CN109913185B - Multilayer structure heat-conducting composite material containing heat-conducting film and preparation method thereof - Google Patents
Multilayer structure heat-conducting composite material containing heat-conducting film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a multilayer structure heat-conducting composite material containing a heat-conducting film and a preparation method thereof. The method has the advantages that the flaky hexagonal boron nitride is horizontally oriented under the hot-pressing condition, and a heat conduction path in the horizontal direction is constructed together with the horizontally spread heat conduction film; and the other granular heat-conducting filler plays a role in bridging in the system, fills gaps among the flaky hexagonal nitrides, enables a heat-conducting network to be more perfect, and simultaneously constructs a heat-conducting path in the vertical direction. The horizontal thermal conductivity of the composite material obtained by the invention is improved by 4639%, the vertical thermal conductivity is improved by 439%, and the composite material has the advantages of high thermal conductivity, good thermal stability, low dielectric constant and dielectric loss, excellent mechanical property and the like.
Description
Technical Field
The invention belongs to the technical field of heat conduction materials, and particularly relates to a multilayer structure heat conduction composite material containing a heat conduction film and a preparation method thereof.
Background
In recent years, microelectronic integration and assembly technologies have been rapidly developed, electronic devices and components have been increasingly miniaturized and multifunctional, the operating frequency thereof has been rapidly increased, heat generated during operation has been rapidly accumulated, and the ambient temperature has been continuously raised. If the accumulated heat can not be diffused outwards in time, the use reliability of equipment and components can be greatly influenced, and the service life is shortened. Therefore, how to dissipate heat in time becomes a problem to be solved urgently in the field of microelectronic packaging in order to ensure that equipment and components can operate stably and efficiently. At present, heat is generally led out in time through heat conduction materials with high heat conduction performance, so that normal operation of instrument and equipment is guaranteed. Among them, the polymer-based heat conductive composite material is most widely used due to its excellent processability and low cost.
Epoxy resin is a polymer matrix which is most commonly applied due to a series of advantages of excellent electrical insulation performance, thermal performance, mechanical performance, simple forming process, low viscosity, small curing and forming shrinkage rate and the like. However, epoxy resins have low thermal conductivity (0.18 m/W × K), and a thermally conductive filler is usually added to increase the thermal conductivity of the composite. Hexagonal boron nitride (h-BN) is a white layered crystal with a structure similar to graphite, and is called "white graphite". h-BN has higher thermal conductivity, lower dielectric constant and dielectric loss and excellent electrical insulation. Therefore, research on the hexagonal boron nitride/epoxy resin heat-conducting composite material becomes a hot spot.
For example, in a boron nitride/epoxy resin heat-conducting and insulating composite material disclosed in patent application CN 109280332 a of chinese invention in 2019, 1 month and 29 days, the invention discloses that a silane coupling agent is used for modifying the surface of boron nitride, and then the modified hexagonal boron nitride micro powder and the modified cubic boron nitride micro powder are filled in epoxy resin according to a certain ratio. The modified hexagonal boron nitride is well combined with the interface of the resin matrix, two boron nitrides in different forms are mutually overlapped in the matrix, a heat conduction path is constructed, and the heat conduction performance of the composite material is improved to a certain extent. But also has the problems of small thermal conductivity improvement amplitude, chemical reagent pollution in surface modification and environmental protection. In addition, since the B-N bond of h-BN has the characteristic of partial ionic bond, the interlayer acting force is strong, the surface modification is difficult in practice, and the modification effect is not ideal in general. h-BN has remarkable anisotropic heat conduction, horizontal heat conduction is about 20-30 times of thickness direction, and higher heat conductivity can be obtained along the orientation direction. Therefore, the hexagonal boron nitride is subjected to orientation treatment, and the heat conduction network is constructed in the matrix, so that the heat conductivity of the composite material is improved more effectively. The invention prepares a heat-conducting orientation film with high-level heat conductivity and good flexibility by a shearing induction orientation method, organically combines the high-level heat conductivity of h-BN with the excellent mechanical property of epoxy resin, introduces the heat-conducting film and another granular filler as other heat-conducting components, and constructs heat-conducting networks in horizontal and vertical directions in an epoxy matrix, thereby achieving the purposes of effectively improving the heat conductivity of the composite material and improving the mechanical property of the composite material.
Disclosure of Invention
The invention aims to construct a heat-conducting network structure in an epoxy resin matrix by using simple and easy methods such as mechanical shearing induced orientation, layer-by-layer stacking, hot press molding and the like, so as to prepare a multilayer-structure heat-conducting composite material containing a heat-conducting film, which has high heat conductivity and excellent comprehensive performance.
In order to achieve the above object, the present invention provides the following technical solutions:
a multilayer structure heat conduction composite material containing a heat conduction film comprises the heat conduction film, flaky heat conduction fillers, granular heat conduction fillers and a resin matrix, wherein under the condition of hot pressing, the flaky heat conduction fillers are oriented along the horizontal direction, heat conduction paths in the horizontal direction are constructed in the matrix together with the heat conduction film spread horizontally, the granular heat conduction fillers play a role of bridging in a system, gaps of the flaky heat conduction fillers are filled, a horizontal heat conduction network is perfected, and meanwhile, the heat conduction paths in the vertical direction are constructed to contribute to vertical heat conductivity.
The heat-conducting film is any one of a boron nitride heat-conducting film, a graphene heat-conducting film and a carbon nano tube heat-conducting film, the matrix phase is any one of nano cellulose, polyvinyl alcohol, polyimide and polylactic acid, the heat-conducting film is prepared by a specific device through liquid-phase ultrasonic stripping, solution blending and mechanical shearing induced orientation methods, and has a highly oriented structure, high heat conductivity, good flexibility, uniform thickness of the heat-conducting film, mold thickness control and uniform mechanical shearing speed, and is controlled by a machine, strong interaction can be formed between the filler phase and the matrix phase in the heat-conducting film, and interface bonding is good.
The number of layers of the heat-conducting film is 0-15, the content is 0-1.9wt%, the total content of the heat-conducting filler is 10-30wt%, the content of the resin matrix is 0-70wt%, and the sum of the content percentages of all the components is 100%.
The flaky heat-conducting filler is hexagonal boron nitride h-BN, the particle size is 15-25 mu m, and the granular heat-conducting filler is aluminum nitride AlN or aluminum oxide Al3O2Silicon dioxide SiO2And any one of magnesium oxide and MgO, the particle diameter is 1-5 μm, and the adding proportion of the two fillers is (1-3): 1.
the resin matrix also comprises a curing agent and a curing accelerator, wherein the resin matrix is one of low-viscosity epoxy resins, the curing agent is any one of amines, acid anhydrides and synthetic resins, the content of the curing agent is 80-90%, and the curing accelerator is any one of amines, acid anhydrides and imidazoles, and the content of the curing accelerator is 1-3%.
The invention also provides a preparation method of the multilayer structure heat-conducting composite material containing the heat-conducting film, which comprises the following steps:
(1) preparing a heat-conducting orientation film by a mechanical shearing and orientation induction method by using a specific device;
(2) weighing a certain amount of liquid epoxy, weighing a curing agent and a curing accelerator according to a proportion, and then placing the mixture in a constant-temperature water bath kettle for heating and stirring;
(3) according to (1-3): 1, weighing two heat-conducting fillers according to the proportion, adding the heat-conducting fillers into the epoxy resin mixture obtained in the step 2, and heating and stirring the mixture in a constant-temperature water bath kettle to be in a uniform state;
(4) mechanically perforating the heat-conducting film obtained in the step 1 by using a needle roller, and pre-impregnating the heat-conducting film in the uniform mixture of the epoxy resin and the heat-conducting filler obtained in the step 3;
(5) stacking the pre-impregnated heat-conducting film and the uniform mixture of the epoxy resin and the heat-conducting filler obtained in the step (3) in a mould in a middle layer manner, placing the mould in an oven for pre-curing to obtain a semi-solid material, transferring the semi-solid material into a flat vulcanizing machine, and carrying out hot pressing;
(6) and after the hot pressing is finished, transferring the sample into an oven for further curing, and finally obtaining the heat-conducting composite material with the multilayer structure.
In the step 2, the temperature of the constant-temperature water bath is controlled to be 40-50 ℃, and the heating time is 30-50 minutes.
And 3, heating and stirring the mixture of the heat-conducting filler and the resin matrix at the temperature of 40-50 ℃ for 2-3 hours.
The aperture size and the gap of the needle roller used in the step 4 are respectively 1-2mm and 2-3 mm.
In the step 4, the heat-conducting film is soaked in the mixture of the heat-conducting filler and the resin matrix for 10-20 minutes.
The size of the die in the step 5 is as follows: 30mm, thickness: 2 mm.
The pre-curing temperature in the step 5 is 90-100 ℃, the pre-curing time is 90-120 minutes, the hot-pressing temperature is 100-; the conditions for further curing in the step 6 are as follows: 110 ℃ and 120 ℃ for 2-3 h; 150 ℃ and 160 ℃ for 4-5 h.
The principle of the invention is as follows:
the h-BN is horizontally oriented under the hot pressing condition, a heat conduction passage in the horizontal direction is constructed together with the heat conduction film which is horizontally spread, the granular heat conduction filler is taken as another component of heat conduction particles to be introduced into the system to play a role of bridging, and gaps among h-BN sheet layers are filled, so that a heat conduction network is more perfect. In addition, because the thermal conductivity of the h-BN is high along the orientation direction and low perpendicular to the orientation direction after the h-BN is oriented, the introduction of the granular filler can well compensate the defect and contribute to the thermal conductivity in the perpendicular direction.
The invention has the advantages that:
(1) the method for preparing the heat-conducting composite material is very simple and convenient, the filler is oriented by the methods of shear induction and hot pressing, the effect is obvious, and compared with other orientation methods such as magnetic field induction, electric field induction, vacuum filtration and the like, the method is simpler and more efficient.
(2) The heat-conducting composite material comprises a heat-conducting film, wherein a matrix phase and a filler phase in the heat-conducting film form chemical bonding, the interface bonding is good, the heat-conducting composite material has excellent horizontal heat conductivity, and the flexibility is good. The introduction of the heat-conducting film is beneficial to the construction of a heat-conducting network of the composite material in the horizontal direction, and the horizontal heat conductivity of the composite material can be effectively improved.
(3) The heat conduction composite material provided by the invention constructs heat conduction paths in the horizontal direction and the vertical direction, the heat conductivity of the composite material in the two directions is greatly improved, and most of the current researches on the heat conduction composite material only aim at improving the heat conductivity in a certain direction.
(4) The preparation process of the heat-conducting composite material is environment-friendly, no chemical solvent pollution is caused, the price of experimental materials is low, and large-scale production is easy to realize.
Drawings
FIG. 1 is a cross-sectional scan of the BNNS/CNF thermal conductive film obtained in example 1 and a thermal conductive composite material containing 6 layers of thermal conductive films.
FIG. 2 is an infrared spectrum of the BNNS/CNF thermal conductive film obtained in example 1.
Fig. 3 shows the horizontal thermal conductivity and the vertical thermal conductivity of the thermally conductive composite materials containing different numbers of thermally conductive films obtained in examples 1, 2 and 3, as a function of the number of thermally conductive films.
Fig. 4 is a graph showing a comparison of infrared thermal imaging of the multilayer-structured heat conductive composite material with a heat conductive film and the heat conductive composite material without a heat conductive film obtained in example 1 and example 4 as a comparative example.
Fig. 5 is a graph showing a comparison of horizontal thermal conductivity and vertical thermal conductivity between a mixed filler-filled multilayer structure thermally conductive composite material containing a thermally conductive film obtained in example 2 and a single filler-filled multilayer structure thermally conductive composite material containing a thermally conductive film obtained in example 5 as a comparative example.
Fig. 6 is a graph showing storage modulus and dissipation factor curves of the thermal conductive composite materials of examples 1, 2, and 3, which contain different numbers of layers of thermal conductive films.
Detailed Description
The technical scheme of the invention is further explained by combining the specific examples as follows:
example 1
The method comprises the following steps of taking nano-Cellulose (CNF) as a matrix and hexagonal boron nitride as a heat-conducting filler, carrying out liquid-phase ultrasonic stripping on the hexagonal boron nitride to obtain a Boron Nitride Nanosheet (BNNS), and preparing the boron nitride nanosheet/nano-cellulose (BNNS/CNF) heat-conducting orientation film by utilizing a shear induced orientation method with the aid of a specific instrument;
according to the following steps of 100: 90: 1, weighing 10g of epoxy resin, 9g of amine curing agent and 0.1g of imidazole curing accelerator, placing the epoxy resin, the amine curing agent and the imidazole curing accelerator in a constant-temperature water bath kettle, and stirring the epoxy resin, the amine curing agent and the imidazole curing accelerator for 30 minutes at 45 ℃;
according to the following steps of 1: 1, respectively weighing 4.1g of h-BN with the particle size of 25 mu m and 4.1g of AlN particles with the particle size of 1 mu m (namely the filler content is 30wt percent), gradually adding the two fillers into the epoxy resin mixture in sequence, and continuously stirring for 3 hours at the temperature of 45 ℃;
mechanically drilling a BNNS/CNF heat-conducting orientation film by using a needle roller, and pre-impregnating the film in the mixture of the epoxy resin and the filler for 15 minutes;
stacking the preimpregnated orientation film and the mixture of the epoxy resin/the filler layer by layer (6 layers of films), placing the stacked orientation film and the mixture into a mold, and then transferring the mold into an oven to perform precuring for 120 minutes at 90 ℃;
obtaining a semi-solid sample after the pre-curing is finished, quickly transferring the sample into a flat vulcanizing machine after demolding, and carrying out hot pressing for 15 minutes at 100 ℃ and under the pressure of 10 MPa;
after the hot pressing is finished, the sample is transferred into an oven for further curing, and the curing conditions are as follows: 110 ℃ for 2 h; and (4) at 150 ℃ for 4h, and finally obtaining the heat-conducting composite material with the multilayer structure.
Fig. 1 is a cross-sectional scan of the BNNS/CNF thermal conductive film obtained in example 1 and a thermal conductive composite material containing 6 layers of thermal conductive films, from which it can be seen that the BNNS/CNF thermal conductive film has a good layered structure, boron nitride nanosheets are highly oriented under the action of mechanical shear force, the thermal conductive composite material has a distinct multilayer structure, and the thermal conductive film is spread in an epoxy matrix along a horizontal direction.
FIG. 2 is an infrared spectrum of the BNNS/CNF thermal conduction film obtained in example 1, and it can be seen from the spectrum that the hydroxyl peak of the BNNS/CNF thermal conduction film is shifted to a lower wave number than that of BNNS and CNF, indicating that hydrogen bonds are formed between BNNS and CNF, and thus the interface bonding between the BNNS and the CNF is good.
Example 2
The method comprises the following steps of taking nano-Cellulose (CNF) as a matrix and hexagonal boron nitride as a heat-conducting filler, carrying out liquid-phase ultrasonic stripping on the hexagonal boron nitride to obtain a Boron Nitride Nanosheet (BNNS), and preparing the boron nitride nanosheet/nano-cellulose (BNNS/CNF) heat-conducting orientation film by utilizing a shear induced orientation method with the aid of a specific instrument;
according to the following steps of 100: 90: 1, weighing 10g of epoxy resin, 9g of amine curing agent and 0.1g of imidazole curing accelerator, placing the epoxy resin, the amine curing agent and the imidazole curing accelerator in a constant-temperature water bath kettle, and stirring the epoxy resin, the amine curing agent and the imidazole curing accelerator for 30 minutes at 45 ℃;
according to the following steps of 1: 1, respectively weighing 4.1g of h-BN with the particle size of 25 mu m and 4.1g of AlN particles with the particle size of 1 mu m (namely the filler content is 30wt percent), gradually adding the two fillers into the epoxy resin mixture in sequence, and continuously stirring for 3 hours at the temperature of 45 ℃;
mechanically drilling a BNNS/CNF heat-conducting orientation film by using a needle roller, and pre-impregnating the film in the mixture of the epoxy resin and the filler for 15 minutes;
stacking the preimpregnated orientation film and the mixture of the epoxy resin/filler layer by layer (9 layers of films), placing the stacked orientation film and the mixture into a mold, and then transferring the mold into an oven to perform precuring for 120 minutes at 90 ℃;
obtaining a semi-solid sample after the pre-curing is finished, quickly transferring the sample into a flat vulcanizing machine after demolding, and carrying out hot pressing for 15 minutes at 100 ℃ and under the pressure of 10 MPa;
after the hot pressing is finished, the sample is transferred into an oven for further curing, and the curing conditions are as follows: 110 ℃ for 2 h; and (4) at 150 ℃ for 4h, and finally obtaining the heat-conducting composite material with the multilayer structure.
Example 3
The method comprises the following steps of taking nano-Cellulose (CNF) as a matrix and hexagonal boron nitride as a heat-conducting filler, carrying out liquid-phase ultrasonic stripping on the hexagonal boron nitride to obtain a Boron Nitride Nanosheet (BNNS), and preparing the boron nitride nanosheet/nano-cellulose (BNNS/CNF) heat-conducting orientation film by utilizing a shear induced orientation method with the aid of a specific instrument;
according to the following steps of 100: 90: 1, weighing 10g of epoxy resin, 9g of amine curing agent and 0.1g of imidazole curing accelerator, placing the epoxy resin, the amine curing agent and the imidazole curing accelerator in a constant-temperature water bath kettle, and stirring the epoxy resin, the amine curing agent and the imidazole curing accelerator for 30 minutes at 45 ℃;
according to the following steps of 1: 1, respectively weighing 4.1g of h-BN with the particle size of 25 mu m and 4.1g of AlN particles with the particle size of 1 mu m (namely the filler content is 30wt percent), gradually adding the two fillers into the epoxy resin mixture in sequence, and continuously stirring for 3 hours at the temperature of 45 ℃;
mechanically drilling a BNNS/CNF heat-conducting orientation film by using a needle roller, and pre-impregnating the film in the mixture of the epoxy resin and the filler for 15 minutes;
stacking the preimpregnated orientation film and the mixture of the epoxy resin/the filler layer by layer (12 layers of films), placing the stacked orientation film and the mixture into a mold, and then transferring the mold into an oven to perform precuring for 120 minutes at 90 ℃;
obtaining a semi-solid sample after the pre-curing is finished, quickly transferring the sample into a flat vulcanizing machine after demolding, and carrying out hot pressing for 15 minutes at 100 ℃ and under the pressure of 10 MPa;
after the hot pressing is finished, the sample is transferred into an oven for further curing, and the curing conditions are as follows: 110 ℃ for 2 h; and (4) at 150 ℃ for 4h, and finally obtaining the heat-conducting composite material with the multilayer structure.
Fig. 3 shows that the horizontal thermal conductivity and the vertical thermal conductivity of the heat-conducting composite materials containing different numbers of heat-conducting films obtained in examples 1, 2 and 3 vary with the number of the heat-conducting films, and it can be seen that the horizontal thermal conductivity of the composite materials gradually increases with the increase of the number of the heat-conducting films, and the vertical thermal conductivity does not change much, but is greatly improved compared with the thermal conductivity (0.18W/m × K) of a pure epoxy resin matrix.
Fig. 4 is a graph showing storage modulus and loss factor of the thermal conductive composite materials containing different numbers of layers of thermal conductive films obtained in examples 1, 2, and 3, and it can be seen from the graph that the thermal conductive composite material prepared by the present invention has a higher storage modulus, that is, the rigidity of the composite material is greatly improved compared with that of pure epoxy resin, and as the number of layers increases, the glass transition temperature of the composite material gradually increases (the temperature corresponding to the peak value of the loss factor).
Example 4
As a comparative example
The method comprises the following steps of taking nano-Cellulose (CNF) as a matrix and hexagonal boron nitride as a heat-conducting filler, carrying out liquid-phase ultrasonic stripping on the hexagonal boron nitride to obtain a Boron Nitride Nanosheet (BNNS), and preparing the boron nitride nanosheet/nano-cellulose (BNNS/CNF) heat-conducting orientation film by utilizing a shear induced orientation method with the aid of a specific instrument;
according to the following steps of 100: 90: 1, weighing 10g of epoxy resin, 9g of amine curing agent and 0.1g of imidazole curing accelerator, placing the epoxy resin, the amine curing agent and the imidazole curing accelerator in a constant-temperature water bath kettle, and stirring the epoxy resin, the amine curing agent and the imidazole curing accelerator for 30 minutes at 45 ℃;
weighing 8.2g of h-BN (namely the filler content is 30wt percent) with the particle size of 25 mu m, adding the filler into the epoxy resin mixture, and continuously stirring for 3 hours at the temperature of 45 ℃;
mechanically drilling a BNNS/CNF heat-conducting orientation film by using a needle roller, and pre-impregnating the film in the mixture of the epoxy resin and the filler for 15 minutes;
stacking the preimpregnated orientation film and the mixture of the epoxy resin/filler layer by layer (9 layers of films), placing the stacked orientation film and the mixture into a mold, and then transferring the mold into an oven to perform precuring for 120 minutes at 90 ℃;
obtaining a semi-solid sample after the pre-curing is finished, quickly transferring the sample into a flat vulcanizing machine after demolding, and carrying out hot pressing for 15 minutes at 100 ℃ and under the pressure of 10 MPa;
after the hot pressing is finished, the sample is transferred into an oven for further curing, and the curing conditions are as follows: 110 ℃ for 2 h; and (4) at 150 ℃ for 4h, and finally obtaining the heat-conducting composite material with the multilayer structure.
Fig. 5 is a graph comparing the horizontal thermal conductivity and vertical thermal conductivity of the mixed filler filled multi-layer structure thermal conductive composite containing the thermal conductive film obtained in example 2 and the single filler filled multi-layer structure thermal conductive composite containing the thermal conductive film obtained in example 4, and it can be seen that the use of the mixed filler filling is more effective in improving the thermal conductivity of the composite, particularly the vertical thermal conductivity, and the vertical thermal conductivity of the composite is significantly improved after the addition of the granular aluminum nitride.
Example 5
As a comparative example
The method comprises the following steps of taking nano-Cellulose (CNF) as a matrix and hexagonal boron nitride as a heat-conducting filler, carrying out liquid-phase ultrasonic stripping on the hexagonal boron nitride to obtain a Boron Nitride Nanosheet (BNNS), and preparing the boron nitride nanosheet/nano-cellulose (BNNS/CNF) heat-conducting orientation film by utilizing a shear induced orientation method with the aid of a specific instrument;
according to the following steps of 100: 90: 1, weighing 10g of epoxy resin, 9g of amine curing agent and 0.1g of imidazole curing accelerator, placing the epoxy resin, the amine curing agent and the imidazole curing accelerator in a constant-temperature water bath kettle, and stirring the epoxy resin, the amine curing agent and the imidazole curing accelerator for 30 minutes at 45 ℃;
according to the following steps of 1: 1, respectively weighing 4.1g of h-BN with the particle size of 25 mu m and 4.1g of AlN particles with the particle size of 1 mu m (namely the filler content is 30wt percent), gradually adding the two fillers into the epoxy resin mixture in sequence, and continuously stirring for 3 hours at the temperature of 45 ℃;
transferring the obtained mixture into a mold, and pre-curing the mixture in an oven at 90 ℃ for 120 minutes;
obtaining a semi-solid sample after the pre-curing is finished, quickly transferring the sample into a flat vulcanizing machine after demolding, and carrying out hot pressing for 15 minutes at 100 ℃ and under the pressure of 10 MPa;
after the hot pressing is finished, the sample is transferred into an oven for further curing, and the curing conditions are as follows: 110 ℃ for 2 h; and (4) at 150 ℃ for 4h, and finally obtaining the heat-conducting composite material without the multilayer structure.
Fig. 6(a) and 6(b) are comparative infrared thermal imaging graphs of the multi-layer structure heat-conductive composite material containing the heat-conductive film and the heat-conductive composite material without the heat-conductive film obtained in examples 1 and 5, and it can be seen from the comparative graphs that the multi-layer structure heat-conductive composite material containing the heat-conductive film has a faster temperature change speed and a better heat transfer effect than the heat-conductive composite material without the heat-conductive film, which illustrates that the introduction of the heat-conductive film in the present invention and the specific multi-layer structure are very effective in improving the heat conductivity of the composite material.
Claims (5)
1. A multilayer structure heat conduction composite material containing a heat conduction film is characterized by comprising the heat conduction film, flaky heat conduction fillers, granular heat conduction fillers and a resin matrix, wherein under the condition of hot pressing, the flaky heat conduction fillers are oriented along the horizontal direction, and form a heat conduction path in the horizontal direction with the heat conduction film spread horizontally in the matrix;
the heat-conducting film is a boron nitride heat-conducting film, the matrix phase is nano-cellulose, the heat-conducting film is prepared by a specific device through liquid-phase ultrasonic stripping, solution blending and mechanical shearing induced orientation, and the heat-conducting film has a highly oriented structure, high heat conductivity and good flexibility;
the number of layers of the heat-conducting film is 6-15, the total content of the heat-conducting filler is 30wt%, the content of the resin matrix is 70wt%, and the sum of the content percentages of all the components is 100%;
the flaky heat-conducting filler is hexagonal boron nitride h-BN, the particle size is 15-25 mu m, and the granular heat-conducting filler is aluminum nitride AlN or aluminum oxide Al2O3Silicon dioxide SiO2And any one of magnesium oxide and MgO, the particle diameter is 1-5 μm, and the adding proportion of the two fillers is (1-3): 1;
the resin matrix further comprises a curing agent and a curing accelerator, wherein the resin matrix is one of low-viscosity epoxy resins, the curing agent is amines, and the curing accelerator is imidazoles, wherein the ratio of the epoxy resin to the amine curing agent to the imidazoles curing accelerator is 100: 90: 1;
the preparation method of the multilayer structure heat-conducting composite material containing the heat-conducting film comprises the following steps:
(1) preparing a heat-conducting orientation film by a mechanical shearing and orientation induction method by using a specific device;
(2) weighing a certain amount of liquid epoxy resin, weighing a curing agent and a curing accelerator according to a certain proportion, and then placing the mixture in a constant-temperature water bath kettle for heating and stirring;
(3) according to (1-3): weighing two heat-conducting fillers according to the proportion of 1, adding the heat-conducting fillers into the epoxy resin mixture obtained in the step (2), and heating and stirring the mixture in a constant-temperature water bath kettle to be in a uniform state;
(4) mechanically perforating the heat-conducting film obtained in the step (1) by using a needle roller, and pre-impregnating the heat-conducting film in the uniform mixture of the epoxy resin and the heat-conducting filler obtained in the step (2);
(5) stacking the pre-impregnated heat-conducting film and the uniform mixture of the epoxy resin and the heat-conducting filler obtained in the step (3) in a mould in a layer manner, placing the mould in an oven for pre-curing to obtain a semi-solid material, transferring the semi-solid material into a flat vulcanizing machine, and carrying out hot pressing;
(6) and after the hot pressing is finished, transferring the sample into an oven for further curing, and finally obtaining the heat-conducting composite material with the multilayer structure.
2. The thermally conductive composite material with a multi-layer structure comprising a thermally conductive film as claimed in claim 1, wherein the temperature of the constant temperature water bath in the step (2) is controlled to be 40-50 ℃ and the heating time is 30-50 minutes.
3. The thermally conductive composite material having a multi-layered structure comprising a thermally conductive film as claimed in claim 1, wherein the mixture of the thermally conductive filler and the resin matrix in the step (3) is heated and stirred at a temperature of 40 to 50 ℃ for 2 to 3 hours.
4. The thermally conductive composite material having a multi-layered structure comprising a thermally conductive film as claimed in claim 1, wherein the thermally conductive film is impregnated in the mixture of the thermally conductive filler and the resin matrix for 10 to 20 minutes in the step (4).
5. The heat conductive composite material with a multilayer structure comprising a heat conductive film as claimed in claim 1, wherein the temperature of pre-curing in step (5) is 90-100 ℃, the pre-curing time is 90-120 minutes, the temperature of hot pressing is 100-; the conditions for further curing in the step (6) are as follows: 110 ℃ and 120 ℃ for 2-3 h; 150 ℃ and 160 ℃ for 4-5 h.
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