ester resin and graphene loaded TiO 2 The weight parts of the nano material, the curing agent, the initiator, the defoaming agent, the flatting agent, the anti-settling agent and the pigment are respectively 100 parts by weight of phenolic epoxy vinyl ester resin and 35 parts by weight of graphene-loaded TiO 2 The coating comprises a nano material, 40 parts by weight of a curing agent, 6.4 parts by weight of an initiator, 7.4 parts by weight of a defoaming agent, 6.4 parts by weight of a leveling agent, 4 parts by weight of an anti-settling agent and 6 parts by weight of a pigment.
8. The graphene-supported TiO of claim 1 2 The manufacturing method of the phenolic epoxy vinyl ester resin anticorrosive paint is characterized by comprising the following steps:
(1) graphene/TiO 2 Preparing a nano composite material: firstly, a proper amount of nano TiO is added 2 Uniformly dispersing the graphene into an ethanol solution, mixing the graphene with the ethanol solution, and performing ultrasonic dispersion on the mixture for 40min to obtain a suspension; then, taking nitrogen as protective atmosphere of reaction, and reacting for 15h under the condition of ultraviolet irradiation; finally, carrying out suction filtration on the reaction liquid, cleaning filter residues and carrying out vacuum drying to finally obtain graphene/TiO 2 A nanocomposite material;
(2) Get40 parts by weight of aldehyde epoxy vinyl ester resin is placed in a mixing kettle, and graphene/TiO is added 2 Stirring the nano composite material at the stirring speed of 200r/min for 10 to 20min to obtain a component A;
(3) Adding the remaining aldehyde epoxy vinyl ester resin into a defoaming agent, a curing agent, an initiator, a flatting agent and an anti-settling agent, adjusting the stirring speed to 400/min, continuously stirring for 20 to 40min, and simultaneously carrying out ultrasonic vibration of 15-40KHz in the stirring process to obtain a component B;
(4) Stirring the component A at the rotation speed of 200r/min, adding the component B, adding pigment, stirring for 40min, and filtering to obtain the final product.
CN202211284377.5A 2022-10-20 2022-10-20 Graphene-loaded titanium dioxide composite anticorrosive paint and preparation method thereof Pending CN115449278A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115851058A (en) * 2022-12-26 2023-03-28 江苏绿能电力科技有限公司 Anti-corrosion coating for surface of distributed photovoltaic module

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CN103965736A (en) * 2014-05-08 2014-08-06 江苏山力漆业有限公司 Acid-resistant high-temperature-resistant corrosion-proof glue mud for inner wall of desulfurization device
CN105903462A (en) * 2016-05-23 2016-08-31 中国科学院城市环境研究所 Method for synthesizing titanium dioxide/graphene nano composite material
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115851058A (en) * 2022-12-26 2023-03-28 江苏绿能电力科技有限公司 Anti-corrosion coating for surface of distributed photovoltaic module

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Application publication date: 20221209

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