CN114561139A - Heat-conducting coating utilizing synergistic effect of three fillers and preparation method and application thereof - Google Patents
Heat-conducting coating utilizing synergistic effect of three fillers and preparation method and application thereof Download PDFInfo
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- CN114561139A CN114561139A CN202210181793.6A CN202210181793A CN114561139A CN 114561139 A CN114561139 A CN 114561139A CN 202210181793 A CN202210181793 A CN 202210181793A CN 114561139 A CN114561139 A CN 114561139A
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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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
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
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Abstract
The invention discloses a heat-conducting coating utilizing synergistic effect of three fillers, and a preparation method and application thereof. The heat-conducting coating is formed by mixing a dispersion liquid A and a dispersion liquid B, wherein the dispersion liquid A is prepared by stirring and mixing 20-35 parts by mass of boron nitride, 2-3 parts by mass of a modifier and 30-50 parts by mass of water, and filtering and washing; re-dispersing filter residues in the first organic solvent, adding 50-150 parts of epoxy resin, and uniformly stirring to obtain the organic solvent; and the dispersion liquid B is obtained by mixing 5-9 parts of graphene, 0.6-3 parts of carbon tubes and 15-40 parts of a second organic solvent and carrying out ultrasonic treatment. The thermal conductivity of the heat-conducting coating obtained by the invention is more than or equal to 2.5W (m)‑1K‑1) The paint can resist high temperature of 1000 ℃, is water-resistant for up to 30 days, has good adhesive force and acid and alkali resistance, can be applied to a steam generator of a nuclear power station, and meets the requirements of quick heat dissipation, high temperature resistance and high temperature resistanceThe water requirement.
Description
Technical Field
The invention relates to a heat-conducting coating, in particular to a heat-conducting coating utilizing the synergistic effect of three fillers and a preparation method and application thereof; belongs to the field of material science and surface technology.
Background
The nuclear power station is a common power generation facility, in the power generation process, a nuclear reactor directly heats liquid sodium, the liquid sodium absorbs heat of the reactor and then conducts the heat to a steam-water system through a steam generator, and generated steam pushes a steam turbine to generate power. Wherein as middle heat transfer equipment's steam generator can produce a large amount of heats in the reaction process, reaches high temperature, and these heats need in time be dispelled, and the simultaneous generator produces a large amount of steam, and vapor contacts the pipeline wall for a long time, causes destruction to the pipeline wall easily, does not have a coating at present and can satisfy steam generator fast heat dissipation, high temperature resistant and water-fast demand simultaneously.
At present, most of filled heat-conducting coatings prepared at home and abroad only improve the heat-conducting property of the coatings, and cannot simultaneously meet various requirements of a steam generator, meanwhile, the coatings are formed by means of hot pressing and the like in an auxiliary mode, the process is complex, the processing time is long, the energy consumption is high, the application range is limited due to different technical means, and the quality, the yield and the cost of coating production are influenced. Therefore, the conventional process for preparing the heat-conducting coating is time-consuming and energy-consuming, and the application range is limited by the film-forming process means.
The Chinese patent application CN202010350768.7 discloses a method for preparing a composite heat-conducting film by mixing GO water dispersion and hexagonal boron nitride water dispersion, wherein the film has good heat-conducting effect, but needs to be annealed at 800-3000 ℃ for 2 hours, the application range of the film is not as wide as that of a coating, the preparation process flow is complex, and the energy consumption is relatively high.
The chinese patent application CN201810830682.7 discloses a coating material containing film-forming agents such as polyurethane glue as a coating matrix, graphene as a filler, and graphene oxide, one-dimensional carbon tubes, inorganic metal compound heat-conducting agents dispersed and distributed in the coating material, but high-speed stirring and ball-milling are required in the preparation process, which consumes more energy, and the used filler is expensive.
The Chinese patent application CN201911152581.X discloses a preparation method of a high-thermal-conductivity boron nitride/epoxy resin composite material, although the filler is boron nitride with low cost, the boron nitride boron alkylation time is 5-10 hours, the time is consumed, the material preparation needs a hot pressing process, and the application range is limited.
Disclosure of Invention
The invention aims to solve the technical problem of providing a heat-conducting coating which simultaneously meets the requirements of efficient heat dissipation, high temperature resistance and water resistance and utilizes the synergistic effect of three fillers and a preparation method thereof, wherein the heat conductivity of a coating formed by the coating is more than or equal to 2.5W (m)-1K-1) Can reach 5.65W (m)-1K-1) The high-temperature resistant paint can resist high temperature up to 1000 ℃, resist water for 30 days, and simultaneously have good hardness, adhesive force and acid and alkali resistance.
Another problem to be solved by the present invention is to provide the use of the thermally conductive coating on a steam generator using the synergistic effect of three fillers.
The purpose of the invention is realized by the following technical scheme:
a heat-conducting coating utilizing synergistic effect of three fillers is formed by mixing a dispersion liquid A and a dispersion liquid B, and when the heat-conducting coating is used, a curing agent is added, mixed and evenly coated on the surface of a metal heat-conducting device; the dispersion liquid A is prepared by stirring and mixing 20-35 parts by mass of boron nitride, 2-3 parts by mass of a modifier and 30-50 parts by mass of water, and filtering and washing; re-dispersing filter residues in the first organic solvent, adding 50-150 parts of epoxy resin, and uniformly stirring to obtain the organic solvent; the dispersion liquid B is obtained by mixing 5-9 parts of graphene, 0.6-3 parts of carbon tubes and 15-40 parts of a second organic solvent and carrying out ultrasonic treatment; the boron nitride is hexagonal boron nitride, the length of a long shaft is 150-450 nm, and the boron nitride is elliptic disc-shaped; when the length of the long axis of the hexagonal boron nitride is 150-250nm, the particle size of the graphene is 2.5-2.7 microns, and the length of the carbon tube is 0.5-1 micron; when the length of the long axis of the hexagonal boron nitride is 250-350nm, the particle size of the graphene is 2.7-3.0 microns, and the length of the carbon tube is 1-2.5 microns; when the length of the long axis of the hexagonal boron nitride is 350-450nm, the particle size of the graphene is 3.0-3.5 microns, and the length of the carbon tube is 2.3-3.5 microns.
To further achieve the object of the present invention, preferably, when the length of the long axis of the boron nitride is between 150-250nm, the first solvent is one of tetrahydrofuran, ethyl acetate and isopropanol; when the length of the long axis of the boron nitride is between 250-350nm, the first solvent is one of acetone, acetic acid, acetonitrile and DMF; when the length of the long axis of the boron nitride is between 350-450nm, the first solvent is one of dimethyl sulfoxide, methanol and ethylene glycol.
Preferably, the boron nitride particles are contained in an amount of 80 wt% or more within a range of ± 30% of the length of the major axis, and have an elliptical disk shape, and the minor axis La, the major axis Lb, and the thickness t satisfy the following equation: lb is more than or equal to 150nm and less than or equal to 450nm, t is more than or equal to 30nm and less than or equal to 200nm, t is more than or equal to La, and La/Lb is more than or equal to 0.5 and less than or equal to 1.0.
Preferably, the graphene is expanded graphite, the length of the long axis is 2.5-3.5 microns, and more than 80 wt% of particles are contained in the range of the length of the long axis +/-30%.
Preferably, the carbon tubes are one or more of multi-wall carbon tubes and single-wall carbon tubes, and have an average diameter of 2-2.2nm and a length of 0.5-3.5 microns.
Preferably, the epoxy resin is one or more of bisphenol A epoxy resin, brominated bisphenol A epoxy resin or hydrogenated bisphenol A epoxy resin; the modifier is one or more of tannic acid, sodium hydroxide and potassium hydroxide.
Preferably, the second organic solvent is one or more of ethyl acetate, acetone, DMF, DMSO and isopropanol.
Preferably, the curing agent is one of methyl hexahydro anhydride, methyl tetrahydrogen anhydride, phthalic anhydride, hexamethoxy methyl melamine and lauric acid; the adding amount of the curing agent is 50-150 parts by mass; and (3) after the curing agent is added, controlling the stirring speed to be 300-400 rpm, and stopping stirring after mechanical stirring for 5-10 minutes.
The preparation method of the heat-conducting coating utilizing the synergistic effect of the three fillers comprises the following steps:
1) preparation of dispersion A: stirring and mixing boron nitride, a modifier and water, filtering and washing; re-dispersing filter residues in the first organic solvent, adding epoxy resin, and stirring to obtain a dispersion liquid A;
2) preparation of dispersion B: mixing graphene, a carbon tube and a second organic solvent, and performing ultrasonic treatment to obtain a dispersion liquid B;
3) and adding the dispersion liquid B into the dispersion liquid A under low-speed stirring to obtain the heat-conducting coating.
The application of the heat-conducting coating utilizing the synergistic effect of the three fillers to the steam generator is disclosed.
Hydroxyl exists on the surface of the modified hexagonal boron nitride, and the hydroxyl can perform ring-opening reaction with epoxy resin, so that the dispersibility of the boron nitride in the epoxy resin is greatly improved. It should be noted that, as the size of boron nitride increases, the polarity of the solvent required increases, and when the size of boron nitride is adapted to the polarity of the solvent, the boron nitride forms a "boron nitride-epoxy resin" system which is uniformly dispersed and stably present in the epoxy resin, and the boron nitride in the system is uniformly and stably distributed.
According to the invention, graphene which is larger and thinner than boron nitride and a carbon tube with a long length-diameter ratio are added into the system, and the newly added filler can be subjected to secondary distribution on the basis of boron nitride distribution, so that the phenomenon of agglomeration which often occurs when the graphene and the carbon tube are dispersed in resin can be avoided due to the secondary distribution, and the mutual overlapping of the three fillers and the uniform and stable dispersion state of the three fillers in the resin are realized. When the resin containing the filler is formed into a film on a metal base material, the boron nitride sheets in the resin are in a flaky structure due to the fact that the density of the boron nitride sheets is higher than that of epoxy resin, and the boron nitride sheets are in a disordered turn to a flat arrangement under the action of gravity. In the process, graphene which is larger and lighter than boron nitride is needed to assist, on one hand, the graphene is larger in size and can be prevented from agglomerating in the middle of the boron nitride, and on the other hand, the graphene is small in density, so that the graphene can be pulled and driven by boron nitride sheets and also turns to a tiled state to form a layer-by-layer stacked morphology. The combination of the three fillers enables the three fillers to jointly form close connection under the action of gravity only, and the laminated three-dimensional network structure with a regular structure greatly reduces phonon scattering of heat in the resin film transfer process, thereby improving the heat transfer efficiency, and meanwhile, the coating has good high temperature resistance and water resistance.
Compared with the prior art, the invention has the beneficial effects that:
1) according to the invention, modified hexagonal boron nitride is added into epoxy resin, ring-opening reaction can be carried out on the modified boron nitride and the epoxy resin, and the boron nitride is dispersed by the aid of organic solvents with different polarities, so that a stable dispersion system is formed. And then introducing a mixed solution of graphene and carbon tubes, and constructing a layer-by-layer stacked heat-conducting network structure in a film forming process by utilizing the characteristic that the density of boron nitride is greater than that of epoxy resin and the synergistic effect of the shape and the size of fillers, so that the heat-conducting and heat-resisting properties of the coating prepared from the coating are greatly improved.
2) According to the invention, hexagonal boron nitride is used as a main heat-conducting filler, epoxy resin is used as a film-forming agent, firstly, the hexagonal boron nitride is subjected to hydroxylation modification, so that the hexagonal boron nitride and the epoxy resin firstly undergo a ring-opening reaction, the boron nitride is assisted to be dispersed in the epoxy resin by virtue of organic solvents with different polarities, a boron nitride stable dispersion system is formed, and the added graphene and the carbon tubes are assisted to realize the same good dispersion effect. Because the density of boron nitride is higher, the graphene and the graphene are in a hexagonal sheet structure under the action of gravity in the film forming process, the morphology of the graphene is similar to that of the graphene, the graphene and the graphene are in a flat arrangement under the influence of the boron nitride, and the carbon tubes with ultrahigh length-diameter ratio are inserted between the graphene and the graphene, so that the graphene, the graphene and the graphene form a laminated network structure. The invention improves the quality of the heat-conducting coating and realizes the normal-temperature, rapid and energy-saving preparation of the heat-conducting coating; the invention utilizes the matching effect of the shape and the size of the fillers and the gravity effect.
3) The method utilizes solvents with different polarity sizes to assist in dispersing boron nitride with different sizes so as to achieve the state that the boron nitride is stably dispersed in the epoxy resin for a long time;
4) according to the invention, the boron nitride dispersion system is utilized to help graphene and carbon tubes to realize an excellent stable dispersion state in the epoxy resin, the process technology is simple, and the graphene and the carbon tubes do not need to be additionally treated;
5) the invention utilizes the characteristic that the density of boron nitride is higher than that of epoxy resin, and leads the fillers to form ordered arrangement only through the action of gravity, thereby greatly reducing the economic loss caused by using auxiliary means such as hot pressing, magnetic fields and the like in the prior preparation process;
6) the invention utilizes the similarity and complementarity of the sizes and the shapes of the fillers to ensure the completeness and the order of the network structure and the stability of the heat conduction effect.
Drawings
Fig. 1 is a scanning electron microscope picture of the composite heat-conducting coating and the epoxy resin coating obtained in example 1 at the same scale, and the magnification is 500 times.
FIG. 2 is a scanning electron micrograph of a cross section of the coating obtained in example 1 magnified 4000 times.
FIG. 3 is a scanning electron microscope image of a 50000 times magnified cross section of the composite thermal conductive coating of example 1.
FIG. 4 is a scanning electron micrograph at 4000 Xmagnification of a cross section of the resulting coating of comparative example 1.
FIG. 5 is a scanning electron micrograph at 4000 Xmagnification of a cross section of the resulting coating of comparative example 2.
FIG. 6 is a scanning electron micrograph at 4000 Xmagnification of a cross section of the resulting coating of comparative example 3.
FIG. 7 is a scanning electron micrograph at 4000 Xmagnification of a cross section of the resulting coating of comparative example 4.
Fig. 8 is a comparison graph of the composite thermal conductive coating obtained in example 1 after being burned at 1000 ℃ for 30 minutes and the epoxy resin coating after being burned at 300 ℃ for 30 minutes.
Fig. 9 is a graph comparing the in-plane thermal conductivity of the composite thermally conductive coating obtained in example 1 with comparative examples 1, 2, 3, 4 and epoxy resin coatings.
Detailed Description
For better understanding of the present invention, the present invention is further illustrated by the following specific examples, which are not intended to limit the scope of the claims of the present invention, and other examples obtained by those skilled in the art without inventive efforts shall fall within the scope of the present invention.
The appearance of the composite heat-conducting coating is evaluated according to the GB11376-89 specification; testing the film thickness of the composite heat-conducting coating according to the GB4956 specification; the hardness of the coatings was tested according to the GB/T6739-1996 protocol; testing the adhesion of the coating by adopting a cross-cut method according to the GB/T9286-1998; the coatings were tested for water resistance as specified in GB/T1733-1993A; testing the acid resistance of the coating according to the GB/T9274-1988A method; the coatings were tested for alkali resistance as specified in GB/T9274-1998A; the thermal conductivity of the coating was evaluated according to the rule E14616.
The appearance and morphology of the embodiment of the invention are characterized by using a scanning electron microscope (FE-SEM, SU-8200, Japan).
Inventive examples the film thickness variation was measured using a film thickness meter (kett, LZ-990).
The embodiment of the invention uses a laser thermal conductivity meter which is Hotdisk, 2500 s.
In the embodiment of the invention, a muffle furnace is 3ctest, SX-8-10P.
Example 1
Weighing the following raw material components in parts by weight:
hexagonal boron nitride plate (major axis length 300nm, powder shape is elliptic disk, minor axis La, major axis LbAnd the thickness t satisfies: la-280 nm, Lb＝300nm，t＝20nm，La/Lb0.93), 2 parts of tannic acid and 45 parts of water were put in a flask, and the stirring speed was controlled at 500 rpm, and the mixture was mechanically stirred for 90 minutes, then the stirring was stopped, and the mixture was filtered and washed. Re-dispersing the filter residue in acetone, adding 50 parts of bisphenol A epoxy resin, controlling the stirring speed at 400 r/min, mechanically stirring for 120 min, and stopping stirring to obtain a dispersion A;
putting 7 parts of graphene (with the average diameter of 2.5 microns and the powder shape of hexagonal sheets), 1 part of multi-walled carbon tube (with the average diameter of 2nm and the length of 1.6 microns) and 15 parts of DMF (dimethyl formamide) into a flask, and carrying out ultrasonic dispersion for 20 minutes to obtain a dispersion liquid B;
and slowly adding the dispersion liquid B into the dispersion liquid A, controlling the stirring speed at 30 revolutions per minute, and stopping stirring after the dispersion liquid B is added. 60 parts of methylhexahydroanhydride curing agent are added and mechanically stirred for 5 minutes. And uniformly and quickly brushing the prepared composite heat-conducting coating on the titanium alloy substrate after rust and oil removal, waiting for the surface of the coating to be dried at room temperature, and transferring the coating into an oven for drying for 30 minutes to obtain the composite heat-conducting coating.
The appearance of the composite heat-conducting coating obtained in the embodiment 1 is pure black, the film layer is fine and smooth, and the measured film thickness is 20.3 micrometers according to the test method of GB 4956. The thermal conductivity of the composite coating is tested according to the specification E1461, and the result shows that the thermal conductivity of the coating is 5.65W (m)-1K-1)。
Example 2
Hexagonal boron nitride sheet (major axis length 150nm, powder shape is elliptic disk, minor axis La, major axis LbAnd the thickness t satisfies: la 140nm, Lb＝150nm，t＝20nm，La/Lb0.93), 2 parts of sodium hydroxide and 50 parts of water were put in a flask, and the stirring speed was controlled at 500 rpm, and the mechanical stirring was stopped after 90 minutes, followed by filtration and washing. Re-dispersing filter residues in ethyl acetate, adding 70 parts of brominated bisphenol A epoxy resin, controlling the stirring speed at 400 revolutions per minute, mechanically stirring for 120 minutes, and stopping stirring to obtain a dispersion liquid A;
putting 5 parts of graphene (with the average diameter of 2.7 microns and the powder shape of hexagonal sheets), 1 part of multi-walled carbon tube (with the average diameter of 2nm and the length of 0.7 micron) and 20 parts of DMF (dimethyl formamide) into a flask, and carrying out ultrasonic dispersion for 20 minutes to obtain a dispersion liquid B;
and slowly adding the dispersion liquid B into the dispersion liquid A, controlling the stirring speed at 35 revolutions per minute, and stopping stirring after the addition of the dispersion liquid B is finished. 65 parts of methyltetrahydroanhydride curing agent was added and mechanically stirred for 5 minutes. And uniformly and quickly brushing the prepared composite heat-conducting coating on the titanium alloy substrate after rust and oil removal, waiting for the surface of the coating to be dried at room temperature, and transferring the coating into an oven to be dried for 30 minutes to obtain the composite heat-conducting coating.
The appearance of the composite heat-conducting coating obtained in this embodiment 2 is pure black, the film layer is fine and smooth, and the measured film thickness is 23.9 micrometers according to the test method of GB 4956. The thermal conductivity of the composite coating is tested according to the specification E1461, and the result shows that the thermal conductivity of the coating is 3.244W (m)-1K-1)。
Example 3
Hexagonal boron nitride flakes (major axis length 260nm, powder shape oval disk, minor axis La, major axis LbAnd the thickness t satisfies: la-200 nm, Lb＝260nm，t＝30nm，La/Lb0.77) of tannic acid, 3 parts of tannic acid and 50 parts of water were put in a flask, and stirred at 500 rpm for 100 minutes by mechanical stirring, and then the stirring was stopped, followed by filtration and washing. Dispersing the filter residue in acetone again, adding 150 parts of brominated bisphenol A epoxy resin, controlling the stirring speed at 300 revolutions per minute, mechanically stirring for 120 minutes, and stopping stirring to obtain a dispersion liquid A;
putting 10 parts of graphene (with the average diameter of 3 microns and the powder shape of hexagonal sheets), 1 part of multi-walled carbon tube (with the average diameter of 2nm and the length of 2.3 microns) and 17 parts of acetone into a flask, and performing ultrasonic dispersion for 20 minutes to obtain a dispersion liquid B;
and slowly adding the dispersion liquid B into the dispersion liquid A, controlling the stirring speed at 30 revolutions per minute, and stopping stirring after the dispersion liquid B is added. 150 parts of phthalic anhydride curing agent was added and mechanically stirred for 5 minutes. And uniformly and quickly brushing the prepared composite heat-conducting coating on the titanium alloy substrate after rust and oil removal, waiting for the surface of the coating to be dried at room temperature, and transferring the coating into an oven for drying for 30 minutes to obtain the composite heat-conducting coating.
The appearance of the composite heat-conducting coating obtained in this embodiment 3 is pure black, the film layer is fine and smooth, and the thickness of the measured film is 25.7 micrometers according to the test method of GB 4956. The thermal conductivity of the composite coating is tested according to the specification E1461, and the result shows that the thermal conductivity of the coating is 2.875W (m)-1K-1)。
Example 4
Hexagonal boron nitride tablet (major axis length 450nm, powder shape is elliptic disk, minor axis La, major axis LbAnd the thickness t satisfies: la 420nm, Lb＝450nm，t＝30nm，La/Lb0.93), 2 parts of potassium hydroxide and 50 parts of water were put into a flask, and the mixture was mechanically stirred at 500 rpm for 90 minutes while controlling the stirring speed, and then the stirring was stopped, followed by filtration and washing. Re-dispersing the filter residue in methanol, adding 70 parts of hydrogenated bisphenol A epoxy resin, controlling the stirring speed at 400 rpm, and mechanically stirringStirring for 120 minutes, and then stopping stirring to obtain a dispersion liquid A;
putting 5 parts of graphene (with the average diameter of 2.8 microns and the powder shape of hexagonal sheets), 1 part of multi-walled carbon tube (with the average diameter of 2nm and the length of 3.2 microns), 0.5 part of multi-walled carbon tube and 15 parts of ethyl acetate into a flask, and performing ultrasonic dispersion for 20 minutes to obtain a dispersion liquid B;
and slowly adding the dispersion liquid B into the dispersion liquid A, controlling the stirring speed at 45 revolutions per minute, and stopping stirring after the addition of the dispersion liquid B is finished. 75 parts of methylhexahydroanhydride curing agent are added and mechanically stirred for 5 minutes. And uniformly and quickly brushing the prepared composite heat-conducting coating on the titanium alloy substrate after rust and oil removal, waiting for the surface of the coating to be dried at room temperature, and transferring the coating into an oven for drying for 30 minutes to obtain the composite heat-conducting coating.
The appearance of the composite heat-conducting coating obtained in this embodiment 4 is pure black, the film layer is fine and smooth, and the measured film thickness is 20.4 micrometers according to the test method of GB 4956. The thermal conductivity of the composite coating is tested according to the specification E1461, and the result shows that the thermal conductivity of the coating is 4.105W (m)-1K-1)。
Comparative example 1
A composite heat-conducting coating, similar to the preparation method of embodiment 1 of the present invention, is different in that: and (3) directly adding the methyl hexahydroic anhydride curing agent into the dispersion liquid A without preparing the dispersion liquid B, and carrying out subsequent operation to obtain the composite epoxy resin coating only containing the hexagonal boron nitride sheets.
The composite heat-conducting coating obtained in the comparative example 1 is grey white in appearance, the film layer is fine and smooth, and the thickness of the measured film is 30.1 micrometers according to a test method of GB 4956. The thermal conductivity of the composite coating is tested according to the specification E1461, and the result shows that the thermal conductivity of the coating is 1.414W (m)-1K-1)。
Comparative example 2
A composite heat-conducting coating, similar to the preparation method of embodiment 1 of the present invention, is different in that: after modification treatment, the hexagonal boron nitride sheet is directly dispersed in acetone together with graphene and a multi-wall carbon tube, and bisphenol A type epoxy resin is added for subsequent operation to obtain the epoxy resin composite coating formed by directly mixing three fillers.
The appearance of the composite heat-conducting coating obtained in the comparative example 2 is pure black, the film layer is fine and smooth, and the thickness of the measured film is 15.7 microns according to the test method of GB 4956. The thermal conductivity of the composite coating is tested according to the specification E1461, and the result shows that the thermal conductivity of the coating is 3.177W (m)-1K-1)。
Comparative example 3
A composite heat-conducting coating, similar to the preparation method of embodiment 1 of the present invention, is different in that: modified hexagonal boron nitride tablet (major axis length 300nm, powder shape is elliptic disk, minor axis La, major axis LbAnd the thickness t satisfies: la 240nm, Lb＝300nm，t＝20nm，La/Lb0.80) is re-dispersed by DMF with polarity higher than that of acetone, and subsequent operation is carried out to obtain the epoxy resin composite coating dispersed by the high-polarity solvent.
The composite heat-conducting coating obtained in the comparative example 3 is pure black in appearance, the film layer is fine and smooth, and the thickness of the measured film is 28.1 micrometers according to the test method of GB 4956. The thermal conductivity of the composite coating is tested according to the specification E1461, and the result shows that the thermal conductivity of the coating is 2.102W (m)-1K-1)。
Comparative example 4
A composite heat conductive coating, similar to the preparation method of embodiment 1 of the present invention, is different in that: the hexagonal boron nitride sheet was changed to have a major axis length of 1.2 μm (the powder shape was an elliptical disk, and minor axis La and major axis LbAnd the thickness t satisfies: la-0.9 μm, Lb1.2 micron, t 200nm, La/Lb0.75), and changing the average diameter of graphene to 700nm to obtain the large-size boron nitride-small-size graphene epoxy resin composite coating.
The appearance of the composite heat-conducting coating obtained in the comparative example 4 is pure black, the film layer is fine and smooth, and the thickness of the measured film is 17.9 microns according to the test method of GB 4956. The thermal conductivity of the composite coating is tested according to the specification E1461, and the result shows that the thermal conductivity of the coating is 2.178W (m)-1K-1)。
Table 1 shows the hardness and adhesion of the coatings obtained in examples 1 to 4Strength, water resistance and weather resistance. It can be seen that the hardness of the coating reaches 3H, the adhesive force reaches 1 level, the coating can be well attached to the surface of the metal base material, and meanwhile, the coating has excellent water resistance (no foaming and no discoloration of the coating 30 d) and weather resistance. The coating has excellent heat-conducting property (the heat conductivity of the coating is more than or equal to 2.5W (m)-1K-1) 1000 ℃, and water resistance for up to 30 days, can be completely suitable for the operating environment of the steam generator, meets the requirements that the steam generator generates a large amount of heat in the operating process and needs to timely dissipate and protect equipment, and can bear the extremely high temperature generated in the operating process and the coating is not damaged when contacting steam for a long time. The composite coating completely meets the protection requirement of the steam generator due to the performances, and the composite coating is simple and convenient in preparation process, low in energy consumption and applicable to industrial production.
TABLE 1
Fig. 1 is a scanning electron microscope picture of the composite thermal conductive coating and the epoxy resin coating obtained in example 1 at the same scale, and the magnification is 100 times. The pure epoxy resin coating (left) is seen to be smooth in surface, while the filler-doped composite coating (right) is seen to be significantly rough in surface, and the presence of fillers such as boron nitride flakes is observed, indicating that the fillers are successfully combined with the epoxy resin.
FIGS. 2 to 6 are scanning electron microscope pictures of the cross sections of the coatings obtained in example 1, comparative example 2, comparative example 3 and comparative example 4 on the same scale, respectively, with a magnification of 4000 times; fig. 3 is a 50000 times enlarged cross section of the composite thermally conductive coating of example 1. The laminated three-dimensional network formed by the boron nitride, the graphene and the carbon tubes is more clearly displayed, the boron nitride is accumulated in the graphene with large particle size, and the carbon tubes are inserted between the boron nitride and the graphene to form the shape of longitudinal connection. Comparing fig. 1, 2 and fig. 4-7, it can be clearly seen that only the cross section of the composite heat-conducting coating obtained in example 1 presents an ordered laminated three-dimensional network structure, while the cross section of the composite heat-conducting coating obtained in comparative examples 1-4 presents a state that the fillers are randomly distributed and arranged. FIG. 4 shows that, in comparative example 1, which contains only one filler of boron nitride, the single filler exhibits an agglomerated morphology, absent the synergistic effect of graphene and carbon nanotubes; fig. 5 shows that, in comparative example 2, three fillers are directly mixed, and a step of adding boron nitride into epoxy resin in advance to help the graphene and the carbon nanotube to disperse is omitted, so that the three fillers can only be simply mixed, and thus the three fillers are randomly arranged; FIG. 6 shows that, in comparative example 3, a solvent with polarity higher than a suitable range is used, so that boron nitride cannot be stably dispersed due to the influence of the polarity of the solvent when the boron nitride is dispersed into an epoxy resin system, and therefore, all three fillers cannot be stably dispersed finally, and the fillers in the coating also have the randomly arranged morphology; fig. 7 shows that, in comparative example 4, large-sized boron nitride is used together with small-sized graphene, and although the boron nitride still has a gravity traction effect on the graphene, the boron nitride is too large in size, so that light and thin graphene is directly pressed together to form a stacked morphology, and the morphology also lacks order. The scanning electron microscope results of example 1 and comparative example above show that an ordered three-dimensional network can only be created when the three fillers are in a solvent of appropriate polarity, with a certain order of addition and a certain particle size ratio. The ordered three-dimensional network can effectively reduce phonon scattering in the heat transfer process and improve the heat transfer efficiency, and further shows that the heat conductivity of the composite coating is improved as can be seen in a figure 9, and the heat conductivity of the coating obtained in example 1 is far higher than that of the coatings obtained in comparative examples 1-4 and the epoxy resin coating.
Fig. 8 is a comparison graph of the composite thermal conductive coating obtained in example 1 after being burned at 1000 ℃ for 30 minutes and the epoxy resin coating after being burned at 300 ℃ for 30 minutes. The left graph is a comparison graph before and after the epoxy resin coating is burnt, and it can be seen that the epoxy resin surface is obviously discolored after being burnt at 300 ℃ for 30 minutes, and burnt odor is emitted in the actual operation. The right graph is a comparison graph of the composite coating obtained in example 1 before and after being burned at 1000 ℃, and the surface of the composite coating is not changed after being burned, which shows that the composite coating has better heat resistance.
Fig. 9 is a graph comparing thermal conductivity of the composite thermal conductive coating obtained in example 1 with that of epoxy resin coatings, comparative example 1, comparative example 2, comparative example 3 and comparative example 4. As seen from the figure: the thermal conductivity of the composite coating doped with the filler is obviously higher than that of other coatings, because the coating of the comparative example 1 only contains hexagonal boron nitride sheets and lacks the synergistic effect of the three fillers; in the comparative example 2, the three fillers are directly and mechanically mixed, and the graphene and the carbon tube cannot realize a good dispersion effect by virtue of a stable dispersion system of boron nitride, so that the thermal conductivity is low; comparative example 3 a small-sized boron nitride sheet was dispersed using an incompatible high-polarity solvent, so that boron nitride could not form a uniform dispersion state in the epoxy resin, thereby affecting the construction of the subsequent laminated structure, resulting in a reduction in thermal conductivity; comparative example 4 uses large-sized boron nitride and small-sized graphene, which are incompatible in size, and cannot construct a layer-by-layer stacked network structure, so that the thermal conductivity is lower than that of the composite thermal conductive coating of example 1. The above comparative example illustrates that the three fillers can construct a laminated heat-conducting network under the conditions of a solvent with proper polarity, a certain adding sequence and a certain proportion of sizes, and the construction of the laminated heat-conducting network can obviously improve the heat-conducting performance of the coating. The applicant finds that the particle size of the graphene is 2.5-2.7 microns and the length of the carbon tube is 0.5-1 micron only when the length of the long axis of the hexagonal boron nitride is 150-250 nm; when the length of the long axis of the hexagonal boron nitride is 250-350nm, the particle size of the graphene is 2.7-3.0 microns, and the length of the carbon tube is 1-2.5 microns; when the length of the long axis of the hexagonal boron nitride is 350-450nm, the particle size of the graphene is 3.0-3.5 microns, and the length of the carbon tube is 2.3-3.5 microns, the invention can realize the construction of the laminated heat-conducting network, obviously improve the heat-conducting property of the coating, and simultaneously realize the high-temperature resistance, excellent water resistance and other comprehensive properties of the heat-conducting coating.
Compared with the graphene-boron nitride composite film with insulating and heat conducting properties reported in Chinese patent application CN202010350768.7, the epoxy resin composite coating can be applied to heat dissipation protection of metal electronic equipment, and the maximum film interfacial heat conductivity is only 2.931W (m)-1K-1) The thermal conductivity of the coating of the invention is as high as 5.65W (m)-1K-1) Not only has higher heat conductivity, but also has simpler preparation process than a film as a coating, has low requirement on equipment, has obvious cost advantage and preparation process advantage,the heat-conducting coating also has high temperature resistance and water resistance, realizes heat conduction of the coating by using the coating, and has more advantages than a film.
Compared with the heat-conducting coating reported by the prior art such as Chinese patent CN201810830682.7, the epoxy resin composite coating has good heat-conducting property, the high-temperature resistance is as high as 1000 ℃, the temperature resistance is superior to 200 ℃ of the coating, the coating can be suitable for a higher-temperature application environment, high-speed stirring and ball milling treatment are avoided in the preparation process of the coating, and the energy consumption is obviously reduced.
Compared with the boron nitride/epoxy resin composite material with high thermal conductivity reported in Chinese invention patent application No. CN201911152581.X, the thermal conductivity of the epoxy resin film obtained by the invention is 5.86W (m)-1K-1) The heat-dissipation coating is a heat-dissipation coating, does not need a hot-pressing process, is not limited by a preparation process when applied to a metal component, and also has the advantage of a heat-conduction coating.
A steam generator serving as intermediate heat exchange equipment in a nuclear power station needs a coating, and most of the conventional high-molecular polymer coatings have poor heat dissipation performance, are not high temperature resistant and poor in water resistance, or cannot meet the three requirements at the same time. The invention provides an efficient heat dissipation coating which can be applied to various metal equipment with heat dissipation requirements, and the heat conductivity of the obtained heat conduction coating is more than or equal to 2.5W (m)-1K-1) The maximum can reach 5.65W (m)-1K-1) The high-temperature-resistant heat-conducting filler has the advantages of high temperature resistance of 1000 ℃, water resistance of 30 days, good hardness and adhesion, good acid and alkali resistance, excellent comprehensive performance, low cost, simple process flow and high cost performance, is mainly boron nitride with low price, and can realize high-temperature resistance and quick heat dissipation aiming at the conventional common metal equipment.
It should be noted that the present invention is not limited by the above-mentioned embodiments, and various changes and modifications can be made in the present invention without departing from the spirit and scope of the present invention, and these changes and modifications fall into the protection scope of the claimed invention; the scope of the invention is defined by the following claims.
Claims (10)
1. A heat-conducting coating utilizing synergistic effect of three fillers is characterized in that the heat-conducting coating is formed by mixing a dispersion liquid A and a dispersion liquid B, and a curing agent is added during use and is uniformly mixed and coated on the surface of a metal heat-conducting device; the dispersion liquid A is prepared by stirring and mixing 20-35 parts by mass of boron nitride, 2-3 parts by mass of a modifier and 30-50 parts by mass of water, and filtering and washing; re-dispersing filter residues in the first organic solvent, adding 50-150 parts of epoxy resin, and uniformly stirring to obtain the organic solvent; the dispersion liquid B is obtained by mixing 5-9 parts of graphene, 0.6-3 parts of carbon tubes and 15-40 parts of a second organic solvent and carrying out ultrasonic treatment; the boron nitride is hexagonal boron nitride, the length of a long shaft is 150-450 nm, and the boron nitride is elliptic disc-shaped; when the length of the long axis of the hexagonal boron nitride is 150-250nm, the particle size of the graphene is 2.5-2.7 microns, and the length of the carbon tube is 0.5-1 micron; when the length of the long axis of the hexagonal boron nitride is 250-350nm, the particle size of the graphene is 2.7-3.0 microns, and the length of the carbon tube is 1-2.5 microns; when the length of the long axis of the hexagonal boron nitride is 350-450nm, the particle size of the graphene is 3.0-3.5 microns, and the length of the carbon tube is 2.3-3.5 microns.
2. The heat-conducting paint utilizing the synergistic effect of the three fillers as claimed in claim 1, wherein when the length of the long axis of the boron nitride is between 150nm and 250nm, the first solvent is one of tetrahydrofuran, ethyl acetate and isopropanol; when the length of the long axis of the boron nitride is between 250-350nm, the first solvent is one of acetone, acetic acid, acetonitrile and DMF; when the length of the long axis of the boron nitride is between 350-450nm, the first solvent is one of dimethyl sulfoxide, methanol and glycol.
3. The thermally conductive coating material according to claim 1, wherein the particles of boron nitride in an amount of 80 wt% or more are included in a range of a major axis length ± 30%, and have an elliptic disk shape, and the minor axis La, the major axis Lb and the thickness t satisfy the following formula: lb is more than or equal to 150nm and less than or equal to 450nm, t is more than or equal to 30nm and less than or equal to 200nm, t is more than or equal to La, and La/Lb is more than or equal to 0.5 and less than or equal to 1.0.
4. The thermally conductive coating material according to claim 1, wherein said graphene is expanded graphite, the length of the long axis is 2.5 to 3.5 μm, and 80 wt% or more of particles are included in the range of the length of the long axis ± 30%.
5. The heat conductive coating material using the synergistic effect of three fillers as claimed in claim 1, wherein the carbon tubes are one or more of multi-walled carbon tubes and single-walled carbon tubes, and have an average diameter of 2 to 2.2nm and a length of 0.5 to 3.5 μm.
6. The thermally conductive coating utilizing three fillers in synergy according to claim 1, wherein the epoxy resin is one or more of bisphenol a type epoxy resin, brominated bisphenol a type epoxy resin or hydrogenated bisphenol a type epoxy resin; the modifier is one or more of tannic acid, sodium hydroxide and potassium hydroxide.
7. The thermally conductive coating using three fillers in cooperation according to claim 1, wherein the second organic solvent is one or more of ethyl acetate, acetone, DMF, DMSO, and isopropyl alcohol.
8. The thermally conductive coating material using the synergistic effect of three fillers as claimed in claim 1, wherein the curing agent is one of methylhexahydroanhydride, methyltetrahydroanhydride, phthalic anhydride, hexamethoxymethylmelamine and lauric acid; the adding amount of the curing agent is 50-150 parts by mass; and (3) after the curing agent is added, controlling the stirring speed to be 300-400 rpm, and stopping stirring after mechanical stirring for 5-10 minutes.
9. The method for preparing a thermally conductive coating material using the synergistic effect of three fillers as set forth in any one of claims 1 to 8, characterized by comprising the steps of:
1) preparation of dispersion A: stirring and mixing boron nitride, a modifier and water, filtering and washing; re-dispersing filter residues in the first organic solvent, adding epoxy resin, and stirring to obtain a dispersion liquid A;
2) preparation of dispersion B: mixing graphene, a carbon tube and a second organic solvent, and performing ultrasonic treatment to obtain a dispersion liquid B;
3) and adding the dispersion liquid B into the dispersion liquid A under low-speed stirring to obtain the heat-conducting coating.
10. Use of a thermally conductive coating according to any one of claims 1 to 8 with three fillers acting in synergy on a steam generator.
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Cited By (1)
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| CN115505309A (en) * | 2022-10-26 | 2022-12-23 | 天津中电立正石墨烯科技有限公司 | Water-based graphene heat dissipation coating and preparation method thereof |
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