CN112430418A - Preparation method and application of biomass-based carbon nanosheet/epoxy composite coating - Google Patents

Preparation method and application of biomass-based carbon nanosheet/epoxy composite coating Download PDF

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CN112430418A
CN112430418A CN202011342178.6A CN202011342178A CN112430418A CN 112430418 A CN112430418 A CN 112430418A CN 202011342178 A CN202011342178 A CN 202011342178A CN 112430418 A CN112430418 A CN 112430418A
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biomass
coating
epoxy
composite coating
based carbon
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CN112430418B (en
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马生华
王惠
王刚
崔春婷
张贝贝
白晋波
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Northwestern University
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • 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

Abstract

A preparation method and application of a biomass-based carbon nanosheet/epoxy composite coating relate to a preparation method and application of an epoxy coating. The invention aims to solve the problems that the existing epoxy coating is used for corrosion prevention of the surfaces of various pipelines, ships and the like, the surface of the epoxy coating has the defects of a large number of holes, the physical isolation performance of the coating is poor, and the corrosion resistance level is low. The method comprises the following steps: firstly, pretreating biomass powder; secondly, preparing a biomass-based nano carbon sheet; and thirdly, preparing the biomass-based carbon nanosheet/epoxy composite coating. A biomass-based carbon nanosheet/epoxy composite coating is used for improving the corrosion resistance of petroleum pipelines and ships. The method has the advantages of simple operation, high corrosion speed, good effect, clear boundary, low cost and the like, and is mainly used for improving the corrosion resistance of the anticorrosive paint for the petroleum pipelines and the ships. The invention can obtain a biomass-based carbon nanosheet/epoxy composite coating.

Description

Preparation method and application of biomass-based carbon nanosheet/epoxy composite coating
Technical Field
The invention relates to a preparation method and application of an epoxy coating.
Background
Metal corrosion is a serious global problem, which causes direct loss to national economy, and a novel and efficient metal protection technical means is urgently needed to be developed. Among a plurality of material anticorrosion strategies, a simple, effective and cost-effective method is to protect through an anticorrosion coating. In order to improve the holes and defects of the traditional anticorrosive paint and improve the anticorrosive performance of the paint, various anticorrosive paints taking polymer resin as a raw material are produced.
The prior epoxy coating is used for corrosion prevention of various pipelines, ships and other surfaces, the surface of the epoxy coating has the defects of a large number of holes, the physical isolation performance of the coating is poor, and the corrosion resistance level is low, so that the modification of the epoxy coating has important significance for corrosion prevention, and the corrosion resistance of various pipelines, ships and other surfaces is improved.
Disclosure of Invention
The invention aims to solve the problems that the existing epoxy coating is used for corrosion prevention of the surfaces of various pipelines, ships and the like, a large number of holes exist on the surface of the epoxy coating, the physical isolation performance of the coating is poor, and the corrosion resistance level is low, and provides a preparation method and application of a biomass-based carbon nanosheet/epoxy composite coating.
A preparation method of a biomass-based carbon nanosheet/epoxy composite coating is completed according to the following steps:
firstly, pretreatment of biomass powder:
firstly, cleaning wheat straws, then drying the wheat straws to constant weight, crushing the wheat straws by using a crusher, and then screening the wheat straws to obtain wheat straw powder with the particle size of 75 mu m;
secondly, putting the wheat straw powder with the particle size of 75 mu m, deionized water, hydrogen peroxide solution and acetic acid into a reaction kettle, uniformly stirring, and then sealing the reaction kettle; heating the sealed reaction kettle from room temperature to 80-200 ℃, then preserving heat for 2-24 h at 80-200 ℃, and cooling to room temperature to obtain the reacted wheat straw powder;
the mass ratio of the deionized water, the hydrogen peroxide solution, the acetic acid and the wheat straw powder with the particle size of 75 mu m in the first step is (20-50): 5-20): 1-10): 1;
thirdly, washing the reacted wheat straw powder to be neutral by using distilled water, dispersing the wheat straw powder in the distilled water, adding the distilled water into a probe type ultrasonic dispersion instrument for ultrasonic dispersion, performing suction filtration by using a vacuum suction filtration device, and finally performing freeze drying to obtain the pretreated wheat straw powder;
secondly, preparing the biomass-based nano carbon sheet:
firstly, the pretreated wheat straw powder, urea and Na2CO3Mixing with NaCl, and stirring to obtain a mixture;
the wheat straw powder, the urea and the Na in the second step2CO3The mass ratio of NaCl to NaCl is 1 (0.1-1): (1-5): 1-5);
secondly, placing the mixture into an alumina porcelain boat, placing the alumina porcelain boat in a tubular furnace, continuously introducing nitrogen into the tubular furnace, removing air in the tubular furnace, heating the tubular furnace from room temperature to 200-1600 ℃ at the heating rate of 3-5 ℃/min under the flow rate of the nitrogen being 100-200 mL/min, keeping the temperature at 200-1600 ℃ for 30-180 min, and cooling to room temperature to obtain a reaction product;
thirdly, immersing the reaction product into hydrochloric acid for cleaning to obtain the reaction product cleaned by the hydrochloric acid; washing the reaction product washed by the hydrochloric acid to be neutral by using distilled water, and then carrying out suction filtration and drying to obtain a biomass-based nano carbon sheet;
thirdly, preparing the biomass-based carbon nanosheet/epoxy composite coating:
polishing a Q235 steel plate by using sand paper of 400 meshes, 600 meshes and 1000 meshes in sequence to obtain a bright Q235 steel plate; firstly, cleaning a bright Q235 steel plate by using absolute ethyl alcohol, cleaning the bright Q235 steel plate by using acetone, and finally drying in an oven to obtain a treated Q235 steel plate;
dispersing the biomass-based nano carbon sheets into an organic solvent, performing ultrasonic dispersion at room temperature, centrifuging, and removing supernatant to obtain biomass-based nano carbon sheets after ultrasonic treatment;
thirdly, adding the biomass-based nano carbon sheets subjected to ultrasonic treatment into the epoxy coating, stirring for 10-100 min at the stirring speed of 100-1000 r/min, adding the curing agent, stirring uniformly, and putting into a vacuum drying oven for vacuumizing for 10-15 min to obtain a uniformly mixed coating;
the mass of the biomass-based nano carbon sheet subjected to ultrasonic treatment and the epoxy coating is (0.1-2): 100;
the mass ratio of the epoxy coating to the curing agent in the third step is 5: 1;
and fourthly, coating the uniformly mixed coating on the treated Q235 steel plate, and drying at room temperature to obtain the biomass-based carbon nanosheet/epoxy composite coating.
A biomass-based carbon nanosheet/epoxy composite coating is used for improving the corrosion resistance of petroleum pipelines and ships.
The principle and the advantages of the invention are as follows:
the biomass-based nano carbon sheet is prepared by mainly utilizing chemical dissociation and carbonization treatment of biomass, has a similar two-dimensional lamellar structure, can effectively make up the defect that a large number of holes exist on the surface of an epoxy coating when being used in the epoxy coating, and improves the physical isolation performance of the coating; meanwhile, the corrosion resistance of the coating is researched by adopting an electrochemical alternating-current impedance method and a neutral salt spray resistance test, and the result shows that after the biomass-based nano carbon sheet prepared by the method is used in the epoxy coating, the resistance of the coating is about 109Omega, resistance of pure epoxy coatingAbout 2500 omega, which shows that after the biomass-based nano carbon sheet prepared by the invention is added into a pure epoxy coating, the coating has excellent corrosion resistance, and the biomass-based nano carbon sheet with a similar two-dimensional lamellar structure can enable the epoxy coating to have smaller porosity;
exposing the pure epoxy coating and the biomass-based carbon nanosheet/epoxy composite coating prepared by the method in a salt spray box of a NaCl solution with the mass fraction of 5%, wherein a large area of corrosion rust exists on the surface of the pure epoxy coating, the biomass-based carbon nanosheet/epoxy composite coating prepared by adding the biomass-based carbon nanosheet is almost free from rust generation, and the corrosion expansion area is greatly reduced; the addition of the biomass-based nano carbon sheet effectively enhances the barrier property of the surface of the coating and greatly improves the protective property of the coating to the steel substrate;
the method has the advantages of simple operation, high corrosion speed, good effect, clear boundary, low cost and the like, and is mainly used for improving the corrosion resistance of the anticorrosive paint for the petroleum pipelines and the ships.
The invention can obtain a biomass-based carbon nanosheet/epoxy composite coating.
Drawings
FIG. 1 is an SEM image of a pure epoxy coating prepared by a comparative example;
fig. 2 is an SEM image of a biomass-based carbon nanosheet/epoxy composite coating prepared in example one;
fig. 3 is a contact angle test chart of the biomass-based carbon nanosheet/epoxy composite coating prepared in the first example;
fig. 4 is a contact angle test chart of the biomass-based carbon nanosheet/epoxy composite coating prepared in example two.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
The first embodiment is as follows: the preparation method of the biomass-based carbon nanosheet/epoxy composite coating according to the embodiment is completed according to the following steps:
firstly, pretreatment of biomass powder:
firstly, cleaning wheat straws, then drying the wheat straws to constant weight, crushing the wheat straws by using a crusher, and then screening the wheat straws to obtain wheat straw powder with the particle size of 75 mu m;
secondly, putting the wheat straw powder with the particle size of 75 mu m, deionized water, hydrogen peroxide solution and acetic acid into a reaction kettle, uniformly stirring, and then sealing the reaction kettle; heating the sealed reaction kettle from room temperature to 80-200 ℃, then preserving heat for 2-24 h at 80-200 ℃, and cooling to room temperature to obtain the reacted wheat straw powder;
the mass ratio of the deionized water, the hydrogen peroxide solution, the acetic acid and the wheat straw powder with the particle size of 75 mu m in the first step is (20-50): 5-20): 1-10): 1;
thirdly, washing the reacted wheat straw powder to be neutral by using distilled water, dispersing the wheat straw powder in the distilled water, adding the distilled water into a probe type ultrasonic dispersion instrument for ultrasonic dispersion, performing suction filtration by using a vacuum suction filtration device, and finally performing freeze drying to obtain the pretreated wheat straw powder;
secondly, preparing the biomass-based nano carbon sheet:
firstly, the pretreated wheat straw powder, urea and Na2CO3Mixing with NaCl, and stirring to obtain a mixture;
the wheat straw powder, the urea and the Na in the second step2CO3The mass ratio of NaCl to NaCl is 1 (0.1-1): (1-5): 1-5);
secondly, placing the mixture into an alumina porcelain boat, placing the alumina porcelain boat in a tubular furnace, continuously introducing nitrogen into the tubular furnace, removing air in the tubular furnace, heating the tubular furnace from room temperature to 200-1600 ℃ at the heating rate of 3-5 ℃/min under the flow rate of the nitrogen being 100-200 mL/min, keeping the temperature at 200-1600 ℃ for 30-180 min, and cooling to room temperature to obtain a reaction product;
thirdly, immersing the reaction product into hydrochloric acid for cleaning to obtain the reaction product cleaned by the hydrochloric acid; washing the reaction product washed by the hydrochloric acid to be neutral by using distilled water, and then carrying out suction filtration and drying to obtain a biomass-based nano carbon sheet;
thirdly, preparing the biomass-based carbon nanosheet/epoxy composite coating:
polishing a Q235 steel plate by using sand paper of 400 meshes, 600 meshes and 1000 meshes in sequence to obtain a bright Q235 steel plate; firstly, cleaning a bright Q235 steel plate by using absolute ethyl alcohol, cleaning the bright Q235 steel plate by using acetone, and finally drying in an oven to obtain a treated Q235 steel plate;
dispersing the biomass-based nano carbon sheets into an organic solvent, performing ultrasonic dispersion at room temperature, centrifuging, and removing supernatant to obtain biomass-based nano carbon sheets after ultrasonic treatment;
thirdly, adding the biomass-based nano carbon sheets subjected to ultrasonic treatment into the epoxy coating, stirring for 10-100 min at the stirring speed of 100-1000 r/min, adding the curing agent, stirring uniformly, and putting into a vacuum drying oven for vacuumizing for 10-30 min to obtain a uniformly mixed coating;
the mass of the biomass-based nano carbon sheet subjected to ultrasonic treatment and the epoxy coating is (0.1-2): 100;
the mass ratio of the epoxy coating to the curing agent in the third step is 5: 1;
and fourthly, coating the uniformly mixed coating on the treated Q235 steel plate, and drying at room temperature to obtain the biomass-based carbon nanosheet/epoxy composite coating.
The principle and advantages of the embodiment are as follows:
the biomass-based nano carbon sheet is prepared by mainly utilizing chemical dissociation and carbonization treatment on biomass, has a similar two-dimensional lamellar structure, can effectively make up the defect that a large number of holes exist on the surface of an epoxy coating when being used in the epoxy coating, and improves the physical isolation performance of the coating; meanwhile, the corrosion resistance of the coating is researched by adopting an electrochemical alternating-current impedance method and a neutral salt spray resistance test, and the result shows that the raw material prepared by the embodiment is usedAfter the material-based nanocarbon chips were used in an epoxy coating, the resistance of the coating was about 109Omega, the resistance of the pure epoxy coating is about 2500 omega, which shows that after the biomass-based nano carbon sheet prepared by the embodiment is added into the pure epoxy coating, the coating has excellent corrosion resistance, and the biomass-based nano carbon sheet with a similar two-dimensional lamellar structure can enable the epoxy coating to have smaller porosity;
secondly, after the pure epoxy coating and the biomass-based carbon nanosheet/epoxy composite coating prepared by the embodiment are exposed in a salt spray box of a NaCl solution with the mass fraction of 5%, a large area of corrosion rust exists on the surface of the pure epoxy coating, the biomass-based carbon nanosheet/epoxy composite coating prepared by adding the biomass-based carbon nanosheet is almost free from rust generation, and the corrosion expansion area is greatly reduced; the addition of the biomass-based nano carbon sheet effectively enhances the barrier property of the surface of the coating and greatly improves the protective property of the coating to the steel substrate;
the method has the advantages of simple operation, high corrosion speed, good effect, clear boundary, low cost and the like, and is mainly used for improving the corrosion resistance of the anticorrosive paint for the petroleum pipelines and the ships.
The embodiment can obtain the biomass-based carbon nanosheet/epoxy composite coating.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the drying temperature in the first step is 60 ℃; firstly, cleaning the wheat straws by using distilled water until the distilled water is not turbid, then drying the wheat straws to constant weight at 60 ℃, crushing the wheat straws by using a crusher, and then screening the wheat straws by using a 200-mesh stainless steel screen to obtain the wheat straw powder with the particle size of 75 mu m. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the mass fraction of the hydrogen peroxide solution in the first step is 5-20%; the mass fraction of the acetic acid in the first step is 5-40%; in the first step, the temperature of the sealed reaction kettle is raised from room temperature to 80-200 ℃ at a heating rate of 1-10 ℃/min. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: the power of ultrasonic dispersion in the step one is 200-1500W, and the time of ultrasonic dispersion is 0.5-12 h; the volume ratio of the mass of the wheat straw powder after reaction to the distilled water in the step one is 1g (50 mL-100 mL); the temperature of the freeze drying in the step one is-10 ℃ to-40 ℃, and the time of the freeze drying is 10h to 12 h. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the stirring speed in the second step is 200 r/min-500 r/min, and the stirring time is 30 min-60 min. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: secondly, the mixture is put into an alumina porcelain boat and then is put into a tubular furnace, nitrogen is continuously introduced into the tubular furnace for 30-40 min, the flow rate of the nitrogen is 100-200 mL/min, and air in the tubular furnace is removed. The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: the concentration of the hydrochloric acid in the second step is 1 mol/L; soaking the reaction product into hydrochloric acid to clean for 2-4 times, wherein the cleaning time is 10-50 min each time; the drying temperature in the second step is 60-100 ℃, and the drying time is 10-24 h. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the mass ratio of the biomass-based nano carbon sheet to the volume of the organic solvent in the third step is 1g:50 mL; the organic solvent in the third step is methanol; and step three, the power of ultrasonic dispersion is 40-80W, and the time of ultrasonic dispersion is 1-2 h. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: the curing agent in the third step is modified amine curing agent 593 purchased from Shanghai Limited company; the epoxy coating in the third step is epoxy resin E-51; the thickness of the evenly mixed paint coated on the processed Q235 steel plate is 100-150 mu m; the drying time in the step III-80 h. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the embodiment is that the biomass-based carbon nanosheet/epoxy composite coating is used for improving the corrosion resistance of petroleum pipelines and ships.
The present invention will be described in detail below with reference to the accompanying drawings and examples.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: a preparation method of a biomass-based carbon nanosheet/epoxy composite coating is completed according to the following steps:
firstly, pretreatment of biomass powder:
firstly, cleaning wheat straws by using distilled water until the distilled water is not turbid, then drying the wheat straws to constant weight at 60 ℃, crushing the wheat straws by using a crusher, and screening the wheat straws by using a 200-mesh stainless steel screen to obtain wheat straw powder with the particle size of 75 mu m;
secondly, putting the wheat straw powder with the particle size of 75 mu m, deionized water, hydrogen peroxide solution and acetic acid into a reaction kettle, uniformly stirring, and then sealing the reaction kettle; heating the sealed reaction kettle from room temperature to 140 ℃, then preserving heat at 140 ℃ for 12h, and cooling to room temperature to obtain reacted wheat straw powder;
the mass ratio of the deionized water, the hydrogen peroxide solution, the acetic acid and the wheat straw powder with the particle size of 75 mu m in the first step is 20:20:2: 1;
the mass fraction of the hydrogen peroxide solution in the first step is 10 percent;
the mass fraction of the acetic acid in the first step is 30 percent;
heating the sealed reaction kettle from room temperature to 140 ℃ at a heating rate of 10 ℃/min;
thirdly, washing the reacted wheat straw powder to be neutral by using distilled water, dispersing the wheat straw powder in the distilled water, adding the distilled water into a probe type ultrasonic dispersion instrument for ultrasonic dispersion, performing suction filtration by using a vacuum suction filtration device, and finally performing freeze drying to obtain the pretreated wheat straw powder;
the power of ultrasonic dispersion in the step one is 600W, and the time of ultrasonic dispersion is 2 h;
the volume ratio of the mass of the wheat straw powder after reaction to the distilled water in the step one is 1g to 50 mL;
the temperature of the freeze drying in the step one is-40 ℃, and the time of the freeze drying is 12 hours;
secondly, preparing the biomass-based nano carbon sheet:
firstly, the pretreated wheat straw powder, urea and Na2CO3Mixing with NaCl, and stirring to obtain a mixture;
the stirring speed in the second step is 500r/min, and the stirring time is 60 min;
the wheat straw powder, the urea and the Na in the second step2CO3The mass ratio of NaCl to NaCl is 1:1:2: 1;
secondly, putting the mixture into an alumina porcelain boat, putting the alumina porcelain boat into a tubular furnace, continuously introducing nitrogen into the tubular furnace, removing air in the tubular furnace, heating the tubular furnace to 800 ℃ from room temperature at the heating rate of 3 ℃/min under the flow rate of the nitrogen of 100mL/min, keeping the temperature at 800 ℃ for 180min, and cooling to room temperature to obtain a reaction product;
secondly, putting the mixture into an alumina porcelain boat, putting the alumina porcelain boat into a tubular furnace, continuously introducing nitrogen into the tubular furnace for 30-40 min at the flow rate of 100mL/min, and removing air in the tubular furnace;
thirdly, immersing the reaction product into hydrochloric acid for cleaning to obtain the reaction product cleaned by the hydrochloric acid; washing the reaction product washed by the hydrochloric acid to be neutral by using distilled water, and then carrying out suction filtration and drying to obtain a biomass-based nano carbon sheet;
the concentration of the hydrochloric acid in the second step is 1 mol/L;
soaking the reaction product into hydrochloric acid for cleaning for 3 times, wherein the cleaning time is 10min each time;
the drying temperature in the second step is 80 ℃, and the drying time is 12 hours;
thirdly, preparing the biomass-based carbon nanosheet/epoxy composite coating:
polishing a Q235 steel plate by using sand paper of 400 meshes, 600 meshes and 1000 meshes in sequence to obtain a bright Q235 steel plate; firstly, cleaning a bright Q235 steel plate by using absolute ethyl alcohol, cleaning the bright Q235 steel plate by using acetone, and finally drying in an oven to obtain a treated Q235 steel plate;
dispersing the biomass-based nano carbon sheets into an organic solvent, performing ultrasonic dispersion at room temperature, centrifuging, and removing supernatant to obtain biomass-based nano carbon sheets after ultrasonic treatment;
the mass ratio of the biomass-based nano carbon sheet to the volume of the organic solvent in the third step is 1g:50 mL;
the organic solvent in the third step is methanol;
the power of ultrasonic dispersion in the third step is 60W, and the time of ultrasonic dispersion is 1 h;
thirdly, adding the biomass-based nano carbon sheets subjected to ultrasonic treatment into the epoxy coating, stirring at the stirring speed of 300r/min for 60min, adding the curing agent, stirring uniformly, and putting into a vacuum drying oven for vacuumizing for 30min to obtain a uniformly mixed coating;
the mass ratio of the biomass-based nano carbon sheet subjected to ultrasonic treatment to the epoxy coating is 0.1: 100;
the curing agent in the third step is modified amine curing agent 593 purchased from Shanghai Limited company;
the epoxy coating in the third step is epoxy resin E-51;
the mass ratio of the epoxy coating to the curing agent in the third step is 5: 1;
fourthly, coating the uniformly mixed coating on the processed Q235 steel plate, and drying at room temperature to obtain a biomass-based carbon nanosheet/epoxy composite coating;
the thickness of the coating which is uniformly mixed and is coated on the processed Q235 steel plate in the step III is 120 mu m;
the drying time in the step III-IV is 72 hours.
Example two: the present embodiment is different from the first embodiment in that: and thirdly, the mass ratio of the biomass-based nano carbon sheet subjected to ultrasonic treatment to the epoxy coating is 1: 100. Other steps and parameters are the same as those in the first embodiment.
Example three: the present embodiment is different from the first embodiment in that: and thirdly, the mass ratio of the biomass-based nano carbon sheet subjected to ultrasonic treatment to the epoxy coating is 2: 100. Other steps and parameters are the same as those in the first embodiment.
Comparative example: the preparation method of the pure epoxy coating is completed according to the following steps:
polishing a Q235 steel plate by using sand paper of 400 meshes, 600 meshes and 1000 meshes in sequence to obtain a bright Q235 steel plate; firstly, cleaning a bright Q235 steel plate by using absolute ethyl alcohol, cleaning the bright Q235 steel plate by using acetone, and finally drying in an oven to obtain a treated Q235 steel plate;
secondly, adding a curing agent into the epoxy coating, stirring for 60min at the stirring speed of 300r/min, and then putting the epoxy coating into a vacuum drying oven for vacuumizing for 30min to obtain a uniformly mixed coating;
the curing agent in the third step is a modified amine curing agent 593 purchased from Shanghai Limited company; (ii) a
The epoxy coating in the third step is epoxy resin E-51;
thirdly, coating the uniformly mixed paint on the processed Q235 steel plate, and drying at room temperature to obtain a pure epoxy coating;
the thickness of the coating which is uniformly mixed and is coated on the processed Q235 steel plate is 120 mu m;
and the drying time in the third step is 72 hours.
FIG. 1 is an SEM image of a pure epoxy coating prepared by a comparative example;
fig. 2 is an SEM image of a biomass-based carbon nanosheet/epoxy composite coating prepared in example one;
as can be seen from fig. 1 and 2, after the biomass-based carbon nanosheet is added to the epoxy coating, the surface of the coating is smoother, and the pores of the coating are smaller and more compact.
Fig. 3 is a contact angle test chart of the biomass-based carbon nanosheet/epoxy composite coating prepared in the first example;
fig. 4 is a contact angle test chart of the biomass-based carbon nanosheet/epoxy composite coating prepared in example two;
as can be seen from fig. 3 to 4, after the biomass-based carbon nanosheet is added to the epoxy coating, the surface of the coating is more hydrophobic, so that the water resistance of the coating is improved.
An electrochemical alternating-current impedance spectrum is an important index for evaluating the corrosion resistance of a coating, a pure epoxy composite coating prepared in a comparative example and a biomass-based carbon nanosheet/epoxy composite coating prepared in the first example are tested by an electrochemical alternating-current impedance method, the electrochemical impedance spectrum of the experiment is tested by a three-electrode testing system, the pure epoxy composite coating prepared in the comparative example and the biomass-based carbon nanosheet/epoxy composite coating prepared in the first example are respectively used as working electrodes, the counter electrode is replaced by a platinum electrode, the reference electrode is replaced by a saturated calomel electrode, and the working area of a steel plate is 1.33cm2The electrochemical impedance test was carried out in a 3.5% by mass NaCl solution. The corrosion protection efficiency increased from 67.01% for the neat epoxy coating to 98.58% for the biomass-based carbon nanoplate/epoxy composite coating. After the biomass-based carbon nanosheet is doped into the coating, the defect of loose surface of the coating is effectively overcome, the coating has good hydrophobicity and barrier property, corrosive media can be prevented from permeating into the steel substrate, and the corrosion of the steel substrate is effectively protected.
The pure epoxy composite coating prepared in the comparative example and the biomass-based carbon nanosheet/epoxy composite coating prepared in the first example were subjected to a neutral salt spray resistance test, in which a sample was exposed to a NaCl solution with a neutral mass fraction of 5%, and changes in bubbles and peeling degrees of the coating sample were observed after a certain period of time. The tests show that the scratches on the surface of the coating are damaged to different degrees, particularly the pure epoxy coating has a large amount of corrosion products and bubbles on the surface, and the corrosion area is large. In contrast, the biomass-based carbon nanosheet/epoxy composite coating prepared in the first embodiment has few corrosion products and bubbles, the corrosion area is greatly reduced, only a few corrosion spots exist at the edge, and the adhesion of the coating above the scratches is still good. The addition of the biomass-based nano carbon sheet effectively enhances the bonding strength between the coating and the steel substrate.

Claims (10)

1. A preparation method of a biomass-based carbon nanosheet/epoxy composite coating is characterized in that the preparation method of the biomass-based carbon nanosheet/epoxy composite coating is completed according to the following steps:
firstly, pretreatment of biomass powder:
firstly, cleaning wheat straws, then drying the wheat straws to constant weight, crushing the wheat straws by using a crusher, and then screening the wheat straws to obtain wheat straw powder with the particle size of 75 mu m;
secondly, putting the wheat straw powder with the particle size of 75 mu m, deionized water, hydrogen peroxide solution and acetic acid into a reaction kettle, uniformly stirring, and then sealing the reaction kettle; heating the sealed reaction kettle from room temperature to 80-200 ℃, then preserving heat for 2-24 h at 80-200 ℃, and cooling to room temperature to obtain the reacted wheat straw powder;
the mass ratio of the deionized water, the hydrogen peroxide solution, the acetic acid and the wheat straw powder with the particle size of 75 mu m in the first step is (20-50): 5-20): 1-10): 1;
thirdly, washing the reacted wheat straw powder to be neutral by using distilled water, dispersing the wheat straw powder in the distilled water, adding the distilled water into a probe type ultrasonic dispersion instrument for ultrasonic dispersion, performing suction filtration by using a vacuum suction filtration device, and finally performing freeze drying to obtain the pretreated wheat straw powder;
secondly, preparing the biomass-based nano carbon sheet:
firstly, the pretreated wheat straw powder, urea and Na2CO3Mixing with NaCl, and stirring to obtain a mixture;
the wheat straw powder, the urea and the Na in the second step2CO3The mass ratio of NaCl to NaCl is 1 (0.1-1): (1-5): 1-5);
secondly, placing the mixture into an alumina porcelain boat, placing the alumina porcelain boat in a tubular furnace, continuously introducing nitrogen into the tubular furnace, removing air in the tubular furnace, heating the tubular furnace from room temperature to 200-1600 ℃ at the heating rate of 3-5 ℃/min under the flow rate of the nitrogen being 100-200 mL/min, keeping the temperature at 200-1600 ℃ for 30-180 min, and cooling to room temperature to obtain a reaction product;
thirdly, immersing the reaction product into hydrochloric acid for cleaning to obtain the reaction product cleaned by the hydrochloric acid; washing the reaction product washed by the hydrochloric acid to be neutral by using distilled water, and then carrying out suction filtration and drying to obtain a biomass-based nano carbon sheet;
thirdly, preparing the biomass-based carbon nanosheet/epoxy composite coating:
polishing a Q235 steel plate by using sand paper of 400 meshes, 600 meshes and 1000 meshes in sequence to obtain a bright Q235 steel plate; firstly, cleaning a bright Q235 steel plate by using absolute ethyl alcohol, cleaning the bright Q235 steel plate by using acetone, and finally drying in an oven to obtain a treated Q235 steel plate;
dispersing the biomass-based nano carbon sheets into an organic solvent, performing ultrasonic dispersion at room temperature, centrifuging, and removing supernatant to obtain biomass-based nano carbon sheets after ultrasonic treatment;
thirdly, adding the biomass-based nano carbon sheets subjected to ultrasonic treatment into the epoxy coating, stirring for 10-100 min at the stirring speed of 100-1000 r/min, adding the curing agent, stirring uniformly, and putting into a vacuum drying oven for vacuumizing for 10-30 min to obtain a uniformly mixed coating;
the mass of the biomass-based nano carbon sheet subjected to ultrasonic treatment and the epoxy coating is (0.1-2): 100;
the mass ratio of the epoxy coating to the curing agent in the third step is 5: 1;
and fourthly, coating the uniformly mixed coating on the treated Q235 steel plate, and drying at room temperature to obtain the biomass-based carbon nanosheet/epoxy composite coating.
2. The preparation method of the biomass-based carbon nanosheet/epoxy composite coating according to claim 1, wherein the drying temperature in the first step is 60 ℃; firstly, cleaning the wheat straws by using distilled water until the distilled water is not turbid, then drying the wheat straws to constant weight at 60 ℃, crushing the wheat straws by using a crusher, and then screening the wheat straws by using a 200-mesh stainless steel screen to obtain the wheat straw powder with the particle size of 75 mu m.
3. The preparation method of the biomass-based carbon nanosheet/epoxy composite coating according to claim 1, wherein the hydrogen peroxide solution in the first step is 5-20% by mass; the mass fraction of the acetic acid in the first step is 5-40%; in the first step, the temperature of the sealed reaction kettle is raised from room temperature to 80-200 ℃ at a heating rate of 1-10 ℃/min.
4. The preparation method of the biomass-based carbon nanosheet/epoxy composite coating according to claim 1, wherein the ultrasonic dispersion power in the first step is 200W-1500W, and the ultrasonic dispersion time is 0.5 h-12 h; the volume ratio of the mass of the wheat straw powder after reaction to the distilled water in the step one is 1g (50 mL-100 mL); the temperature of the freeze drying in the step one is-10 ℃ to-40 ℃, and the time of the freeze drying is 10h to 12 h.
5. The preparation method of the biomass-based carbon nanosheet/epoxy composite coating according to claim 1, wherein the stirring speed in the second r is 200r/min to 500r/min, and the stirring time is 30min to 60 min.
6. The preparation method of the biomass-based carbon nanosheet/epoxy composite coating according to claim 1, wherein the mixture is placed in an alumina porcelain boat and then placed in a tubular furnace, nitrogen is continuously introduced into the tubular furnace for 30 to 40 minutes at a flow rate of 100 to 200mL/min, and air in the tubular furnace is removed.
7. The preparation method of the biomass-based carbon nanosheet/epoxy composite coating according to claim 1, wherein the concentration of the hydrochloric acid in the second step is 1 mol/L; soaking the reaction product into hydrochloric acid to clean for 2-4 times, wherein the cleaning time is 10-50 min each time; the drying temperature in the second step is 60-100 ℃, and the drying time is 10-24 h.
8. The preparation method of the biomass-based carbon nanosheet/epoxy composite coating according to claim 1, wherein the volume ratio of the mass of the biomass-based carbon nanosheet to the organic solvent in the third step is 1g:50 mL; the organic solvent in the third step is methanol; and step three, the power of ultrasonic dispersion is 40-80W, and the time of ultrasonic dispersion is 1-2 h.
9. The preparation method of the biomass-based carbon nanosheet/epoxy composite coating according to claim 1, wherein the curing agent in the third step is a modified amine curing agent 593; the epoxy coating in the third step is epoxy resin E-51; the thickness of the evenly mixed paint coated on the processed Q235 steel plate is 100-150 mu m; the drying time in the step III-80 h.
10. The use of a biomass-based carbon nanosheet/epoxy composite coating of claim 1, wherein a biomass-based carbon nanosheet/epoxy composite coating is used to improve the corrosion resistance of petroleum pipelines and ships.
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CN103332687A (en) * 2013-07-11 2013-10-02 黑龙江大学 Method for preparing boron and nitrogen codoped graphitized nano carbon by taking biomass as carbon source
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CN103332687A (en) * 2013-07-11 2013-10-02 黑龙江大学 Method for preparing boron and nitrogen codoped graphitized nano carbon by taking biomass as carbon source
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