CN111334140A - Micro-nano carbon composite heat dissipation coating and preparation method thereof - Google Patents
Micro-nano carbon composite heat dissipation coating and preparation method thereof Download PDFInfo
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- CN111334140A CN111334140A CN202010221974.8A CN202010221974A CN111334140A CN 111334140 A CN111334140 A CN 111334140A CN 202010221974 A CN202010221974 A CN 202010221974A CN 111334140 A CN111334140 A CN 111334140A
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- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention discloses a micro-nano carbon composite heat dissipation coating, which comprises graphitized solid carbon spheres and acrylic resin as raw materials, and also comprises graphitized hollow carbon spheres, graphitized hollow carbon spheres and graphene. The invention also discloses a preparation method of the coating, and the preparation method adopts an in-situ polymerization method to compound different graphitized micro-nano carbon materials, has simple process and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a micro-nano carbon composite heat dissipation coating and a preparation method thereof.
Background
The heat dissipation coating is a special coating for improving the heat dissipation efficiency of the surface of an object and reducing the temperature of the system. The composition is not limited to oil-based and water-based paints, and is a novel paint having various compositions. Mainly aims at the problem of heat dissipation of industrial production or industrial products. The heat dissipation coating with high heat conductivity coefficient and high radiation characteristic can be adopted, and the effect of rapid heat dissipation is achieved. The preparation of the heat-dissipating coating usually requires the addition of a filler with high thermal conductivity, and the commonly used heat-dissipating filler comprises an oxide system, a nitride system, a carbide system and a carbon single-substance system.
The carbon material has excellent physical and chemical properties, such as different appearances, porous structures, wider specific surface area range, adjustable crystal types, stronger acid and alkali resistance and the like, is easy to obtain raw materials, has lower preparation cost, and can be used as an important filler of the heat dissipation coating. Most of the novel carbon material heat dissipation coating at present adopts graphite alkene, carbon nanotube and carbon fiber as the filler, along with the development of science and technology and the demand of society constantly increases, and the index requirement to novel heat dissipation coating is stricter, needs it not only to have higher heat dispersion, still need compromise other conventional properties to satisfy the product to the high-efficient heat dissipation of coating, high stability, high adhesive force and the high demand of resistance to acids and alkalis. The nano-coating is prepared by simply compounding nano-filler and the traditional coating, so that the performance of the nano-coating is difficult to be considered, and the nano-coating cannot meet various use environments in the aspect of actual use.
Although the heat conductivity coefficient of the current novel nano heat-dissipation coating is greatly improved compared with that of a common coating, the composite coating still has a larger gap with practical application due to various technical problems, and the specific problems are as follows:
(1) the physical properties of the coating layer do not reach a normal level. Because the matching property of the inorganic filler particles and the matrix is poor, the adhesion (the lower grade, the better grade, the 0 grade and the worst grade, the 5 grade) of the coating is poor (lower than grade 2), the coating is poor in hardness (lower than grade B), impact resistance and the like, and the coating is easy to peel off and scratch and the like after being used for a long time at a high temperature.
(2) The overall performance is inferior to that of conventional coatings. The current research shows that the carbon material composite coating can reach 11 wt% at mostThe heat conductivity coefficient of the adhesive is poor, and the adhesive force is only 200N/cm2(class 2 ISO, not industrially usable) and poor heat resistance, and melting occurs at temperatures higher than 200 ℃.
(3) The preparation process is complex, the yield is low, the raw material cost is high, and the large-scale production and preparation are restricted.
(4) The research on the heat conduction mechanism of the coating is less, so that the heat conduction mechanism is unknown, and the theory of systematization is lacked.
Disclosure of Invention
The invention aims to provide a micro-nano carbon composite heat dissipation coating, which is prepared by compounding different types of graphitized micro-nano carbon materials with different advantages, graphene and the like with acrylic resin, and the prepared coating can give consideration to multiple performances of the heat dissipation coating, such as better performances in the aspects of heat dissipation performance, stability, acid and alkali resistance and adhesive force.
The invention also aims to provide a preparation method of the micro-nano carbon composite heat dissipation coating, and the preparation method adopts an in-situ polymerization method to compound different graphitized micro-nano carbon materials, has simple process and is suitable for industrial production.
The first object of the present invention can be achieved by the following technical solutions: the micro-nano carbon composite heat dissipation coating comprises the following raw materials in percentage by mass:
5-20% of graphitized solid carbon spheres
The balance of acrylic resin.
Preferably, the mass percentage of each raw material is as follows:
graphitized solid carbon ball 15%
The balance of acrylic resin.
The graphitized solid carbon spheres are added into the acrylic resin, so that the thermal conductivity can be improved, and the graphitized solid carbon spheres can be uniformly dispersed in the acrylic resin matrix and fully contact with each other to form a heat conduction chain, so that the thermal conductivity of the composite coating is improved.
In addition, with the increase of the addition amount of the graphitized solid carbon spheres, the time for respectively keeping the first level, the second level and the third level of the composite heat dissipation coating is increased and then reduced, and the adhesive force performance and the acid and alkali resistance level of the composite heat dissipation coating also have similar trends. This is because the nano filler (referring to graphitized solid carbon spheres) will agglomerate when further increased, thereby affecting the overall properties such as thermal conductivity, stability, etc., so that the increase of the overall properties of the composite coating is not favored when the filler is added too much.
According to the invention, the synthesized micro-nano carbon composite coating is tested in the aspects of heat conductivity coefficient, stability, adhesive force, acid and alkali resistance and the like, and the test result shows that: when the using amount of the graphitized solid carbon spheres is 15 wt.%, the four performance indexes reach the optimal values, wherein the maximum value of the thermal conductivity coefficient is 3.2W/(m.K).
As an improvement of the invention: the raw materials also comprise graphitized hollow carbon spheres, and the mass percentage of each raw material is as follows:
1-4% of graphitized hollow carbon spheres
5-20% of graphitized solid carbon spheres
The balance of acrylic resin.
Preferably, the mass percentage of each raw material is as follows:
1-4% of graphitized hollow carbon spheres
Graphitized solid carbon ball 15%
The balance of acrylic resin.
Preferably, the mass percentage of each raw material is as follows:
3 percent of graphitized hollow carbon spheres
Graphitized solid carbon ball 15%
The balance of acrylic resin.
From the performance of overall heat dissipation performance, the heat conductivity coefficient of a sample obtained by adding the graphitized solid carbon balls is higher than that of a sample obtained by only adding the graphitized solid carbon balls, because the hollow structure of the graphitized hollow carbon balls can provide more heat dissipation channels, which is equivalent to providing a bridge for filler and resin molecules, reducing the non-harmonic vibration of resin macromolecules, reducing the adverse effects caused by interfaces and defects, reducing phonon scattering, and further improving the heat conductivity.
Therefore, the graphitized hollow carbon spheres are added into the graphitized solid carbon spheres, so that the thermal conductivity can be further improved, because different fillers have larger difference in aspect ratio, size, thermal conductivity and the like, and the proper compounding of the fillers can synergistically play the role of various fillers, so that the dispersibility and the net forming capability of the fillers in a resin matrix are improved. Meanwhile, due to the characteristics of more heat transfer to the sphere boundary and high specific surface area of the nano-scale hollow carbon spheres, when the solid carbon spheres and the hollow carbon spheres are compounded, the heat can be effectively transferred to the whole coating from a heated point, and the heat dissipation area is effectively improved.
In addition, compared with the composite heat dissipation coating only added with graphitized solid carbon spheres, the composite heat dissipation coating added with the graphitized solid carbon spheres and the graphitized hollow carbon spheres has the advantages that the stability, the adhesive force performance and the acid and alkali resistance are improved integrally.
According to the invention, the synthesized micro-nano carbon composite coating is tested in the aspects of heat conductivity coefficient, stability, adhesive force, acid and alkali resistance and the like, and the test result shows that: when the consumption of the graphitized solid carbon spheres is 15 percent and the consumption of the graphitized hollow carbon spheres is 3.0 percent, the composite coating has better comprehensive performance, and the maximum value of the thermal conductivity coefficient is 3.9W/(m.K).
As a further improvement of the invention: the raw materials also comprise graphene, and the mass percentage of each raw material is as follows:
preferably, the weight percentage of each raw material is as follows:
further preferably, the mass percentage of each raw material is as follows:
preferably, the weight percentage of each raw material is as follows:
the graphene is added into the graphitized hollow carbon spheres and the graphitized solid carbon spheres, so that the thermal conductivity can be further improved, and the reason is that the graphene and the carbon microspheres are uniformly mixed under the action of mechanical external force, so that the graphene and the carbon microspheres are dispersed in a resin matrix, and the carbon microspheres have the functions of bonding and filling among graphite flake layers, so that the graphite flake layers can be formed into the composite coating with a three-dimensional structure. On one hand, the micro-nano carbon spheres are used as a filling agent and enter gaps among graphite layers; on the other hand, the composite coating can be used as a binder to further improve the strength of the composite coating. Meanwhile, the three-dimensional network heat conduction path formed by the graphene heat conduction filler can reduce the interface contact between the filler and the matrix, thereby reducing the thermal resistance and further improving the heat conductivity.
In addition, after the graphene, the graphitized solid microspheres and the graphitized hollow microspheres are added into the formula of the composite heat dissipation coating, the stability, the adhesion and the acid and alkali resistance of the composite heat dissipation coating can reach the optimal state, particularly, the graphene lamellar structure has larger surface energy, and the three-dimensional network framework provided by the graphene can prevent agglomeration, so that each filler is more tightly combined with a resin polymer, the rapid densification of a coating film is promoted, the acid and alkali resistance of the composite heat dissipation coating is integrally improved, and the evaluation grade is mostly 0 grade.
According to the invention, the synthesized micro-nano carbon composite coating is tested in the aspects of heat conductivity coefficient, stability, adhesive force, acid and alkali resistance and the like, and the test result shows that: when 15% of graphitized solid carbon spheres, 3% of graphitized hollow carbon spheres and 1.5% of graphene are added, the composite coating has the highest heat conductivity coefficient which reaches 4.8W/(m.K), and the stability, the adhesion and the acid and alkali resistance of the composite coating are correspondingly improved.
The micro-nano carbon composite heat dissipation coating comprises the following raw materials:
the acrylic resin may be a commercially available product or may be prepared by a method described in the literature.
But preferably, the acrylic resin prepared by the method of the invention is obtained by the following method: selecting monomer mixtures such as ethyl acrylate, butyl acetate, diacetone alcohol and the like, mixing and stirring uniformly, opening a stirrer and a water bath tank, slowly raising the temperature to 85 ℃, adding a small amount of initiator after stable reflux appears, reacting for 15min, beginning to dropwise add the mixture of the monomer mixtures and the initiator, preserving heat for 4h after dropwise adding, and then discharging to obtain the ethyl acrylate.
The graphitized solid carbon spheres in the present invention may be commercially available products, or may be prepared by methods described in the prior art documents.
Preferably, the graphitized solid carbon spheres prepared by the method of the present invention are preferably micro-nano graphitized solid carbon spheres, and the micro-nano graphitized solid carbon spheres can be prepared by the following method: selecting cane sugar and ferric acetate (the mass ratio of the cane sugar to the ferric acetate is preferably 1:0.05), placing the cane sugar and the ferric acetate in deionized water, stirring, transferring the cane sugar and the ferric acetate into a high-temperature reaction kettle after the cane sugar is completely dissolved to form a colorless uniform solution, sealing the reaction kettle, placing the reaction kettle in a well type furnace to react for 5.5-6.5 h at 215-225 ℃, naturally cooling the reaction kettle to room temperature after the reaction is finished, opening the reaction kettle, taking out black powder, washing the black powder with dilute hydrochloric acid, absolute ethyl alcohol and deionized water, filtering and drying the black powder to obtain the micro.
Wherein:
preferably, the mass part ratio of the sucrose to the ferric acetate is preferably 1: 0.05.
more preferably, the reaction mixture is placed in a well type furnace for 6 hours at 220 ℃.
Preferably, the drying temperature is 100 ℃.
The graphitized solid carbon spheres in the present invention may be commercially available products, or may be prepared by methods described in the prior art documents.
Preferably, the micro-nano graphitized hollow carbon spheres prepared by the method provided by the invention are obtained by the following steps:
(1) weighing ethyl orthosilicate, dissolving the ethyl orthosilicate in a mixed solvent of absolute ethyl alcohol and deionized water, uniformly mixing, reacting at 75-85 ℃ for 10-14 h, filtering and washing a white precipitate after the reaction is finished, and placing the white precipitate in an oven at 85-95 ℃ for overnight to prepare a silicon dioxide hard template;
(2) selecting a silicon dioxide hard template and sucrose, stirring in deionized water, transferring to a low-temperature reaction kettle after the sucrose is completely dissolved to form a colorless uniform solution, sealing the low-temperature reaction kettle, and placing in an oven at 175-185 ℃ for reaction for 22-26 h;
(3) naturally cooling to room temperature after the reaction is finished, opening the reaction kettle, taking out brown powder, washing the powder with hydrofluoric acid, absolute ethyl alcohol and deionized water, filtering and drying to obtain hollow carbon spheres;
(4) the method comprises the steps of soaking hollow carbon spheres in a nickel acetate solution, filtering and drying to obtain a graphitized hollow carbon sphere precursor, and calcining the graphitized hollow carbon sphere precursor in a tubular furnace at the temperature of 750-850 ℃ for 1.8-2.2 hours under the protection of nitrogen to obtain the micro-nano graphitized hollow carbon spheres.
Wherein:
preferably, the reaction in step (1) is carried out at 80 ℃ for 12 h.
Preferably, in the step (2), the mass part ratio of the silicon dioxide hard template to the sucrose is 10: 1.
preferably, the step (2) is placed in an oven at 180 ℃ for reaction for 24 hours.
Preferably, the drying temperature in step (3) and step (4) is 100 ℃.
Preferably, the concentration of the nickel acetate solution in the step (4) is 2.8-3.2 mol/L, and more preferably, the concentration of the nickel acetate solution is 3.0 mol/L.
Preferably, in the step (4), the graphitized hollow carbon sphere precursor is calcined in a tube furnace for 2 hours under the protection of nitrogen at 800 ℃.
The graphene in the present invention may be a commercially available product, or may be prepared by a method described in the literature.
Preferably, the graphene prepared by the method of the present invention is preferably a micro-nano graphene, which can be prepared by the following method:
(1) adding graphite powder into a three-neck flask, slowly adding concentrated sulfuric acid, slowly stirring in an ice bath, simultaneously adding potassium permanganate and sodium nitrate, and controlling the temperature to be below 35 ℃ for reaction for 2 hours;
(2) after the reaction is finished, adding deionized water, and heating to 100 ℃ for reaction for 6 hours;
(3) then respectively adding deionized water and hydrogen peroxide, stirring and reacting, and after the reaction is finished, centrifuging, washing, and freeze-drying the mixture to obtain graphene oxide;
(4) weighing the prepared graphene oxide, adding the graphene oxide into deionized water, carrying out ultrasonic treatment for 4 hours, then adding hydrazine hydrate into the suspension, and carrying out water bath for 24 hours at 100 ℃;
(5) and finally, filtering the obtained turbid liquid to obtain a black precipitate, and washing and drying the black precipitate to obtain the micro-nano graphene.
The second object of the present invention can be achieved by the following technical solutions:
the preparation method of the micro-nano carbon composite heat dissipation coating comprises the following steps: selecting raw materials, namely graphitized solid carbon spheres and acrylic resin, uniformly mixing the raw materials and the acrylic resin according to the dosage relationship, reacting for 8-12 hours at the temperature of 50-70 ℃, and then grinding to obtain the micro-nano carbon composite heat dissipation coating.
Further, the raw material also comprises graphitized hollow carbon spheres, or graphitized hollow carbon spheres and graphene.
Preferably, the graphitized solid carbon spheres, the graphitized hollow carbon spheres or the graphene are micro-nano graphitized solid carbon spheres, micro-nano graphitized hollow carbon spheres or micro-nano graphene.
More preferably, the reaction is carried out at a temperature of 60 ℃ for 10 hours.
Preferably, grinding zirconia balls with the mass 1-3 times of the total mass of the materials are added during grinding, the materials are dispersed for 40-80 min at the rotating speed of 1000-1500 r/min, and in-situ polymerization reaction is carried out.
Preferably, grinding zirconia balls with the mass 2 times of the total mass of the materials are added during grinding, the materials are dispersed for 60min at the rotating speed of 1200r/min, and in-situ polymerization reaction is carried out.
The in-situ polymerization reaction refers to a process of dispersing and polymerizing fillers (including graphitized solid carbon spheres, graphitized hollow carbon spheres, graphene and the like) in a coating matrix (acrylate).
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, after the graphitized solid carbon spheres are added into the acrylic resin, the heat conductivity coefficient of the composite coating can be improved, after the graphitized hollow carbon spheres are further added into the acrylic ester, the function of various fillers can be cooperatively exerted through proper compounding of the fillers, the heat conductivity coefficient of the composite coating is further improved, when graphene is added into the graphitized hollow carbon spheres and the graphitized solid carbon spheres, the composite coating has the highest heat conductivity coefficient, and the stability, the adhesive force and the acid and alkali resistance of the composite coating are correspondingly improved;
(2) the composite heat dissipation coating disclosed by the invention is prepared by compounding different types of graphitized micro-nano carbon materials with different advantages (including high crystallinity, high specific surface area, hollow structure, lamellar structure and the like) with acrylic resin, and the heat dissipation coating prepared by compounding multiple micro-nano carbon materials has higher heat dissipation performance, and is better than a common nano heat dissipation coating in the aspects of stability, acid and alkali resistance and adhesive force;
(3) the invention synthesizes three micro-nano carbon composite water-based heat-dissipation coatings by an in-situ polymerization method, which comprise a graphitized solid carbon ball-acrylic resin composite coating, a graphitized solid/hollow carbon ball-acrylic resin composite coating and a graphitized solid/hollow carbon ball/graphene-acrylic resin composite coating, wherein the influence of different dosages of the graphitized solid carbon ball, the graphitized hollow carbon ball and the graphene on the heat dissipation performance, stability, adhesive force and acid and alkali resistance of the composite coating is respectively researched by adopting a single variable control method, the composite heat-dissipation coating with the optimal performance is prepared by comparing experimental results of the heat dissipation performance, the stability, the adhesive force and the acid and alkali resistance, and meanwhile, a certain theoretical basis is provided for researching and developing special coatings with higher comprehensive performance;
(4) the invention adopts an in-situ polymerization method to synthesize various graphitized carbon material composite coatings, and the method has the characteristics of simple flow, high yield and suitability for industrial production;
(5) the raw materials for preparing the composite coating are not high in price, and the production cost can be effectively reduced.
Drawings
Fig. 1 is an SEM image and a TEM image of solid carbon spheres prepared in example 1 of the present invention, wherein a is an SEM image of solid carbon spheres and B is a TEM image of solid carbon spheres;
fig. 2 is an SEM image and a TEM image of hollow carbon spheres prepared in example 2 of the present invention, wherein a is an SEM image of the hollow carbon spheres and B is a TEM image of the hollow carbon spheres;
FIG. 3 is a graph showing the relationship between the thermal conductivity of graphitized solid carbon spheres in example 1 of the present invention;
FIG. 4 is a graph showing the relationship between the stability ratings of graphitized solid carbon spheres at different addition levels in example 1 of the present invention;
FIG. 5 is a graph showing the relationship between adhesion ratings of graphitized solid carbon spheres in example 1 of the present invention at different addition levels;
FIG. 6 is a graph showing the relationship between the acid and alkali resistance ratings of different addition amounts of graphitized solid carbon spheres in example 1 of the present invention;
FIG. 7 is a graph showing the relationship between the thermal conductivity of graphitized hollow carbon spheres in example 2 of the present invention with respect to different amounts of added heat transfer;
FIG. 8 is a graph showing the relationship between the stability ratings of graphitized hollow carbon spheres in example 2 of the present invention at different addition levels;
FIG. 9 is a graph showing the relationship between the adhesion ratings of graphitized hollow carbon spheres in example 2 of the present invention at different addition levels;
FIG. 10 is a graph showing the relationship between the acid and alkali resistance ratings of different addition amounts of graphitized hollow carbon spheres in example 2 of the present invention;
fig. 11 is a graph of the relationship between the thermal conductivity of graphene in different addition amounts in example 3 of the present invention;
fig. 12 is a graph showing the relationship between the stability rating of graphene in example 3 of the present invention at different addition levels.
FIG. 13 is a graph showing adhesion ratings of different amounts of graphene added in example 3 of the present invention;
fig. 14 is a graph of the relationship between the acid and alkali resistance ratings of different addition amounts of graphene in example 3 of the present invention.
Detailed Description
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
Example 1
The micro-nano carbon composite heat dissipation coating provided by the embodiment comprises graphitized solid carbon spheres and acrylic resin.
Graphitized solid carbon spheres are commercially available or may be prepared according to known literature, and preferred graphitized solid carbon spheres may be synthesized by the following method: weighing 1g of sucrose and 0.05g of ferric acetate, putting the mixture into 20mL of deionized water, stirring for 30min, transferring the mixture into a high-temperature reaction kettle after the sucrose is completely dissolved to form a colorless uniform solution, sealing the high-temperature reaction kettle, and placing the high-temperature reaction kettle in a well type furnace for reacting for 6h at 220 ℃. And naturally cooling to room temperature after the reaction is finished, opening the reaction kettle and taking out the black powder. And washing the black powder with dilute hydrochloric acid, absolute ethyl alcohol and deionized water, filtering and drying (at 100 ℃) to obtain the graphitized solid carbon spheres.
SEM images and TEM images of the prepared solid carbon spheres are shown in FIG. 1, wherein A is a solid carbon sphere SEM image, and B is a solid carbon sphere TEM image; as can be seen from FIG. 1, the solid carbon spheres have a particle size of about 400 to 600 nm.
The acrylic resin may be a conventional acrylic resin commercially available, and a preferred acrylic resin may be synthesized by: a four-necked flask with a reflux condenser tube, a constant pressure dropping funnel, a mechanical stirrer and a thermometer is sequentially added with monomer mixtures of ethyl acrylate, butyl acetate, diacetone alcohol and the like, and the mixture is mixed and stirred uniformly. Opening the stirrer and the water bath tank, slowly raising the temperature to 85 ℃ (the reflux temperature of isopropanol), adding a small amount of initiator (conventional initiator) after the reflux is stable, reacting for 15min, and dropwise adding a mixture of monomer mixture (ethyl acrylate, butyl acetate, diacetone alcohol and the like) and initiator (including conventional monomers such as benzoyl peroxide and azodiisobutyronitrile and the like, which can be added as required). After the dropwise addition, the temperature is kept for 4 hours, and then the material is discharged, thus obtaining the ethyl acrylate.
The graphitized solid carbon sphere composite coating is prepared as follows:
adding a certain amount of graphitized solid carbon spheres (according to the mass percentage content of 5%, 10%, 15% and 20% of the graphitized solid carbon spheres) into acrylic resin, reacting for 10 hours at 60 ℃, adding ground zirconia spheres 2 times of the total mass of the reactants, and dispersing the mixture for 1 hour by using a stirrer with the rotation speed of 1200r/min to obtain the micro-nano graphitized solid carbon sphere composite coating.
The prepared nano graphitized solid carbon sphere composite heat dissipation coating is tested in the aspect of comprehensive performance, and comprises the following contents:
(1) and (4) testing the heat dissipation performance, wherein the heat dissipation performance is mainly measured by the heat conductivity coefficient. The obtained coating powder was pressed into a sheet having a diameter of about 3cm by a tablet press. Subsequently, the sheet was calibrated with a calibration instrument and placed in a thermal conductivity meter for 3 tests, and the results were averaged, as shown in table 1 below and fig. 3.
TABLE 1 influence of different addition amounts of graphitized solid carbon spheres on the thermal conductivity of composite coatings
When the addition amounts of the graphitized solid carbon spheres are 5, 10, 15 and 20 wt.%, respectively, the thermal conductivity corresponds to values of 2.1, 2.8, 3.2 and 2.9W/(m · K), respectively, which is about ten times as large as the thermal conductivity (0.25W/(m · K)) of the simple acrylic resin as a whole. With the increasing of the addition amount of the graphitized solid carbon spheres, the thermal conductivity of the composite coating tends to increase first and then decrease. The graphitized solid carbon spheres have higher crystallization degree, dispersion, uniform morphology and size, and higher thermal conductivity, and are beneficial to improving the overall thermal conductivity of the composite coating. Meanwhile, the graphitized solid carbon spheres are added into the acrylic resin, so that the movement of polymer molecular chains can be hindered, the glass transition temperature of the resin is increased, and the heat conductivity coefficient is further increased.
(2) And (5) testing the stability. Weighing a certain amount of samples, putting the samples into test tubes, preparing three parallel samples for each sample, and storing the samples in an oven with the test temperature of about 45 ℃ for a certain time. Then the sample is placed in an environment with the temperature of about 23 ℃ for natural cooling. Then the test tube plug is pulled out, the test tube is placed on the horizontal plane, the tail end of the coating is lightly knocked, and whether the coating powder can move freely or not is observed. The coating powder was then poured onto a clean surface and observed for the presence of lumps. At the same time, the same operation was performed on parallel samples. And finally, evaluating the test result according to the stability test grade.
As shown in table 2 below and fig. 4.
TABLE 2 influence of different addition amounts of graphitized solid carbon spheres on the stability of composite coatings
On the whole, with the increase of the addition amount of the graphitized solid carbon spheres, the time for respectively keeping the first level, the second level and the third level of the composite coating is increased and then reduced. At present, the stability of the coating meeting the actual application requirement is at least kept at the second level, namely the time for keeping the first level and the second level is considered, and the stability of the coating can be effectively judged.
(3) ① cutting marks on the prepared coating plate by using a cutter of a grid cutting tester, uniformly cutting six cuts in parallel, uniformly cutting six cuts vertically, ② brushing the cut squares in a reciprocating manner from the diagonal direction by using a soft brush, ③ inspecting the cut surface of the test coating by using a magnifying glass, and evaluating the adhesive force of the sample through actual conditions.
As shown in table 3 below and fig. 5.
TABLE 3 influence of different addition amounts of graphitized solid carbon spheres on the adhesion of composite coatings
When the addition amounts of the graphitized solid carbon spheres are 5, 10, 15 and 20 wt.%, respectively, the corresponding adhesion evaluation equivalents are 4, 3, 2 and 3 grades, respectively. It can be seen that the adhesive force performance of the composite coating becomes better and then worse with the increase of the amount of the filler (referring to graphitized solid carbon spheres). The most important factor influencing the adhesive force performance of the paint is the internal stress, when the filler is added, the filler does not react with the acrylic resin due to high crystallization degree, and the graphitized solid carbon spheres and the acrylic resin are combined through electrostatic adsorption and van der Waals force, so that the shrinkage stress is reduced in the curing process of the paint, and the adhesive force of a sample is improved.
(4) And (4) testing acid and alkali resistance. And testing the sample by adopting an acid-base tester, and evaluating the result. The method comprises the following specific steps: the samples were individually placed in acid (30% H)2SO4) And soaking the mixture in an alkali (10% NaOH) and salt (3% NaCl) solution for a certain time (24h) to perform a corrosion resistance experiment. The acid and alkali resistance was evaluated according to whether the coating surface was discolored, bubbled, wrinkled or not.
As shown in table 4 below and in fig. 6.
TABLE 4 influence of different addition amounts of graphitized solid carbon spheres on the acid and alkali resistance of the composite coating
When the addition amounts of the graphitized solid carbon spheres are 5, 10, 15 and 20 wt.%, respectively, the corresponding acid-base resistance grades are 2, 1 and 2 grades, respectively. It can be seen that with the increase of the amount of the filler (referring to graphitized solid carbon spheres), the acid and alkali resistance grade of the composite coating is firstly improved and then is worsened. However, when the amount of the filler is further increased, the nano filler is agglomerated, so that the comprehensive properties such as heat conductivity coefficient and stability are affected, and the increase of the comprehensive properties of the composite coating is adversely affected when the amount of the filler is too much.
The test on the aspects of heat conductivity coefficient, stability, adhesive force, acid and alkali resistance and the like is carried out on the synthesized micro-nano carbon composite coating, and the test result shows that:
when the using amount of the graphitized solid carbon spheres is 15 wt.%, the four performance indexes reach the optimal values, wherein the maximum value of the thermal conductivity coefficient is 3.2W/(m.K). This is because when the solid carbon spheres are added in an amount of 15%, they are uniformly dispersed in the resin matrix to be in sufficient contact with each other to form a thermal conductive chain, thereby improving the thermal conductivity of the composite coating.
Example 2
The micro-nano carbon composite heat dissipation coating provided by the embodiment comprises graphitized hollow carbon spheres besides graphitized solid carbon spheres and acrylic resin.
The synthesis method of the graphitized solid carbon spheres and the acrylic resin is the same as that of example 1.
The synthesis method of the graphitized hollow carbon spheres comprises the following steps:
5g of tetraethoxysilane (the amount of tetraethoxysilane can be properly increased and decreased according to the total amount of the composite coating) is weighed and dissolved in a mixed solvent of absolute ethyl alcohol and deionized water (the amount and the proportion can ensure that tetraethoxysilane can be completely dissolved). After mixing well, the mixture was transferred to a three-necked flask and reacted at 80 ℃ for 12 hours. And after the reaction is finished, filtering and washing the white precipitate, and putting the white precipitate in an oven at 90 ℃ overnight to prepare the silicon dioxide hard template.
Respectively weighing a certain amount of silicon dioxide hard template and sucrose, stirring the silicon dioxide hard template and the sucrose in 20mL deionized water for 30min according to the mass ratio of 10:1, transferring the mixture into a low-temperature reaction kettle after the sucrose is completely dissolved to form a colorless uniform solution, sealing the low-temperature reaction kettle, and placing the mixture in an oven at 180 ℃ for reaction for 24 h.
Naturally cooling to room temperature after the reaction is finished, opening the reaction kettle and taking out brown powder. Washing the powder with hydrofluoric acid, absolute ethyl alcohol and deionized water, filtering and drying (100 ℃) to obtain the hollow carbonaceous spheres.
And then, soaking the hollow carbon spheres in 3mol/L nickel acetate solution, and then filtering and drying (100 ℃) to obtain the graphitized hollow carbon sphere precursor.
And placing the graphitized hollow carbon sphere precursor into a tubular furnace, and calcining for 2 hours at 800 ℃ under the protection of nitrogen to obtain the graphitized hollow carbon sphere.
SEM images and TEM images of the prepared hollow carbon spheres are shown in fig. 2, wherein a is an SEM image of the hollow carbon spheres, and B is a TEM image of the hollow carbon spheres; as can be seen from fig. 2, the particle size of the hollow carbon spheres is in the order of nanometers.
And mixing the graphitized solid carbon spheres, the graphitized hollow carbon spheres and acrylic resin, and reacting for 10 hours at the temperature of 60 ℃. Adding ground zirconia balls with the mass 2 times of the total mass of the reactants into the reactants, and dispersing the mixture for 1h by adopting a stirrer at the rotating speed of 1200r/min to obtain the nano graphitized solid/graphitized hollow carbon ball composite coating.
On the basis that the graphitized solid carbon spheres are used as a single heat dissipation filler, the graphitized hollow carbon spheres are added, so that the heat dissipation performance of the coating can be further improved.
In the embodiment, the prepared nano graphitized hollow carbon sphere composite heat dissipation coating is tested in the aspect of comprehensive performance, in the testing process, the addition amount of the graphitized solid carbon spheres is 15%, the addition amounts of the graphitized hollow carbon spheres are respectively 1%, 2%, 3% and 4%, and the balance is acrylic resin, and the nano graphitized hollow carbon sphere composite heat dissipation coating specifically comprises the following contents:
(1) the heat dissipation performance was tested in the same manner as in example 1.
As shown in table 5 below and fig. 7.
TABLE 5 influence of different addition amounts of graphitized hollow carbon spheres on the thermal conductivity of the composite coating
When the graphitized hollow carbon spheres were used in amounts of 1.0, 2.0, 3.0, and 4.0 wt.%, respectively, the thermal conductivities of the samples were 3.4, 3.6, 3.9, and 3.5W/(m · K), respectively. From the aspect of overall heat dissipation performance, the heat conductivity coefficient of the sample is higher than that of the sample obtained by only adding the graphitized solid carbon spheres. The hollow structure of the graphitized hollow carbon sphere can provide more heat dissipation channels, which is equivalent to providing a bridge for filler and resin molecules, reduces the non-harmonic vibration of resin polymers, reduces adverse effects caused by interfaces and defects, and reduces phonon scattering, thereby improving the heat conductivity.
(2) The stability test was carried out in the same manner as in example 1.
As shown in table 6 below and fig. 8.
TABLE 6 influence of different addition amounts of graphitized hollow carbon spheres on the stability of composite coatings
Compared with a sample only added with graphitized solid carbon spheres, the stability of the sample is integrally improved. The results show that when graphitized solid and hollow carbon spheres are used as a common filler, the stability of the composite coating can be further improved.
(3) The adhesion test was carried out in the same manner as in example 1.
As shown in table 7 below and fig. 9.
TABLE 7 influence of different addition amounts of graphitized hollow carbon spheres on the adhesion of the coating
The amount of the graphitized hollow carbon spheres is continuously increased, and the evaluation grades of the adhesive force are 2, 1 and 2. The graphitized hollow carbon spheres have higher specific surface area, can be combined with more resin macromolecules, and have adsorption and desorption effects on the surfaces, so that the shrinkage stress of the coating is further reduced, and the adhesive force performance is improved.
(4) The acid and alkali resistance was measured in the same manner as in example 1.
As shown in table 8 below and fig. 10.
TABLE 8 influence of different addition amounts of graphitized hollow carbon spheres on the acid and alkali resistance of the composite coating
With the increase of the amount (1.0-4.0 wt.%) of graphitized hollow carbon spheres, the acid and alkali resistance of the sample is improved as a whole. The acid and alkali resistance of the composite coating can be effectively improved by utilizing the higher physical and chemical stability of the graphitized carbon material, such as higher crystallinity, corrosion resistance, acid and alkali resistance and the like. In addition, the graphitized hollow carbon spheres provide a larger specific surface for the system, so that the surface energy of the system is improved, the filler and the resin are combined more tightly, a more compact coating film is formed, acid and alkali molecules are effectively prevented from entering the coating, and the acid and alkali resistance is improved.
The test on the aspects of heat conductivity coefficient, stability, adhesive force, acid and alkali resistance and the like is carried out on the synthesized micro-nano carbon composite coating, and the test result shows that:
when the consumption of the graphitized solid carbon spheres is 15 percent and the consumption of the graphitized hollow carbon spheres is 3.0 percent, the composite coating has better comprehensive performance, and the maximum value of the thermal conductivity coefficient is 3.9W/(m.K). The reason is that different fillers have larger difference in aspect ratio, size, thermal conductivity and the like, and the proper compounding of the fillers can synergistically play the role of various fillers, so that the dispersibility and the web forming capability of the fillers in a resin matrix are improved. Meanwhile, due to the characteristics of more heat transfer to the sphere boundary and high specific surface area of the nano-scale hollow carbon spheres, when the solid carbon spheres and the hollow carbon spheres are compounded, the heat can be effectively transferred to the whole coating from a heated point, and the heat dissipation area is effectively improved.
Example 3
The micro-nano carbon composite heat dissipation coating provided by the embodiment is prepared from raw materials including graphitized solid carbon spheres, graphitized hollow carbon spheres and acrylic resin, and further comprises graphene.
The synthesis method of the graphitized solid carbon spheres, the graphitized hollow carbon spheres and the acrylic resin is the same as that in example 1.
The synthesis method of the graphene comprises the following steps:
30g of graphite powder was charged into a three-necked flask, and then 200mL of concentrated sulfuric acid was slowly added thereto, and the mixture was slowly stirred in an ice bath. Meanwhile, 20g of potassium permanganate and 2g of sodium nitrate are added, and the temperature is controlled below 35 ℃ for reaction for 2 hours. After the reaction is finished, 50mL of deionized water is added, and the temperature is raised to 100 ℃ for reaction for 6 hours. Then respectively adding 50mL of deionized water and 15mL of hydrogen peroxide, and stirring for reaction. And after the reaction is finished, centrifuging, washing and freeze-drying the mixture to obtain the graphene oxide.
Accurately weighing 5g of prepared graphene oxide, adding the graphene oxide into deionized water, and carrying out ultrasonic treatment for 4 h. After that, hydrazine hydrate was added to the suspension and the suspension was washed with water at 100 ℃ for 24 hours.
And finally, filtering the obtained turbid liquid to obtain a black precipitate, washing with water, and drying to obtain the graphene.
Synthesizing a nano graphitized solid/graphitized hollow carbon sphere/graphene composite coating:
then mixing the graphene, the graphitized solid carbon spheres and the graphitized hollow carbon spheres with the prepared raw materials of the acrylic resin according to the formula, and reacting for 10 hours at 60 ℃. And then adding ground zirconia balls with the mass 2 times of the total mass of the reactants into the reactants, and dispersing the mixture for 1h (1200r/min) by using a stirrer to obtain the nano graphitized solid/graphitized hollow carbon ball/graphene composite coating.
In the embodiment, the prepared graphene composite heat dissipation coating is tested in the aspect of comprehensive performance, in the test process, the addition amount of graphitized solid carbon spheres is 15%, the addition amounts of graphitized hollow carbon spheres are respectively 3%, the mass percentages of graphene are respectively 0.5%, 1%, 1.5% and 2%, and the balance is acrylic resin, which specifically comprises the following contents:
(1) the heat dissipation performance was tested in the same manner as in example 1.
As shown in table 9 below and fig. 11.
TABLE 9 influence of different addition amounts of graphene on the thermal conductivity of the composite coating
From the above table, it can be seen that the overall thermal conductivity of the obtained coating is improved after the graphene is added. The graphene has high heat conductivity coefficient, so that the heat conductivity coefficient of the composite coating can be improved, and the graphene sheet can promote the three and the resin polymer to form a close three-dimensional network heat conduction structure, so that the heat conductivity coefficient of the composite coating is improved.
(2) The stability test was carried out in the same manner as in example 1.
As shown in table 10 below and in fig. 12.
TABLE 10 influence of different addition amounts of graphene on the stability of composite coatings
The colligative law of the stability and the addition amount of the graphene is similar to the experimental law of the first two implementation cases, and the stability tends to be better and worse along with the increase of the addition amount of the graphene, namely, an optimal value (1.5 wt.%) exists.
(3) The adhesion test was carried out in the same manner as in example 1.
As shown in table 11 below and fig. 13.
TABLE 11 influence of different addition amounts of graphene on the adhesion of composite coatings
When the graphene consumption is 1.5 wt.%, the evaluation level of the sample stability adhesive force reaches 0 level, namely the best state is reached, and the actual requirement can be completely met.
(4) The acid and alkali resistance was measured in the same manner as in example 1.
As shown in table 12 below and fig. 14.
TABLE 12 influence of different addition amounts of graphene on acid and alkali resistance of composite coatings
The graphene lamellar structure has larger surface energy, the three-dimensional network framework provided by the graphene can prevent agglomeration, so that each filler is more tightly combined with a resin polymer, the rapid densification of a coating film is promoted, the acid and alkali resistance of the composite coating is integrally improved, and the evaluation grade is mostly 0 grade.
The test on the aspects of heat conductivity coefficient, stability, adhesive force, acid and alkali resistance and the like is carried out on the synthesized micro-nano carbon composite coating, and the test result shows that:
when 15% of graphitized solid carbon spheres, 3% of graphitized hollow carbon spheres and 1.5% of graphene are added, the composite coating has the highest heat conductivity coefficient which reaches 4.8W/(m.K), and the stability, the adhesion and the acid and alkali resistance of the composite coating are correspondingly improved. The reason is that after the graphene and the carbon microspheres are uniformly mixed by mechanical external force, the graphene and the carbon microspheres are dispersed in the resin matrix, and the carbon microspheres play a role in bonding and filling among graphite sheet layers, so that the composite coating with a three-dimensional structure can be formed. On one hand, the micro-nano carbon spheres are used as a filling agent and enter gaps among graphite layers; on the other hand, the composite coating can be used as a binder to further improve the strength of the composite coating. Meanwhile, the three-dimensional network heat conduction path formed by the graphene heat conduction filler can reduce the interface contact between the filler and the matrix, thereby reducing the thermal resistance and further improving the heat conductivity.
The invention synthesizes three micro-nano carbon composite water-based heat dissipation coatings by an in-situ polymerization method, including a graphitized solid carbon sphere-acrylic resin composite coating, a graphitized solid/hollow carbon sphere-acrylic resin composite coating and a graphitized solid/hollow carbon sphere/graphene-acrylic resin composite coating. The influence of different dosages of the graphitized solid carbon spheres, the graphitized hollow carbon spheres and the graphene on the heat dissipation performance, the stability, the adhesive force and the acid and alkali resistance of the composite coating is respectively researched by adopting a single variable control method. The composite heat dissipation coating with the optimal performance is prepared by comparing experimental results of heat dissipation performance, stability, adhesive force and acid and alkali resistance, and meanwhile, a certain theoretical basis is provided for researching and developing special coatings with high comprehensive performance.
The present invention is illustrated by the following examples, which are not intended to limit the scope of the invention. Other insubstantial modifications and adaptations of the present invention can be made without departing from the scope of the present invention.
Claims (10)
1. The utility model provides a micro-nano carbon composite heat dissipation coating, characterized by: the raw materials of the coating comprise graphitized solid carbon spheres and acrylic resin, and the mass percentage of each raw material is as follows:
5-20% of graphitized solid carbon spheres
The balance of acrylic resin.
2. The micro-nano carbon composite heat dissipation coating of claim 1, wherein: the raw materials also comprise graphitized hollow carbon spheres, and the mass percentage of each raw material is as follows:
1-4% of graphitized hollow carbon spheres
5-20% of graphitized solid carbon spheres
The balance of acrylic resin.
3. The micro-nano carbon composite heat dissipation coating of claim 2, wherein: the raw materials also comprise graphene, and the mass percentage of each raw material is as follows:
4. the micro-nano carbon composite heat dissipation coating as claimed in claim 3, wherein the micro-nano carbon composite heat dissipation coating is prepared from the following raw materials in percentage by mass:
5. the micro-nano carbon composite heat dissipation coating as claimed in claim 4, wherein the micro-nano carbon composite heat dissipation coating is prepared from the following raw materials in percentage by mass:
6. the micro-nano carbon composite heat dissipation coating as claimed in any one of claims 1 to 5, wherein: the graphitized solid carbon spheres are micro-nano graphitized solid carbon spheres, and are prepared by the following method: selecting sucrose and ferric acetate, placing the sucrose and ferric acetate in deionized water, stirring, transferring the solution into a high-temperature reaction kettle after the sucrose is completely dissolved to form a colorless uniform solution, sealing, placing the reaction kettle in a well type furnace at 215-225 ℃ for reaction for 5.5-6.5 h, naturally cooling to room temperature after the reaction is finished, opening the reaction kettle, taking out black powder, washing the black powder with dilute hydrochloric acid, absolute ethyl alcohol and deionized water, filtering and drying to obtain the micro-nano graphitized solid carbon sphere.
7. The micro-nano carbon composite heat dissipation coating as claimed in any one of claims 2 to 5, wherein: the graphitized hollow carbon spheres are micro-nano graphitized hollow carbon spheres, and are prepared by the following method:
(1) weighing ethyl orthosilicate, dissolving the ethyl orthosilicate in a mixed solvent of absolute ethyl alcohol and deionized water, uniformly mixing, reacting at 75-85 ℃ for 10-14 h, filtering and washing a white precipitate after the reaction is finished, and placing the white precipitate in an oven at 85-95 ℃ for overnight to prepare a silicon dioxide hard template;
(2) selecting a silicon dioxide hard template and sucrose, stirring in deionized water, transferring to a low-temperature reaction kettle after the sucrose is completely dissolved to form a colorless uniform solution, sealing the low-temperature reaction kettle, and placing in an oven at 175-185 ℃ for reaction for 22-26 h;
(3) naturally cooling to room temperature after the reaction is finished, opening the reaction kettle, taking out brown powder, washing the powder with hydrofluoric acid, absolute ethyl alcohol and deionized water, filtering and drying to obtain hollow carbon spheres;
(4) the method comprises the steps of soaking hollow carbon spheres in a nickel acetate solution, filtering and drying to obtain a graphitized hollow carbon sphere precursor, and calcining the graphitized hollow carbon sphere precursor in a tubular furnace at the temperature of 750-850 ℃ for 1.8-2.2 hours under the protection of nitrogen to obtain the micro-nano graphitized hollow carbon spheres.
8. The preparation method of the micro-nano carbon composite heat dissipation coating as recited in claim 1, comprising the steps of: selecting raw materials, namely graphitized solid carbon spheres and acrylic resin, uniformly mixing the raw materials and the acrylic resin according to the dosage relationship, reacting for 8-12 hours at the temperature of 50-70 ℃, and then grinding to obtain the micro-nano carbon composite heat dissipation coating.
9. The preparation method of the micro-nano carbon composite heat dissipation coating as recited in claim 8, wherein the steps of: the raw materials also comprise graphitized hollow carbon spheres, or graphitized hollow carbon spheres and graphene.
10. The preparation method of the micro-nano carbon composite heat dissipation coating as recited in claim 8, wherein the steps of: adding grinding zirconia balls with the mass 1-3 times of the total mass of the materials during grinding, dispersing the materials for 40-80 min at the rotating speed of 1000-1500 r/min, and carrying out in-situ polymerization reaction.
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