CN112759790A - Boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler and preparation method thereof, and epoxy resin heat-conducting composite material and preparation method thereof - Google Patents
Boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler and preparation method thereof, and epoxy resin heat-conducting composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of nano materials, and provides a preparation method of a boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler. According to the invention, the silicon carbide nanowires are grown in situ on the boron nitride nanosheets by an in-situ growth method, and a nest-shaped heterostructure is constructed and prepared, so that when the heterostructure with a special morphology is used as a heat-conducting filler, the heterostructure is easier to lap joint in an epoxy resin matrix to form an efficient heat-conducting passage, and the heat-conducting property of the epoxy resin can be improved under the condition that a small amount of filler is added; meanwhile, the introduction of more interface thermal barriers and the agglomeration of the heat-conducting fillers are effectively avoided based on the chemical bonding effect among the heat-conducting fillers, and the heat-conducting property of the epoxy resin can be further improved. Experimental results show that the thermal conductivity of the heat-conducting composite material obtained by compounding the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler prepared by the method with the epoxy resin is as high as 1.17W/mK, and the thermal conductivity of the epoxy resin can be greatly improved.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler and a preparation method thereof, and an epoxy resin heat-conducting composite material and a preparation method thereof.
Background
Epoxy resin is widely applied to the electronic industry and related fields thereof due to the advantages of excellent electrical insulation, chemical stability, good processability, heat resistance, corrosion resistance and the like. However, the pure epoxy resin has a low thermal conductivity (λ) generally around 0.2W/mK, and is difficult to meet the requirement of high-efficiency heat dissipation of high-end electronic components. At present, around the dual requirements of epoxy resin heat conduction and electrical insulation for electronic device equipment, related research works at home and abroad mostly improve the heat conduction performance of the epoxy resin by adding heat conduction fillers into an epoxy resin matrix. However, in order to achieve the desired thermal conductivity of epoxy resin, a large amount of thermal conductive filler is usually added to achieve the desired thermal conductivity, which also causes the problems of increased cost, poor processability, agglomeration of thermal conductive filler, and drastic decrease in mechanical properties of epoxy resin composite materials.
Compared with the directly blended hybrid heat-conducting filler, the heterostructure heat-conducting filler is easier to form an efficient heat-conducting path and can be used for improving the heat-conducting property of the epoxy resin. Although the heat conductive filler of such a heterostructure can improve the heat conductive property of the epoxy resin to some extent, the improvement of the heat conductive property of the epoxy resin is limited. For example, the heat-conducting filler prepared by using boron nitride-silicon carbide in Chinese patent CN110964228A can only improve the thermal conductivity of the epoxy resin heat-conducting composite material to 0.89W/mK at most when the addition amount of the filler is 20 wt%. Therefore, it is highly desirable to develop a thermally conductive filler that can greatly improve the thermal conductivity of epoxy resins.
Disclosure of Invention
The invention aims to provide a boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler and a preparation method thereof, and an epoxy resin heat-conducting composite material and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler, which comprises the following steps:
(1) mixing a biomass carbon source, tetraethoxysilane, hydrochloric acid and absolute ethyl alcohol, and carrying out hydrolysis reaction to obtain BL-Si precursor sol;
(2) mixing the BL-Si precursor sol obtained in the step (1) with boron nitride dispersion liquid to obtain boron nitride-silicon carbide precursor dispersion liquid; the mixing temperature is 40-70 ℃, and the mixing time is 3-6 h;
(3) drying the boron nitride-silicon carbide precursor dispersion liquid obtained in the step (2), and reacting the boron nitride-silicon carbide precursor dispersion liquid with alkali liquor at room temperature for 4-6 hours to obtain a boron nitride-silicon carbide precursor;
(4) carrying out heat treatment on the boron nitride-silicon carbide precursor obtained in the step (3) to obtain a boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler; the heat treatment is carried out under a protective gas.
Preferably, the biomass carbon source in step (1) comprises one or more of bamboo leaves, bamboo charcoal and glucose.
Preferably, the concentration of the hydrochloric acid in the step (1) is 0.1-0.2 mol/L.
Preferably, the volume ratio of the mass of the biomass carbon source and the hydrochloric acid to the volume of the ethyl orthosilicate and the absolute ethyl alcohol in the step (1) is (12-50) g: (0.3-1) g: (50-200) mL: (50-100) mL.
Preferably, the mass ratio of the biomass carbon source in the step (1) to the boron nitride in the boron nitride dispersion liquid in the step (2) is 1: 4-2: 1.
Preferably, the heat treatment in step (4) is performed by: heating to 1400-1600 ℃ at a heating rate of 2-5 ℃/min, and preserving heat for 2-4 h.
The invention also provides the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler prepared by the preparation method in the technical scheme, and the structure of the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler is a 'nest-shaped' heterogeneous structure consisting of the boron nitride nanosheet and the silicon carbide nanowire.
The invention also provides an epoxy resin heat-conducting composite material which is prepared from the following raw materials in parts by weight: 1.23-30.04 parts of boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler, 55.29-78.21 parts of epoxy resin and 14.62-20.69 parts of curing agent.
The invention also provides a preparation method of the epoxy resin heat-conducting composite material, which comprises the following steps: mixing boron nitride nanosheets @ silicon carbide nanowire heterogeneous fillers, epoxy resin and a curing agent to obtain a mixed solution; and curing the mixed solution to obtain the epoxy resin heat-conducting composite material.
Preferably, the curing temperature is 100-125 ℃, and the curing time is 4-7 h.
The invention provides a preparation method of a boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler, which comprises the following steps: mixing a biomass carbon source, tetraethoxysilane, hydrochloric acid and absolute ethyl alcohol, and carrying out hydrolysis reaction to obtain BL-Si precursor sol; mixing the BL-Si precursor sol with the boron nitride dispersion liquid to obtain boron nitride-silicon carbide precursor dispersion liquid; the mixing temperature is 40-70 ℃, and the mixing time is 3-6 h; drying the boron nitride-silicon carbide precursor dispersion liquid, and reacting with an alkali liquor at room temperature for 4-6 hours to obtain a boron nitride-silicon carbide precursor; and carrying out heat treatment on the boron nitride-silicon carbide precursor under protective gas to obtain the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler, wherein the heat treatment is carried out under the protective gas.
Mixing a biomass carbon source, tetraethoxysilane, hydrochloric acid and absolute ethyl alcohol, mixing the tetraethoxysilane, the hydrochloric acid and the absolute ethyl alcohol to perform hydrolysis reaction to form silica-containing sol, and uniformly soaking the silica-containing sol in the biomass carbon source to obtain BL-Si precursor sol; then mixing the BL-Si precursor sol with the boron nitride dispersion liquid, and limiting the mixing temperature and time to ensure that the boron nitride is fully inserted into the BL-Si precursor sol; after drying the boron nitride-silicon carbide precursor dispersion liquid, reacting the boron nitride-silicon carbide precursor dispersion liquid with alkali liquor at room temperature for 4-6 hours, removing silica which does not form sol, and preventing the existence of the silica from influencing the structure of the final boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler; the invention limits the boron nitride-silicon carbide precursor to carry out heat treatment under protective gas, and in the heat treatment process, a biomass carbon source and silicasol in the boron nitride-silicon carbide precursor grow in situ on the boron nitride nanosheet to form the silicon carbide nanowire, so that the obtained boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler has a nest-shaped heterogeneous structure. The heterostructure with the special morphology is easier to lap in an epoxy resin matrix to form a high-efficiency heat conduction path when being used as a heat conduction filler, so that the heat conduction performance of the epoxy resin can be improved under the condition of adding a small amount of filler; meanwhile, the introduction of more interface thermal barriers and the agglomeration of the heat-conducting fillers are effectively avoided based on the chemical bonding effect among the heat-conducting fillers, and the heat-conducting property of the epoxy resin can be further improved. Experimental results show that the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler with the nest-shaped heterogeneous structure can be prepared by the method provided by the invention, and is added into epoxy resin, so that the thermal conductivity of the obtained heat-conducting composite material is as high as 1.17W/mK, and the thermal conductivity of the epoxy resin can be greatly improved.
Drawings
Fig. 1 is an SEM image of a boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler prepared in example 1 of the present invention.
Detailed Description
The invention provides a preparation method of a boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler, which comprises the following steps:
(1) mixing a biomass carbon source, tetraethoxysilane, hydrochloric acid and absolute ethyl alcohol, and carrying out hydrolysis reaction to obtain BL-Si precursor sol;
(2) mixing the BL-Si precursor sol obtained in the step (1) with boron nitride dispersion liquid to obtain boron nitride-silicon carbide precursor dispersion liquid; the mixing temperature is 40-70 ℃, and the mixing time is 3-6 h;
(3) drying the boron nitride-silicon carbide precursor dispersion liquid obtained in the step (2), and reacting the boron nitride-silicon carbide precursor dispersion liquid with alkali liquor at room temperature for 4-6 hours to obtain a boron nitride-silicon carbide precursor;
(4) carrying out heat treatment on the boron nitride-silicon carbide precursor obtained in the step (3) to obtain a boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler; the heat treatment is carried out under a protective gas.
According to the invention, a biomass carbon source, tetraethoxysilane, hydrochloric acid and absolute ethyl alcohol are mixed for hydrolysis reaction to obtain BL-Si precursor sol.
In the present invention, the biomass carbon source preferably includes one or more of bamboo leaves, bamboo charcoal and glucose, more preferably bamboo leaves. The source of the biomass carbon source is not particularly limited in the invention, and the biomass carbon source obtained by the skilled person can be used. In the invention, the biomass carbon source has rich organic matters, can obtain rich carbon structures after heat treatment, and provides a carbon source for the prepared boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler.
In the present invention, the size of the biomass carbon source is preferably 100nm to 5 μm, more preferably 500nm to 4 μm, and most preferably 1 μm to 3 μm. In the invention, when the size of the biomass carbon source is in the range, the biomass carbon source and the silicasol formed by hydrolyzing tetraethoxysilane are more favorable for forming uniformly distributed BL-Si precursor sol.
In the invention, the concentration of the hydrochloric acid is preferably 0.1-0.2 mol/L, and more preferably 0.15-0.2 mol/L. In the invention, the hydrochloric acid provides an acidic environment for the hydrolysis of the tetraethoxysilane and promotes the hydrolysis reaction.
The source of the absolute ethanol is not particularly limited in the present invention, and commercially available products well known to those skilled in the art may be used. In the invention, the anhydrous ethanol provides a solvent for hydrolysis of the ethyl orthosilicate.
In the invention, when the concentration of the hydrochloric acid is 0.1-0.2 mol/L, the volume ratio of the mass of the biomass carbon source and the hydrochloric acid to the volume of the ethyl orthosilicate and the absolute ethyl alcohol is preferably (12-50) g: (0.3-1) g: (50-200) mL: (50-100) mL, more preferably (20-40) g: (0.5-1) g: (100-150) mL: (60-80) mL. In the invention, when the mass ratio of the biomass carbon source and the hydrochloric acid to the volume ratio of the ethyl orthosilicate to the absolute ethyl alcohol is in the above range, the ethyl orthosilicate can be sufficiently hydrolyzed to obtain the silica-containing sol, and the obtained silica-containing sol can be immersed in the biomass carbon source, so that the biomass carbon source is sufficiently wrapped by the silica-containing sol.
In the invention, the operation of mixing the biomass carbon source, the ethyl orthosilicate, the hydrochloric acid and the absolute ethyl alcohol is preferably as follows: mixing a biomass carbon source, tetraethoxysilane and absolute ethyl alcohol to obtain mixed slurry, and then adding hydrochloric acid into the mixed slurry to perform hydrolysis reaction to obtain BL-Si precursor sol. In the invention, in the process of mixing the biomass carbon source, the tetraethoxysilane, the hydrochloric acid and the absolute ethyl alcohol, the tetraethoxysilane is subjected to hydrolysis reaction to form silica sol, and the formed silica sol and the biomass carbon source form uniformly distributed BL-Si precursor sol. In the invention, when the mixing is in the above operation mode, the hydrolysis of the ethyl orthosilicate to form the silicasol is facilitated, and the silicasol is fully immersed in the biomass carbon source.
In the present invention, the biomass carbon source, the ethyl orthosilicate and the absolute ethanol are preferably mixed by mechanical stirring. The stirring speed is not particularly limited, and all the components can be uniformly mixed. In the invention, the stirring time is preferably 10-60 min, and more preferably 30-60 min.
The invention preferably pre-treats the biomass carbon source prior to mixing the biomass carbon source, tetraethoxysilane, hydrochloric acid and absolute ethanol.
In the present invention, the pretreatment preferably comprises subjecting the biomass carbon source to ultrasonic washing in deionized water and absolute ethanol in this order. The dosage of the deionized water and the absolute ethyl alcohol is not specially limited, and the dosage of the biomass carbon source to be treated can be adjusted according to the requirement. In the invention, when the mass of the biomass carbon source to be treated is 12-50 g, the volume of the deionized water is preferably 30-150 mL, and the volume of the absolute ethyl alcohol is preferably 50-250 mL. In the invention, the pretreatment can remove pollutants on the surface of the biomass carbon source.
According to the invention, the ultrasonic treatment and the stirring are preferably carried out in sequence after the hydrochloric acid is added into the mixed slurry. In the invention, the ultrasound can promote the mixed slurry to be uniformly mixed with the hydrochloric acid; the stirring can prevent the generated sol from aggregating, thereby being beneficial to obtaining uniformly distributed BL-Si precursor sol. The time for the ultrasonic treatment and the stirring is not particularly limited, and the time can be adjusted according to the dosage of the mixed slurry and the hydrochloric acid. In the invention, when the mass of the biomass carbon source is 12-50 g, the volume of the deionized water is 30-150 mL, and the volume of the absolute ethyl alcohol is 50-250 mL, the ultrasonic time is preferably 30-180 min, and the stirring time is preferably 1-2 h.
After obtaining BL-Si precursor sol, mixing the BL-Si precursor sol with boron nitride dispersion liquid to obtain boron nitride-silicon carbide precursor dispersion liquid.
In the invention, the mass ratio of the BL-Si precursor sol to the boron nitride in the boron nitride dispersion liquid is preferably 1:4 to 2:1, and more preferably 1:3 to 1: 1. In the invention, when the mass ratio of the BL-Si precursor sol to the boron nitride in the boron nitride dispersion liquid is in the range, the BL-Si precursor sol can grow the silicon carbide nanowire in situ on the boron nitride to construct and prepare the bird-nest-shaped heterostructure.
In the present invention, the concentration of the boron nitride dispersion is preferably 0.1 to 2g/mL, and more preferably 0.5 to 1 g/mL. In the present invention, when the concentration of the boron nitride dispersion is within the above range, it is more advantageous to control the reaction rate. In the present invention, the solvent of the boron nitride dispersion liquid is preferably absolute ethanol.
In the invention, the mixing temperature of the BL-Si precursor sol and the boron nitride dispersion liquid is 40-70 ℃, preferably 50-60 ℃; the mixing time is 3-6 h, preferably 4-5 h. In the present invention, when the temperature and time of the mixing are within the above ranges, it is advantageous for the boron nitride to be sufficiently inserted into the BL-Si precursor sol.
After the boron nitride-silicon carbide precursor dispersion liquid is obtained, the boron nitride-silicon carbide precursor dispersion liquid is dried and then reacts with alkali liquor at room temperature for 4-6 hours to obtain a boron nitride-silicon carbide precursor. In the invention, free silica which does not form sol exists in a product obtained after the boron nitride-silicon carbide precursor dispersion liquid is dried, and the product reacts with alkali liquor at room temperature to remove the free silica, so that the influence of redundant silica on the morphology of the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler is prevented.
The drying method is not particularly limited, and a drying method known to those skilled in the art may be used. In the invention, the drying temperature is preferably 85-110 ℃, and more preferably 90-100 ℃; the drying time is preferably 2-5 h, and more preferably 3-4 h. In the present invention, when the temperature and time for drying are within the above ranges, the boron nitride-silicon carbide precursor dispersion can be sufficiently dried.
In the invention, the alkali liquor is preferably a sodium hydroxide solution, and the concentration of the sodium hydroxide solution is preferably 1-2 mol/L, and more preferably 1.5-2 mol/L. In the present invention, when the concentration of the sodium hydroxide solution is in the above range, it is more advantageous to control the rate of the reaction.
The ratio of the mass of the product obtained after drying the boron nitride-silicon carbide precursor dispersion liquid to the volume of the alkali liquor is not specially limited, and the product can be adjusted as required to remove redundant silicon dioxide.
In the invention, the reaction temperature of the solid obtained by drying the boron nitride-silicon carbide precursor dispersion liquid and the alkali liquor is room temperature, preferably 20-30 ℃; the reaction time is 4-6 h, and more preferably 5-6 h.
After the reaction with the alkali liquor is completed, the system obtained by the reaction is preferably washed to obtain the boron nitride-silicon carbide precursor. The washing method of the present invention is not particularly limited, and a washing method known to those skilled in the art may be used. In the present invention, the washing is preferably washing and suction filtration performed in this order. In the present invention, the washing reagent is preferably deionized water. The invention has no special limitation on the times of washing and suction filtration, and the washed boron nitride-silicon carbide precursor can be washed to be neutral.
After the boron nitride-silicon carbide precursor is obtained, the boron nitride-silicon carbide precursor is subjected to heat treatment to obtain the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler.
The heat treatment apparatus of the present invention is not particularly limited, and a heat treatment apparatus known to those skilled in the art may be used. In the present invention, the heat treatment apparatus is preferably a tube furnace.
In the present invention, the heat treatment process is preferably: heating to 1400-1600 ℃ at a heating rate of 2-5 ℃/min, and preserving heat for 2-4 h; more preferably, the temperature is raised to 1500-1600 ℃ at a heating rate of 3-5 ℃/min, and the temperature is kept for 2-3 h. In the invention, in the heat treatment process, a biomass carbon source is combined with silicasol, and a silicon carbide nanowire is grown in situ on a boron nitride nanosheet by an in-situ growth method to construct a nest-shaped heterostructure. In the present invention, when the parameters of the heat treatment process are in the above ranges, it is advantageous to obtain a "bird's nest-like" heterostructure.
In the present invention, the heat treatment is performed under a protective gas. In the present invention, the shielding gas preferably includes argon or nitrogen, more preferably argon. In the invention, the protective gas can prevent the biomass carbon source from being oxidized and provide necessary conditions for in-situ growth.
According to the preparation method provided by the invention, the silicon carbide nanowires are grown in situ on the boron nitride nanosheets by an in-situ growth method, and the heterostructure boron nitride nano-silicon carbide nanowire heat-conducting filler with a special morphology can be obtained by controlling the preparation method.
The invention also provides the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler prepared by the preparation method in the technical scheme. In the invention, the structure of the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler is a 'nest-shaped' heterogeneous structure consisting of the boron nitride nanosheet and the silicon carbide nanowire.
In the invention, the boron nitride nanosheet and silicon carbide nanowire heterogeneous filler has a special appearance of a bird-nest-shaped heterogeneous structure, and when the boron nitride nanosheet and silicon carbide nanowire heterogeneous filler is used as a heat-conducting filler, the boron nitride nanosheet and silicon carbide nanowire heterogeneous filler is more easily lapped in an epoxy resin matrix to form an efficient heat-conducting passage, so that the heat-conducting property of epoxy resin can be improved under the condition of adding a small amount of filler; meanwhile, the introduction of more interface thermal barriers and the agglomeration of the heat-conducting fillers are effectively avoided based on the chemical bonding effect among the heat-conducting fillers, and the heat-conducting property of the epoxy resin can be further improved.
The invention also provides an epoxy resin heat-conducting composite material which is prepared from the following raw materials in parts by weight: 1.23-30.04 parts of boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler, 55.29-78.21 parts of epoxy resin and 14.62-20.69 parts of curing agent.
In the invention, the raw materials for preparing the epoxy resin heat-conducting composite material comprise 1.23-30.04 parts by weight of the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler in the technical scheme, preferably 2-25 parts by weight, and more preferably 10-20 parts by weight. In the invention, when the dosage of the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler is within the range, the thermal conductivity of the epoxy resin heat-conducting composite material can be obviously improved, and the epoxy resin heat-conducting composite material with different thermal conductivity can be obtained by changing the dosage of the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler.
In the invention, the raw materials for preparing the epoxy resin heat-conducting composite material comprise 55.29-78.21 parts of epoxy resin, preferably 60-75 parts of epoxy resin, and more preferably 65-70 parts of boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler in parts by weight of 1.23-30.04 parts of the heterogeneous filler. The source of the epoxy resin is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used. In the present invention, the source of the Epoxy resin is preferably the commercially available Epoxy 862.
In the invention, the raw materials for preparing the epoxy resin heat-conducting composite material comprise 14.62-20.69 parts of curing agent, preferably 15-20 parts of boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler by weight of 1.23-30.04 parts. The source of the curing agent is not particularly limited in the present invention, and the epoxy resin can be cured using a commercially available product known to those skilled in the art. In the present invention, the curing agent is preferably diethyltoluenediamine.
According to the technical scheme, the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler is used for enhancing the heat-conducting property of the epoxy resin, and the heat-conducting property of the epoxy resin can be improved under the condition that the addition amount of the heat-conducting filler is small.
The invention also provides a preparation method of the epoxy resin heat-conducting composite material, which comprises the following steps: mixing boron nitride nanosheets @ silicon carbide nanowire heterogeneous fillers, epoxy resin and a curing agent to obtain a mixed solution; and curing the mixed solution to obtain the epoxy resin heat-conducting composite material.
According to the invention, the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler is mixed with epoxy resin and a curing agent to obtain a mixed solution. In the invention, the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler, the epoxy resin and the curing agent are preferably mixed, then the mixture is stood, stirred and then mixed with the curing agent. In the invention, the mixing mode can promote the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler to be fully dispersed in the epoxy resin matrix, and is favorable for the subsequent formation of the uniformly distributed epoxy resin heat-conducting composite material.
In the invention, the standing time is preferably 12-36 h, and more preferably 24 h; the stirring time is preferably 2.5-4 h, and more preferably 3-4 h. The stirring speed is not specially limited, and the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler can be promoted to be dispersed with the epoxy resin by adjusting according to needs.
After the mixed liquid is obtained, the mixed liquid is solidified to obtain the epoxy resin heat-conducting composite material.
In the present invention, the mixed solution is preferably solidified in a mold after the preheating treatment. In the invention, the temperature of the preheating treatment is preferably 70-80 ℃, and more preferably 75-80 ℃. In the present invention, the preheating treatment helps the release of the cured resin.
In the invention, the mixed solution is preferably placed in a mold for preheating treatment, and then is stirred and then is solidified. In the present invention, the stirring is performed at a preheated temperature. In the invention, the stirring time is preferably 1-5 h, and more preferably 2-3 h. In the invention, the mixed solution is stirred at the preheating temperature, so that the curing agent in the mixed solution can be promoted to be fully mixed with the epoxy resin, and the uniform epoxy resin heat-conducting composite material can be obtained through subsequent crosslinking and curing.
In the invention, the curing temperature is preferably 100-125 ℃, and more preferably 110-120 ℃; the curing time is preferably 4-7 hours, and more preferably 5-6 hours. In the present invention, the curing temperature and time are within the above ranges to allow the epoxy resin to sufficiently undergo a crosslinking reaction.
The preparation method of the epoxy resin heat-conducting composite material provided by the invention adopts a blending-pouring process to prepare the epoxy resin heat-conducting composite material with excellent heat-conducting property.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Sequentially carrying out ultrasonic cleaning on a biomass carbon source (bamboo leaves) in 50mL of deionized water and 75mL of absolute ethyl alcohol for pretreatment, then stirring 15g of pretreated bamboo leaves, 50mL of ethyl orthosilicate and 50mL of absolute ethyl alcohol for 30min, then adding 0.3g (0.1mol/L) of hydrochloric acid for ultrasonic mixing, then carrying out magnetic stirring for 2h, and carrying out hydrolysis reaction to obtain a BL-Si precursor sol (wherein the volume ratio of the mass of the biomass carbon source and the hydrochloric acid to the volume of the ethyl orthosilicate and the absolute ethyl alcohol is 15 g: 0.3 g: 50 mL: 50 mL);
(2) magnetically stirring the BL-Si precursor sol obtained in the step (1) and 35mL of boron nitride dispersion liquid with the concentration of 0.25g/mL at 70 ℃ for 3 hours to obtain boron nitride-silicon carbide precursor dispersion liquid;
(3) drying the boron nitride-silicon carbide precursor dispersion liquid obtained in the step (2) at 100 ℃ for 3h, and then reacting the dried product with 50mL of 1mol/L sodium hydroxide solution at room temperature for 4h to obtain a boron nitride-silicon carbide precursor;
(4) and (4) placing the boron nitride-silicon carbide precursor obtained in the step (3) in a tube furnace, heating to 1600 ℃ at a heating rate of 5 ℃/min, and reacting for 2h in an argon atmosphere to obtain the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler.
The boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler prepared in the embodiment is tested by using a scanning electron microscope, and an SEM image is shown in FIG. 1.
As can be seen from fig. 1, the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler prepared in this embodiment is composed of a boron nitride nanosheet and a silicon carbide nanowire grown in situ on the nanosheet, and has a "bird nest" structure.
Example 2
The epoxy resin heat-conducting composite material with the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler accounting for 5% of the weight of the epoxy resin heat-conducting composite material is prepared.
5 parts of the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler prepared in example 1 and 75 parts of epoxy resin are mixed and then are kept stand for 24 hours, and then the mixed solution is mechanically stirred for 2 hours at room temperature. At 70 ℃, 20 parts of curing agent is added and stirring is continued for 2.5 h. And then pouring the mixed solution into a mold with the preheating temperature of 70 ℃, curing for 4 hours at the temperature of 120 ℃, naturally cooling to room temperature, and demolding to obtain the epoxy resin heat-conducting composite material.
The thermal conductivity of the epoxy resin heat-conducting composite material prepared in the embodiment was tested by using a TPS2200 thermal constant analyzer manufactured by Hot-Disk Limited, Sweden, and it was found that the thermal conductivity of the epoxy resin heat-conducting composite material was 0.45W/mK when the thermal conductive filler was 5 wt%.
Example 3
(1) Sequentially carrying out ultrasonic cleaning on a biomass carbon source (bamboo leaves) in 75mL of deionized water and 100mL of absolute ethyl alcohol for pretreatment, then stirring 18g of pretreated bamboo leaves, 75mL of ethyl orthosilicate and 75mL of absolute ethyl alcohol for 30min, then adding 0.3g (0.1mol/L) of hydrochloric acid for ultrasonic mixing, then carrying out magnetic stirring for 2h, and carrying out hydrolysis reaction to obtain a BL-Si precursor sol (wherein the volume ratio of the mass of the biomass carbon source and the hydrochloric acid to the volume of the ethyl orthosilicate and the absolute ethyl alcohol is 18 g: 0.3 g: 75 mL: 75 mL);
(2) magnetically stirring the BL-Si precursor sol obtained in the step (1) and 35mL of boron nitride dispersion liquid with the concentration of 0.2g/mL at 70 ℃ for 4 hours to obtain boron nitride-silicon carbide precursor dispersion liquid;
(3) drying the boron nitride-silicon carbide precursor dispersion liquid obtained in the step (2) at 100 ℃ for 3.5 hours, and then reacting the dried product with 50mL of 1mol/L sodium hydroxide solution at room temperature for 4 hours to obtain a boron nitride-silicon carbide precursor;
(4) and (3) placing the boron nitride-silicon carbide precursor obtained in the step (3) into a tube furnace, heating to 1600 ℃ at a heating rate of 5 ℃/min, and reacting for 2h in an argon atmosphere to obtain the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler.
Example 4
Preparing the epoxy resin heat-conducting composite material with the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler accounting for 10% of the weight of the epoxy resin heat-conducting composite material.
Mixing 10 parts of the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler prepared in example 1 with 78.21 parts of an epoxy resin matrix, standing for 24 hours, and mechanically stirring the mixed solution at room temperature for 2.5 hours. 11.79 parts of curing agent are added at 70 ℃ and stirring is continued for 3 hours. And then pouring the mixed solution into a mold with the preheating temperature of 70 ℃, curing for 4 hours at the temperature of 120 ℃, naturally cooling to room temperature, and demolding to obtain the epoxy resin heat-conducting composite material.
The thermal conductivity of the epoxy resin thermal conductive composite material prepared in this example was tested by using a TPS2200 thermal constant analyzer manufactured by Hot-Disk limited, sweden, and it was found that the thermal conductivity of the epoxy resin thermal conductive composite material was 0.76W/mK when the thermal conductive filler was 10 wt%.
Example 5
(1) Sequentially carrying out ultrasonic cleaning on a biomass carbon source (bamboo leaves) in 100mL of deionized water and 125mL of absolute ethyl alcohol for pretreatment, then stirring 50g of the pretreated bamboo leaves, 75mL of ethyl orthosilicate and 75mL of absolute ethyl alcohol for 30min, then adding 0.5g (0.1mol/L) of hydrochloric acid for ultrasonic mixing, then carrying out magnetic stirring for 4h, and carrying out hydrolysis reaction to obtain a BL-Si precursor sol (wherein the volume ratio of the mass of the biomass carbon source and the hydrochloric acid to the volume of the ethyl orthosilicate and the absolute ethyl alcohol is 50 g: 0.5 g: 75 mL: 75 mL);
(2) magnetically stirring the BL-Si precursor sol obtained in the step (1) and 50mL of boron nitride dispersion liquid with the concentration of 1g/mL at 70 ℃ for 5 hours to obtain boron nitride-silicon carbide precursor dispersion liquid;
(3) drying the boron nitride-silicon carbide precursor dispersion liquid obtained in the step (2) at 100 ℃ for 4h, and then reacting the dried product with 75mL of 1mol/L sodium hydroxide solution at room temperature for 4h to obtain a boron nitride-silicon carbide precursor;
(4) and (3) placing the boron nitride-silicon carbide precursor obtained in the step (3) into a tube furnace, heating to 1600 ℃ at a heating rate of 5 ℃/min, and reacting for 2h in an argon atmosphere to obtain the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler.
Example 6
Preparing the epoxy resin heat-conducting composite material with the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler accounting for 15% of the weight of the epoxy resin heat-conducting composite material.
Mixing 15 parts of the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler prepared in example 1 with 68 parts of an epoxy resin matrix, standing for 24 hours, and mechanically stirring the mixed solution at room temperature for 3 hours. At 70 ℃, 17 parts of curing agent is added and stirring is continued for 4 hours. And then pouring the mixed solution into a mold with the preheating temperature of 70 ℃, curing for 5 hours at the temperature of 120 ℃, naturally cooling to room temperature, and demolding to obtain the epoxy resin heat-conducting composite material.
The thermal conductivity of the epoxy resin heat-conducting composite material prepared in the embodiment was tested by using a TPS2200 thermal constant analyzer manufactured by Hot-Disk Limited, Sweden, and it was found that the thermal conductivity of the epoxy resin heat-conducting composite material was 1.03W/mK when the thermal conductive filler was 15 wt%.
Example 7
(1) Sequentially carrying out ultrasonic cleaning on a biomass carbon source (bamboo leaves) in 120mL of deionized water and 150mL of absolute ethyl alcohol for pretreatment, then stirring 50g of the pretreated bamboo leaves, 100mL of ethyl orthosilicate and 75mL of absolute ethyl alcohol for 30min, then adding 0.6g (0.1mol/L) of hydrochloric acid for ultrasonic mixing, then carrying out magnetic stirring for 5h, and carrying out hydrolysis reaction to obtain a BL-Si precursor sol (wherein the volume ratio of the mass of the biomass carbon source and the hydrochloric acid to the volume of the ethyl orthosilicate and the absolute ethyl alcohol is 50 g: 0.6 g: 100 mL: 75 mL);
(2) magnetically stirring the BL-Si precursor sol obtained in the step (1) and 90mL of boron nitride dispersion liquid with the concentration of 0.4g/mL at 70 ℃ for 5 hours to obtain boron nitride-silicon carbide precursor dispersion liquid;
(3) drying the boron nitride-silicon carbide precursor dispersion liquid obtained in the step (2) at 100 ℃ for 5 hours, and then reacting the dried product with 85mL of 1mol/L sodium hydroxide solution at room temperature for 4 hours to obtain a boron nitride-silicon carbide precursor;
(4) and (3) placing the boron nitride-silicon carbide precursor obtained in the step (3) into a tube furnace, heating to 1600 ℃ at a heating rate of 5 ℃/min, and reacting for 2h in an argon atmosphere to obtain the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler.
Example 8
Preparing the epoxy resin heat-conducting composite material with the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler accounting for 20% of the weight of the epoxy resin heat-conducting composite material.
Mixing 20 parts of the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler prepared in example 1 and 64 parts of an epoxy resin matrix, standing for 24 hours, and mechanically stirring the mixed solution at room temperature for 4 hours. At 70 ℃, 16 parts of curing agent is added and stirring is continued for 4 hours. And then pouring the mixed solution into a mold with the preheating temperature of 70 ℃, curing for 5 hours at the temperature of 120 ℃, naturally cooling to room temperature, and demolding to obtain the epoxy resin heat-conducting composite material.
The thermal conductivity of the epoxy resin thermal conductive composite material prepared in this example was tested by using a TPS2200 thermal constant analyzer manufactured by Hot-Disk limited, sweden, and it was found that the thermal conductivity of the epoxy resin thermal conductive composite material was 1.17W/mK when the thermal conductive filler was 20 wt%.
The embodiments show that the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler prepared by the method has a nest-shaped heterogeneous structure, and when the boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler is used as a heat-conducting filler to prepare an epoxy resin heat-conducting composite material, the heat conductivity of the epoxy resin heat-conducting composite material can be greatly improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler comprises the following steps:
(1) mixing a biomass carbon source, tetraethoxysilane, hydrochloric acid and absolute ethyl alcohol, and carrying out hydrolysis reaction to obtain BL-Si precursor sol;
(2) mixing the BL-Si precursor sol obtained in the step (1) with boron nitride dispersion liquid to obtain boron nitride-silicon carbide precursor dispersion liquid; the mixing temperature is 40-70 ℃, and the mixing time is 3-6 h;
(3) drying the boron nitride-silicon carbide precursor dispersion liquid obtained in the step (2), and reacting the boron nitride-silicon carbide precursor dispersion liquid with alkali liquor at room temperature for 4-6 hours to obtain a boron nitride-silicon carbide precursor;
(4) carrying out heat treatment on the boron nitride-silicon carbide precursor obtained in the step (3) to obtain a boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler; the heat treatment is carried out under a protective gas.
2. The preparation method according to claim 1, wherein the biomass carbon source in the step (1) comprises one or more of bamboo leaves, bamboo charcoal and glucose.
3. The method according to claim 1, wherein the concentration of the hydrochloric acid in the step (1) is 0.1 to 0.2 mol/L.
4. The preparation method according to claim 3, wherein the volume ratio of the mass of the biomass carbon source and the hydrochloric acid to the volume of the ethyl orthosilicate and the absolute ethyl alcohol in the step (1) is (12-50) g: (0.3-1) g: (50-200) mL: (50-100) mL.
5. The preparation method according to claim 1, wherein the mass ratio of the biomass carbon source in the step (1) to the boron nitride in the boron nitride dispersion liquid in the step (2) is 1:4 to 2: 1.
6. The method according to claim 1, wherein the heat treatment in the step (4) is performed by: heating to 1400-1600 ℃ at a heating rate of 2-5 ℃/min, and preserving heat for 2-4 h.
7. The boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler prepared by the preparation method of any one of claims 1 to 6 is of a 'bird nest-shaped' heterogeneous structure consisting of the boron nitride nanosheet and the silicon carbide nanowire.
8. An epoxy resin heat-conducting composite material is prepared from the following raw materials in parts by weight: 1.23-30.04 parts of boron nitride nanosheet @ silicon carbide nanowire heterogeneous filler as defined in claim 7, 55.29-78.21 parts of epoxy resin and 14.62-20.69 parts of curing agent.
9. The method for preparing the epoxy resin heat-conducting composite material of claim 8, comprising the following steps: mixing boron nitride nanosheets @ silicon carbide nanowire heterogeneous fillers, epoxy resin and a curing agent to obtain a mixed solution; and curing the mixed solution to obtain the epoxy resin heat-conducting composite material.
10. The preparation method of claim 9, wherein the curing temperature is 100-125 ℃ and the curing time is 4-7 h.
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