CN111391440A - Insulating and heat-conducting polymer composite material with frequency-selective electromagnetic shielding function and preparation method thereof - Google Patents

Insulating and heat-conducting polymer composite material with frequency-selective electromagnetic shielding function and preparation method thereof Download PDF

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CN111391440A
CN111391440A CN202010184196.XA CN202010184196A CN111391440A CN 111391440 A CN111391440 A CN 111391440A CN 202010184196 A CN202010184196 A CN 202010184196A CN 111391440 A CN111391440 A CN 111391440A
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heat
conducting
insulating
polymer
electromagnetic shielding
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CN111391440B (en
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廖霞
王圭
郭富民
陈佳
李光宪
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Sichuan University
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Abstract

The invention provides an insulating and heat-conducting polymer composite material with frequency-selective electromagnetic shielding, which consists of an insulating heat-conducting layer and two electric heat-conducting layers, wherein the two electric heat-conducting layers are respectively positioned at two sides of the insulating heat-conducting layer to form an integrated sandwich structure; the insulating heat conduction layer comprises a polymer matrix and insulating heat conduction fillers, the insulating heat conduction fillers are selectively distributed at the interface of polymer particles to form an insulating heat conduction network, the electric heat conduction layer comprises the polymer matrix and electric and heat conduction fillers, the electric and heat conduction fillers are distributed in the polymer matrix to form an electric and heat conduction network, and the composition of the insulating heat conduction layer and the composition of the polymer matrix of the electric and heat conduction layer are the same; the material has frequency-selective electromagnetic shielding performance and is insulated in the electromagnetic shielding direction. The invention endows the existing heat-conducting electromagnetic shielding material with frequency selective electromagnetic shielding function, and can better meet the new requirements of the heat-conducting electromagnetic shielding material on selective electromagnetic shielding, heat conduction, insulation and the like.

Description

Insulating and heat-conducting polymer composite material with frequency-selective electromagnetic shielding function and preparation method thereof
Technical Field
The invention belongs to the field of heat-conducting electromagnetic shielding materials, and relates to an insulating heat-conducting polymer composite material with frequency-selective electromagnetic shielding and a preparation method thereof.
Background
Breakthrough of 5G communication technology and expansion of application scenarios will promote revolutionary development of communication devices and intelligent terminals, and along with continuous development of intelligent devices towards ultra-high integration, miniaturization and densification, electronic devices are also continuously moving towards integration, miniaturization, high frequency and high power, which makes electromagnetic interference and local heat release problems increasingly prominent. Electromagnetic radiation not only affects the normal operation of electronic equipment, but also damages the natural ecological environment, has hidden danger to human health, and can cause problems of electromagnetic pollution, electromagnetic wave disclosure and the like. Meanwhile, the electronic device is highly integrated and highly powered, so that the heat dissipation problem of an electronic product is increasingly raised, if the electronic component is locally overheated, the working efficiency of the electronic component is reduced, the service life of the electronic component is greatly shortened, and the use reliability and safety of the electronic component are reduced. The problem of electromagnetic radiation can be solved through electromagnetic shielding, but when the material shields electromagnetic waves, electromagnetic energy can be converted into heat energy, and for application scenes with high integration and high power of electronic devices, such as high-power integrated circuits, 5G communication, high-power radars, terahertz communication equipment and the like, if the electronic devices generate heat and the heat energy generated by electromagnetic shielding cannot be effectively dissipated in time, the operation stability, reliability and safety of the electronic devices can be seriously influenced. Therefore, it is of great significance to develop an electromagnetic shielding material having a heat-conducting function.
When heat conduction and electromagnetic shielding are considered, short circuit and even electric leakage are prevented from occurring in order to ensure the safe operation of electronic components, so that the heat conduction electromagnetic shielding material is required to have better insulation property, and the application of the traditional metal-based heat conduction electromagnetic shielding material is greatly limited. The polymer material has the characteristics of insulation, light weight, easiness in processing and forming, high forming freedom degree, corrosion resistance and the like, and can be designed according to the application environment requirements to meet the requirements of insulation, heat conduction, electromagnetic shielding and the like. Therefore, polymer-based insulating and heat-conducting electromagnetic shielding materials have received much attention.
With the continuous expansion of the application field of the heat-conducting electromagnetic shielding material, the application environment of the heat-conducting electromagnetic shielding material becomes more diversified and complicated, for example, the shielding wave band required by some application scenes is narrower, only electromagnetic waves of a certain narrower specific wave band need to be shielded, and for such application scenes, the electromagnetic shielding material capable of selectively shielding the wave band has higher cost performance. CN 108943921A discloses a multilayer insulation thermal interface material and a preparation method thereof, wherein insulation heat-conducting filler filled silicone rubber and electric heat-conducting filler filled silicone rubber are alternately distributed to prepare a material with 2nThe multilayer insulation thermal interface material with the layer (n is more than or equal to 1) has high heat conductivity coefficient, excellent electrical insulation and mechanical property, but the material has no selective electromagnetic shielding property and needs more insulation heat-conducting fillers to form a heat-conducting path, so that the material is difficult to play a role in high-efficiency electromagnetic shielding, insulation and heat dissipation when applied to the fields of high-power integrated circuits, 5G communication, high-power radars, terahertz communication equipment and the like. At present, no report of polymer-based materials with selective electromagnetic shielding and insulating heat conduction functions is found, and the development of materials with selective electromagnetic shielding and insulating heat conduction functions is of great significance in order to meet the requirements of efficient electromagnetic shielding, insulation and heat conduction at the same time.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an insulating and heat-conducting polymer composite material with frequency-selective electromagnetic shielding and a preparation method thereof, so that the existing heat-conducting electromagnetic shielding material is endowed with the frequency-selective electromagnetic shielding function, and the new requirements of the heat-conducting electromagnetic shielding material on selective electromagnetic shielding, heat conduction, insulation and the like are better met.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides an insulating and heat-conducting polymer composite material with frequency-selective electromagnetic shielding, which consists of an insulating heat-conducting layer and two electric heat-conducting layers, wherein the two electric heat-conducting layers are respectively positioned at two sides of the insulating heat-conducting layer to form an integrated sandwich structure; the insulating heat conduction layer comprises a polymer matrix and insulating heat conduction fillers, the insulating heat conduction layer is prepared by hot press molding after the insulating heat conduction fillers coat polymer powder, the insulating heat conduction fillers are selectively distributed at the interface of polymer particles to form an insulating heat conduction network, the electric heat conduction layer comprises the polymer matrix and the electric and heat conduction fillers, the electric and heat conduction fillers are distributed in the polymer matrix to form an electric and heat conduction network, and the composition of the insulating heat conduction layer and the polymer matrix of the electric and heat conduction layer is the same; the material has frequency-selective electromagnetic shielding performance and is insulated in the electromagnetic shielding direction, and the material has heat-conducting performance and surface conductive performance.
In the technical scheme of the insulating and heat-conducting polymer composite material with the frequency-selective electromagnetic shielding function, when the insulating and heat-conducting layer is prepared, in order to enable the insulating and heat-conducting layer to form an insulating and heat-conducting network more easily, the surface area of the adopted polymer powder is matched with the surface area of the insulating and heat-conducting filler which can be coated. The size of the polymer powder adopted when the insulating and heat conducting layer is prepared is preferably 10-1000 microns, and the size of the insulating and heat conducting filler is preferably 0.05-0.2 times of the size of the polymer powder. The shape of the insulating and heat conducting filler can be sheet, granular, fibrous and the like, and in order to make the insulating and heat conducting layer easier to form an insulating and heat conducting network, the sheet insulating and heat conducting filler is preferably used. Furthermore, the size of the insulating and heat conducting filler can be 1-200 μm.
In the technical scheme of the insulating and heat-conducting polymer composite material with frequency-selective electromagnetic shielding, the insulating and heat-conducting filler is selected from one or more of silicon carbide, boron carbide, titanium carbide, zirconium carbide, chromium carbide, tungsten carbide, silicon nitride, boron nitride, aluminum nitride, beryllium oxide, aluminum oxide and zinc oxide.
In the above technical solution of the insulating and heat conducting polymer composite material with frequency selective electromagnetic shielding, the content of the insulating and heat conducting filler in the insulating and heat conducting layer should ensure that the insulating and heat conducting filler can form an insulating and heat conducting network in the polymer matrix of the layer, and the specific content can be adjusted according to the actual application requirements depending on the factors such as the shape and size of the specifically adopted insulating and heat conducting filler, generally, the content of the insulating and heat conducting filler in the insulating and heat conducting layer is 5% to 200% of the mass of the polymer matrix in the layer, further, the content of the insulating and heat conducting filler in the insulating and heat conducting layer is preferably 20% to 150% of the mass of the polymer matrix in the layer, and further, the content of the insulating and heat conducting filler in the insulating and heat conducting layer is preferably 40% to 100% of.
In the technical scheme of the insulating and heat-conducting polymer composite material with the frequency-selective electromagnetic shielding function, the electric and heat-conducting filler is one or more selected from carbon fillers and metal fillers. The carbon-based filler comprises graphite, carbon black, graphene, carbon nanotubes and the like, and the metal filler comprises copper, silver, gold, aluminum, nickel and the like. In order to make it easier to form the electrically and thermally conductive network in the electrically and thermally conductive layer, a sheet-shaped, fibrous, tubular or granular carbon-based filler is preferably used, for example, the electrically and thermally conductive filler may be at least one of graphene, carbon nanotubes, graphite, carbon fibers and carbon black, and a sheet-shaped, fibrous or tubular carbon-based filler is more preferably used, for example, the electrically and thermally conductive filler may be at least one of graphene, carbon nanotubes, carbon fibers and sheet graphite.
In the above technical solution of the insulating and heat conducting polymer composite material with frequency selective electromagnetic shielding, the content of the electrically and heat conducting filler in the electrically and heat conducting layer should ensure that the electrically and heat conducting filler can form an electrically and heat conducting network in the polymer matrix of the layer, and the specific content can be adjusted according to the actual application requirements depending on the specifically adopted factors such as the shape and size of the electrically and heat conducting filler, generally, the content of the electrically and heat conducting filler in the electrically and heat conducting layer is 0.1-50% of the mass of the polymer matrix in the layer, and further, the content of the electrically and heat conducting filler in the electrically and heat conducting layer is preferably 3-30% of the mass of the polymer matrix in the layer.
In the technical scheme of the insulating and heat conducting polymer composite material with the frequency selective electromagnetic shielding function, the polymer matrixes in the insulating and heat conducting layer and the electric and heat conducting layer are thermoplastic resin, thermoplastic elastomer, thermosetting resin or thermosetting elastomer. More specifically, the polymer matrix includes thermoplastic resins such as polyolefin, polyamide, polyester and polyether, thermoplastic elastomers such as thermoplastic polyurethane and ethylene-octene copolymer, thermosetting resins such as unsaturated polyester resin, epoxy resin and phenol resin, and rubbers such as natural rubber, styrene-butadiene rubber, isoprene rubber, silicone rubber and fluororubber.
In the technical scheme of the insulating and heat-conducting polymer composite material with the frequency-selective electromagnetic shielding, the frequency-selective electromagnetic shielding performance of the polymer composite material is closely related to the thickness of the insulating and heat-conducting layer, the thickness of the electric and heat-conducting layer, the content of the electric and heat-conducting filler and other factors in the material, and the specific selective electromagnetic shielding performance, such as the electromagnetic shielding efficiency, the frequency band targeted by the electromagnetic shielding and the like, can be adjusted according to the actual application requirements. Generally, the thickness of the insulating heat conduction layer is 0.1-40 mm, and the thickness of the electric heat conduction layer is 0.1-40 mm.
The invention also provides a preparation method of the insulating and heat-conducting polymer composite material with the frequency selective electromagnetic shielding function, which comprises the following steps:
(1) preparation of electrically and thermally conductive sheet layer and electrically and thermally conductive sheet layer
①, blending 100 parts by mass of a polymer base material and 0.1-50 parts by mass of an electric and heat conducting filler, when the polymer base material is a thermosetting elastomer, adding 1-10 parts by mass of a vulcanizing agent during blending, when the polymer base material is a thermosetting resin, adding 1-10 parts by mass of a curing agent during blending, and carrying out hot press molding on the electric and heat conducting mixture obtained by blending to obtain an electric and heat conducting sheet layer;
when the polymer matrix material is a thermosetting elastomer, controlling the temperature of hot press molding to be +/-20-40 ℃ of the corresponding decomposition temperature when the half-life period of a vulcanizing agent in the thermosetting polymer is 1 h; when the polymer matrix material is thermosetting resin, controlling the temperature of hot-press molding to partially crosslink the polymer matrix material; when the polymer matrix material is a crystalline thermoplastic polymer, controlling the hot-press molding temperature to be 10-30 ℃ above the melting point of the crystalline thermoplastic polymer and lower than the decomposition temperature of the crystalline thermoplastic polymer; when the polymer matrix material is an amorphous thermoplastic polymer, controlling the hot press molding temperature to be above the flow temperature of the amorphous thermoplastic polymer and below the decomposition temperature of the amorphous thermoplastic polymer;
②, mixing 100 parts by mass of polymer matrix material powder and 5-200 parts by mass of insulating heat-conducting filler at a high speed to enable the insulating heat-conducting filler to be selectively distributed at the interface of the polymer matrix material powder to coat the polymer matrix material powder, and carrying out hot press molding on the polymer matrix material powder coated with the insulating heat-conducting filler to obtain an insulating heat-conducting sheet layer, wherein the hot press molding temperature is as follows:
in order to ensure that the insulating heat-conducting filler is selectively distributed at the interface of the polymer matrix material powder, the temperature of the hot-press molding is between the glass transition temperature and the viscous flow temperature of the polymer matrix material powder, so that the polymer matrix material powder is properly welded without obvious flow;
the polymer matrix in steps ① and ② is the same;
(2) press forming
And (2) sequentially laminating the electric and heat conducting sheet layer, the insulating and heat conducting sheet layer and the electric and heat conducting sheet layer, and then performing hot press molding to obtain the integrated sandwich-structured insulating and heat conducting polymer composite material with the frequency selective electromagnetic shielding, wherein the hot press molding temperature is determined according to a specifically adopted polymer base material, and is the same as the hot press molding temperature in the step (1) ②.
In step (1) ① of the above technical solution of the method for preparing an insulating and thermally conductive composite polymer material with frequency selective electromagnetic shielding, when the polymer matrix material is a thermosetting elastomer, the polymer matrix material usually used is rubber raw rubber (unvulcanized), the rubber raw rubber will react with vulcanizing agent to form rubber compound during the hot press molding process, accordingly, when the insulating and thermally conductive polymer composite material with frequency selective electromagnetic shielding of the present invention is prepared with rubber as the matrix, the polymer matrix material used in step (1) ② for blending with the insulating and thermally conductive filler is vulcanized rubber, similarly, in step (1) ①, when the polymer matrix material is a thermosetting resin, it is usually necessary to crosslink the uncrosslinked polymer with the vulcanizing agent to form thermosetting resin during the hot press molding process, and accordingly, when the thermosetting resin is used as the matrix for preparing the insulating and thermally conductive polymer composite material with frequency selective electromagnetic shielding of the present invention, the polymer matrix material used in step (1) ② is crosslinked polymer matrix material used for blending with the insulating and thermally conductive filler.
In the technical scheme of the preparation method of the insulating and heat-conducting composite polymer material with the frequency-selective electromagnetic shield, the addition amount of the electrically and heat-conducting filler in the step (1) ① is preferably 3-30 parts by mass when the electrically and heat-conducting mixture is prepared, and the addition amount of the insulating and heat-conducting filler in the step (1) ② is preferably 20-150 parts by mass, and more preferably 40-100 parts by mass when the polymer base material powder coated with the insulating and heat-conducting filler is prepared.
In the preparation method of the insulating and heat-conducting polymer composite material with the frequency-selective electromagnetic shielding function, the thicknesses of the electric-conduction and heat-conduction sheet layer and the insulating and heat-conduction sheet layer are determined according to the actual application requirements. Preferably, the thickness of the electric conduction and heat conduction polymer sheet layer is 0.1-40 mm, and the thickness of the insulation and heat conduction polymer sheet layer is 0.1-40 mm.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial technical effects:
1. the invention provides an insulating and heat-conducting polymer composite material with frequency-selective electromagnetic shielding, which has frequency-selective electromagnetic shielding performance, is insulating in the electromagnetic shielding direction and has excellent heat-conducting performance. The high-heat-conductivity electromagnetic shielding material has excellent electromagnetic shielding performance and heat-conducting performance, can be applied to application scenes with dual requirements of electromagnetic shielding and heat dissipation, can dissipate heat energy generated by converting electromagnetic energy during electromagnetic shielding in time, is expected to be widely applied to the fields of high-power integrated circuits, 5G communication, high-power radars, terahertz communication equipment and the like, meets the urgent requirements of new-generation equipment on electromagnetic compatibility and heat dissipation, and has wide application prospect. Meanwhile, the material has frequency selectivity electromagnetic shielding performance, so that the material has obvious application advantages in application scenes in which only electromagnetic waves of a certain narrow specific waveband need to be shielded.
2. According to the polymer composite material provided by the invention, the conductive heat conduction layer and the insulating heat conduction layer are designed into an integrated sandwich structure, so that the enhancement of electromagnetic shielding performance and selective electromagnetic shielding are realized, the excellent insulating property in the shielding direction of the material is endowed, meanwhile, the material also has excellent heat conductivity, the surface has certain electric conductivity, and the polymer composite material can be applied to scenes with no requirement on the surface insulating property and insulation requirement in the electromagnetic shielding direction. The position of the selective electromagnetic shielding peak of the polymer composite material can be adjusted by adjusting the thickness of the electric heat conducting layer and the insulating heat conducting layer, the content of the electric heat conducting filler in the electric heat conducting layer and the like, and the heat conducting property of the composite polymer material can be adjusted by adjusting the thickness of the insulating heat conducting layer and the content of the insulating heat conducting filler in the insulating heat conducting layer.
3. In the insulating and heat-conducting polymer composite material with frequency-selective electromagnetic shielding, the insulating and heat-conducting layer is prepared by hot-press molding after the insulating and heat-conducting filler is coated with the polymer powder, and the insulating and heat-conducting filler is selectively distributed at the interface of the polymer particles to form the insulating and heat-conducting network. After the base materials with the same layers are subjected to hot press molding, the layers are tightly combined, the defect of poor interlayer binding force is overcome, and the interface bonding performance is good. These all contribute to increasing the service life of the polymer composite.
4. The invention also provides a preparation method of the insulating and heat-conducting composite polymer material with the frequency-selective electromagnetic shielding function, the method avoids damage to an insulating and heat-conducting network of the insulating and heat-conducting layer through reasonable control of the hot-pressing temperature, the insulating and heat-conducting network has excellent heat-conducting performance while the excellent electromagnetic shielding performance is ensured, and the method also has the characteristics of simple process, low cost, no pollution and easy realization of industrial production.
Drawings
Fig. 1 is a schematic diagram of a process for preparing an insulating and heat-conducting polymer composite material with frequency-selective electromagnetic shielding according to the present invention.
Fig. 2 is a scanning electron micrograph of the insulating and heat-conducting sheet layer prepared in example 1 at different magnifications.
FIG. 3 is an optical photograph of the syntactic polyurethane prepared in example 1.
FIG. 4 is a scanning electron microscope image of the junction of the electrically and thermally conductive layer and the electrically and thermally insulating layer in the composite polyurethane prepared in example 1.
Fig. 5 is a graph showing electromagnetic shielding effectiveness in the X band of the composite material prepared in example 1.
Fig. 6 is a graph showing electromagnetic shielding effectiveness in the X band of the composite material prepared in example 2.
Detailed Description
The present invention provides an insulating and heat conducting polymer composite material with frequency selective electromagnetic shielding and a preparation method thereof, which are further described by the following embodiments. It should be noted that the following examples are only for illustrating the present invention and are not to be construed as limiting the present invention in any way, and that the insubstantial modifications and adaptations of the invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In the following examples, materials, reagents and the like used in the examples are commercially available unless otherwise specified.
Example 1
In this embodiment, the insulating and heat conducting polyurethane composite material with frequency selective electromagnetic shielding is prepared, and a schematic diagram of a preparation process thereof is shown in fig. 1, and the steps are as follows:
(1) preparation of electrically and thermally conductive sheet layer and electrically and thermally conductive sheet layer
① mixing and kneading 100 parts by mass of polyurethane and 5 parts by mass of multi-walled carbon nanotubes uniformly to obtain an electric and heat conducting mixture, and hot-pressing the electric and heat conducting mixture into a sheet shape by a vacuum molding press, wherein the temperature of the vacuum molding press is controlled to be 180 ℃ and the pressure is controlled to be 10MPa during hot-pressing to obtain an electric and heat conducting sheet layer with the thickness of 0.35 mm.
② stirring and blending 100 parts by mass of granular polyurethane with the particle size of about 100 mu m and 20 parts by mass of hexagonal boron nitride with the size of about 20 mu m by a high-speed stirrer, selectively distributing the hexagonal boron nitride at the interface of polypropylene particles to coat the polyurethane particles to obtain the polyurethane particles coated with the hexagonal boron nitride, and hot-pressing the polyurethane particles coated with the hexagonal boron nitride into sheets by a vacuum mould press, wherein the temperature of the vacuum mould press is controlled at 160 ℃ and the pressure is controlled at 10MPa during hot-pressing to obtain the insulating heat-conducting sheet layer with the thickness of 1 mm.
Fig. 2 is a scanning electron micrograph of the insulating and heat-conducting layer prepared in step ② at different magnifications, and it can be seen from fig. 2 that hexagonal boron nitride is distributed at the polyurethane particle interfaces of the insulating and heat-conducting layer to form an insulating and heat-conducting network.
(2) Press forming
And sequentially stacking the electric and heat conducting sheet layer, the insulating and heat conducting sheet layer and the electric and heat conducting sheet layer, and then performing hot press molding by adopting a vacuum film pressing machine, wherein the temperature of the vacuum film pressing machine is controlled to be 160 ℃, and the pressure is 10MPa, so that the insulating and heat conducting polyurethane composite material with the integrated sandwich structure and the frequency selectivity electromagnetic shielding is obtained.
An optical photograph of the composite polyurethane prepared in this embodiment is shown in fig. 3, in which the white layer located in the middle is an insulating heat conducting layer, and the black layers located at both sides are electric and heat conducting layers, and a scanning electron microscope image of a joint of the electric and heat conducting layers and the insulating heat conducting layers in the composite polyurethane is shown in fig. 4, in which an upper left corner portion is the insulating heat conducting layer, and a lower right corner portion is the electric and heat conducting layer.
The composite polyurethane surface layer prepared in this example was found to have an electrical conductivity of 0.10S/cm and a resistance in the shielding direction of 1.89 x 109Ω, which is mainly due to the insulating properties of the electrically and thermally conductive network and the insulating and thermally conductive layer formed in the electrically and thermally conductive layers on both sides. The thermal conductivity of the composite polyurethane prepared in this example is 0.57W/(mK).
The electromagnetic shielding performance of the composite polyurethane prepared in this example in the frequency range of 8.2 to 12.4GHz was tested by using an N5247 type vector network analyzer (usa), and as a result, as shown in fig. 5, it can be seen from fig. 5 that the composite polyurethane exhibits frequency-selective electromagnetic shielding performance.
Example 2
In this embodiment, the insulating and heat-conducting polypropylene composite material with frequency-selective electromagnetic shielding is prepared, and a schematic diagram of a preparation process thereof is shown in fig. 1, and the steps are as follows:
(1) preparation of electrically and thermally conductive sheet layer and electrically and thermally conductive sheet layer
① mixing and kneading 100 parts by mass of polypropylene and 10 parts by mass of multi-walled carbon nanotubes uniformly to obtain an electric and heat conducting mixture, and hot-pressing the electric and heat conducting mixture into sheets by a vacuum molding press, wherein the temperature of the vacuum molding press is controlled to be 180 ℃ and the pressure is controlled to be 10MPa during hot-pressing to obtain an electric and heat conducting sheet layer with the thickness of 0.35 mm.
② stirring and blending 100 parts by mass of granular polypropylene with the particle size of about 100 μm and 40 parts by mass of hexagonal boron nitride with the size of about 20 μm by a high-speed stirrer, so that the hexagonal boron nitride is selectively distributed at the interface of the polypropylene particles to coat the polypropylene particles to obtain polypropylene particles coated with the hexagonal boron nitride, and hot-pressing the polypropylene particles coated with the hexagonal boron nitride into sheets by a vacuum molding press, wherein the temperature of the vacuum molding press is controlled at 160 ℃ and the pressure is controlled at 10MPa during hot-pressing to obtain the insulating heat-conducting sheet layer with the thickness of 1.3 mm.
(2) Press forming
And sequentially stacking the electric and heat conducting sheet layer, the insulating and heat conducting sheet layer and the electric and heat conducting sheet layer, and then performing hot press molding by adopting a vacuum film pressing machine, wherein the temperature of the vacuum film pressing machine is controlled to be 160 ℃, and the pressure is 10MPa, so that the integrated insulating and heat conducting polypropylene composite material with the sandwich structure and the frequency selectivity electromagnetic shielding is obtained.
The test shows that the conductivity of the composite polypropylene surface layer prepared in the embodiment is 0.40S/cm, and the resistance in the shielding direction is 3.77 x 109Ω, which is mainly due to the insulating properties of the electrically and thermally conductive network and the insulating and thermally conductive layer formed in the electrically and thermally conductive layers on both sides. The thermal conductivity of the composite polypropylene prepared by the embodiment is 0.93W/(mK).
The N5247 type vector network analyzer (usa) is used to test the electromagnetic shielding performance of the composite polypropylene prepared in this embodiment in the frequency range of 8.2 to 12.4GHz, and as shown in fig. 6, it can be seen from fig. 6 that the composite polypropylene exhibits frequency selective electromagnetic shielding performance.
By combining the embodiment 1 and the embodiment 2, it can be known that the thermal conductivity, the resistance in the shielding direction, the position of the selective electromagnetic shielding peak, and other properties of the composite polymer material can be adjusted by adjusting the thicknesses of the electrically and thermally conductive sheet layer and the insulating and thermally conductive sheet layer and the contents of the electrically and thermally conductive filler and the insulating and thermally conductive filler therein.
Example 3
In this embodiment, an insulating and heat-conducting polyhexamethylene adipamide composite material with frequency-selective electromagnetic shielding is prepared, and a schematic diagram of a preparation process thereof is shown in fig. 1, and the steps are as follows:
(1) preparation of electrically and thermally conductive sheet layer and electrically and thermally conductive sheet layer
① mixing and kneading 100 parts by mass of polyhexamethylene adipamide and 50 parts by mass of carbon black uniformly to obtain an electric and heat conducting mixture, and hot-pressing the electric and heat conducting mixture into a sheet shape by a vacuum molding press, wherein the temperature of the vacuum molding press is controlled at 235 ℃ and the pressure is controlled at 10MPa during hot-pressing to obtain an electric and heat conducting sheet layer with the thickness of 40 mm.
② mixing 100 parts by mass of powdered polyhexamethylene adipamide with a particle size of about 50 μm and 5 parts by mass of silicon carbide with a particle size of about 3 μm by a high-speed mixer, so that the silicon carbide is selectively distributed on the interface of the polyhexamethylene adipamide particles to coat the polyhexamethylene adipamide particles, thus obtaining the polyhexamethylene adipamide particles coated with the silicon carbide, hot-pressing the polyhexamethylene adipamide particles coated with the silicon carbide into sheets by a vacuum molding press, and controlling the temperature of the vacuum molding press to 225 ℃ and the pressure to 10MPa during hot-pressing, thus obtaining the insulating heat-conducting sheet layer with a thickness of 40 mm.
(2) Press forming
And sequentially stacking the electric and heat conducting sheet layer, the insulating and heat conducting sheet layer and the electric and heat conducting sheet layer, and then performing hot press molding by adopting a vacuum film pressing machine, wherein the temperature of the vacuum film pressing machine is controlled to be 225 ℃, and the pressure is controlled to be 10MPa, so that the insulating and heat conducting composite polyhexamethylene adipamide with an integrated sandwich structure and frequency selective electromagnetic shielding is obtained.
Example 4
In this embodiment, the insulating and heat-conducting natural rubber composite material with frequency-selective electromagnetic shielding is prepared, and a schematic diagram of a preparation process thereof is shown in fig. 1, and the steps are as follows:
(1) preparation of electrically and thermally conductive sheet layer and electrically and thermally conductive sheet layer
① mixing and kneading 100 parts by mass of raw rubber of natural rubber, 2 parts by mass of sulfur and 0.1 part by mass of graphene uniformly to obtain an electric and heat conducting mixture, and hot-pressing the electric and heat conducting mixture into a sheet shape by a vacuum molding press, wherein the temperature of the vacuum molding press is controlled at 150 ℃ and the pressure is controlled at 10MPa during hot-pressing to obtain an electric and heat conducting sheet layer with the thickness of 0.4 mm.
② mixing 100 parts by mass of powdered natural rubber with a particle size of about 1000 μm and 60 parts by mass of zinc oxide with a particle size of about 200 μm by a high-speed mixer, so that the zinc oxide is selectively distributed at the interface of the natural rubber particles to coat, mix and coat the natural rubber particles to obtain zinc oxide coated natural rubber particles, and hot-pressing the zinc oxide coated natural rubber particles into sheets by a vacuum molding press, wherein the temperature of the vacuum molding press is controlled at 140 ℃ and the pressure is controlled at 10MPa during hot-pressing to obtain an insulating heat-conducting sheet layer with a thickness of 0.1 mm.
(2) Press forming
And sequentially stacking the electric and heat conducting sheet layer, the insulating and heat conducting sheet layer and the electric and heat conducting sheet layer, and then performing hot press molding by adopting a vacuum film pressing machine, wherein the temperature of the vacuum film pressing machine is controlled to be 140 ℃, and the pressure is 10MPa, so that the insulating and heat conducting composite natural rubber with the integrated sandwich structure and the frequency selective electromagnetic shielding is obtained.
Example 5
In this embodiment, the insulating and heat-conducting butadiene rubber composite material with frequency-selective electromagnetic shielding is prepared, and a schematic diagram of the preparation process is shown in fig. 1, and the steps are as follows:
(1) preparation of electrically and thermally conductive sheet layer and electrically and thermally conductive sheet layer
① mixing and kneading 100 parts by mass of raw butadiene rubber, 1 part by mass of sulfur and 3 parts by mass of aluminum powder uniformly to obtain an electric and heat conducting mixture, and hot-pressing the electric and heat conducting mixture into a sheet shape by a vacuum molding press, wherein the temperature of the vacuum molding press is controlled at 160 ℃ and the pressure is controlled at 10MPa during hot-pressing to obtain an electric and heat conducting sheet layer with the thickness of 0.1 mm.
② stirring 100 parts by mass of powdered vulcanized butadiene rubber with the grain diameter of about 10 μm and 20 parts by mass of titanium carbide with the grain diameter of about 0.5 μm by a high-speed stirrer, mixing to ensure that the titanium carbide is selectively distributed at the interface of the butadiene rubber particles to coat the butadiene rubber particles to obtain the titanium carbide coated butadiene rubber particles, hot-pressing the titanium carbide coated butadiene rubber particles into sheets by a vacuum molding press, and controlling the temperature of the vacuum molding press to be 150 ℃ and the pressure to be 10MPa during hot-pressing to obtain the insulating heat-conducting sheet layer with the thickness of 2 mm.
(2) Press forming
And sequentially stacking the electric and heat conducting sheet layer, the insulating and heat conducting sheet layer and the electric and heat conducting sheet layer, and then performing hot press molding by adopting a vacuum film pressing machine, wherein the temperature of the vacuum film pressing machine is controlled to be 150 ℃, and the pressure is 10MPa, so that the insulating and heat conducting composite butadiene rubber with the integrated sandwich structure and the frequency selective electromagnetic shielding is obtained.
Example 6
In this embodiment, the insulating and heat-conducting silicone rubber composite material with frequency-selective electromagnetic shielding is prepared, and a schematic diagram of a preparation process thereof is shown in fig. 1, and the steps are as follows:
(1) preparation of electrically and thermally conductive sheet layer and electrically and thermally conductive sheet layer
① mixing and kneading 100 parts by mass of raw silicone rubber, 2 parts by mass of dibenzoyl peroxide and 50 parts by mass of flake graphite uniformly to obtain an electric and heat conducting mixture, and hot-pressing the electric and heat conducting mixture into flakes by a vacuum molding press, wherein the temperature of the vacuum molding press is controlled at 150 ℃ and the pressure is controlled at 10MPa during hot-pressing to obtain an electric and heat conducting flake layer with the thickness of 10 mm.
② stirring and blending 100 parts by mass of powdered vulcanized silicone rubber with the grain diameter of about 500 μm and 200 parts by mass of boron carbide with the size of about 50 μm by a high-speed stirrer, so that the boron carbide is selectively distributed at the interface of the silicone rubber particles to coat, mix and coat the silicone rubber particles to obtain the silicon rubber particles coated with the boron carbide, and hot-pressing the silicon rubber particles coated with the boron carbide into sheets by a vacuum molding press, wherein the temperature of the vacuum molding press is controlled to be 120 ℃ during hot pressing, and the pressure is controlled to be 10MPa, so that the insulating heat-conducting sheet layer with the thickness of 20mm is obtained.
(2) Press forming
The electric and heat conducting sheet layer, the insulating and heat conducting sheet layer and the electric and heat conducting sheet layer are sequentially stacked, then hot-press molding is carried out by adopting a vacuum film pressing machine, the temperature of the vacuum film pressing machine is controlled to be 120 ℃, and the pressure is 10MPa, so that the integrated sandwich-structured insulating and heat conducting composite silicone rubber with the frequency selective electromagnetic shielding function is obtained.

Claims (10)

1. The insulating and heat-conducting polymer composite material with the frequency-selective electromagnetic shielding function is characterized by comprising an insulating heat-conducting layer and two electric heat-conducting layers, wherein the two electric heat-conducting layers are respectively positioned at two sides of the insulating heat-conducting layer to form an integrated sandwich structure; the insulating heat conduction layer comprises a polymer matrix and insulating heat conduction fillers, the insulating heat conduction layer is prepared by hot press molding after the insulating heat conduction fillers coat polymer powder, the insulating heat conduction fillers are selectively distributed at the interface of polymer particles to form an insulating heat conduction network, the electric heat conduction layer comprises the polymer matrix and the electric and heat conduction fillers, the electric and heat conduction fillers are distributed in the polymer matrix to form an electric and heat conduction network, and the composition of the insulating heat conduction layer and the polymer matrix of the electric and heat conduction layer is the same; the material has frequency-selective electromagnetic shielding performance and is insulated in the electromagnetic shielding direction, and the material has heat-conducting performance and surface conductive performance.
2. The insulated heat-conducting polymer composite material with frequency-selective electromagnetic shielding of claim 1, wherein the size of the polymer powder used for preparing the insulated heat-conducting layer is 10-1000 μm.
3. The insulated heat-conducting polymer composite material with the frequency-selective electromagnetic shielding function according to claim 2, wherein the size of the insulated heat-conducting filler is 0.05-0.2 times of the size of the polymer powder, and the insulated heat-conducting filler is preferably a flake filler.
4. The insulated heat-conducting polymer composite material with frequency-selective electromagnetic shielding according to any one of claims 1 to 3, wherein the content of the insulated heat-conducting filler in the insulated heat-conducting layer is 5 to 200 percent of the mass of the polymer matrix in the layer.
5. The insulated thermally conductive polymer composite material with frequency selective electromagnetic shielding according to any one of claims 1 to 3, wherein the insulated thermally conductive filler is selected from one or more of silicon carbide, boron carbide, titanium carbide, zirconium carbide, chromium carbide, tungsten carbide, silicon nitride, boron nitride, aluminum nitride, beryllium oxide, aluminum oxide and zinc oxide.
6. The insulated thermally conductive polymer composite material with frequency selective electromagnetic shielding according to any one of claims 1 to 3, wherein the electrically and thermally conductive filler content in the electrically and thermally conductive layer is 0.1 to 50% by mass of the polymer matrix in the layer.
7. The insulated thermally conductive polymer composite material with frequency selective electromagnetic shielding according to any one of claims 1 to 3, wherein the electrically and thermally conductive filler is selected from one or more of carbon-based fillers and metal fillers.
8. The insulated thermally conductive polymer composite with frequency-selective electromagnetic shielding of any one of claims 1 to 3, wherein the polymer matrix in the insulated thermally conductive layer and the electrically and thermally conductive layer is a thermoplastic resin, a thermoplastic elastomer, a thermosetting resin, or a thermosetting elastomer.
9. The insulated heat-conducting polymer composite material with frequency selective electromagnetic shielding according to any one of claims 1 to 3, wherein the thickness of the insulated heat-conducting layer is 0.1-40 mm, and the thickness of the electrically and thermally conducting layer is 0.1-40 mm.
10. A method for preparing the insulated thermally conductive polymer composite material with frequency selective electromagnetic shielding according to any one of claims 1 to 3, comprising the steps of:
(1) preparation of electrically and thermally conductive sheet layer and electrically and thermally conductive sheet layer
①, blending 100 parts by mass of a polymer base material and 0.1-50 parts by mass of an electric and heat conducting filler, when the polymer base material is a thermosetting elastomer, adding 1-10 parts by mass of a vulcanizing agent during blending, when the polymer base material is a thermosetting resin, adding 1-10 parts by mass of a curing agent during blending, and carrying out hot press molding on the electric and heat conducting mixture obtained by blending to obtain an electric and heat conducting sheet layer;
when the polymer matrix material is a thermosetting elastomer, controlling the temperature of hot press molding to be +/-20-40 ℃ of the corresponding decomposition temperature when the half-life period of a vulcanizing agent in the thermosetting polymer is 1 h; when the polymer matrix material is thermosetting resin, controlling the temperature of hot-press molding to partially crosslink the polymer matrix material; when the polymer matrix material is a crystalline thermoplastic polymer, controlling the hot-press molding temperature to be 10-30 ℃ above the melting point of the crystalline thermoplastic polymer and lower than the decomposition temperature of the crystalline thermoplastic polymer; when the polymer matrix material is an amorphous thermoplastic polymer, controlling the hot press molding temperature to be above the flow temperature of the amorphous thermoplastic polymer and below the decomposition temperature of the amorphous thermoplastic polymer;
②, mixing 100 parts by mass of polymer matrix material powder and 5-200 parts by mass of insulating heat-conducting filler at a high speed to enable the insulating heat-conducting filler to be selectively distributed at the interface of the polymer matrix material powder to coat the polymer matrix material powder, and carrying out hot press molding on the polymer matrix material powder coated with the insulating heat-conducting filler to obtain an insulating heat-conducting sheet layer, wherein the hot press molding temperature is as follows:
in order to ensure that the insulating heat-conducting filler is selectively distributed at the interface of the polymer matrix material powder, the temperature of the hot-press molding is between the glass transition temperature and the viscous flow temperature of the polymer matrix material powder, so that the polymer matrix material powder is properly welded without obvious flow;
the polymer matrix in steps ① and ② is the same;
(2) press forming
And (2) sequentially laminating the electric and heat conducting sheet layer, the insulating and heat conducting sheet layer and the electric and heat conducting sheet layer, and then performing hot press molding to obtain the insulating and heat conducting polymer composite material with the integrated sandwich structure and the frequency selective electromagnetic shielding, wherein the hot press molding temperature is determined according to a specifically adopted polymer base material, and is the same as the hot press molding temperature in the step (1) ②.
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CN113774674A (en) * 2021-09-13 2021-12-10 西北工业大学 Preparation method of multifunctional silicone rubber composite material with sandwich structure
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WO2023060739A1 (en) * 2021-10-12 2023-04-20 中国科学院深圳先进技术研究院 Self-healing electromagnetic shielding material, preparation method therefor and application thereof

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CN113214583A (en) * 2021-04-07 2021-08-06 复旦大学 Thermal interface material with vertical sandwich structure and preparation method thereof
CN113214583B (en) * 2021-04-07 2022-04-12 复旦大学 Thermal interface material with vertical sandwich structure and preparation method thereof
CN113321928A (en) * 2021-06-02 2021-08-31 深圳市黑金工业制造有限公司 Preparation method of graphene insulation heat-conducting sheet for electric vehicle power supply
CN113774674A (en) * 2021-09-13 2021-12-10 西北工业大学 Preparation method of multifunctional silicone rubber composite material with sandwich structure
WO2023060739A1 (en) * 2021-10-12 2023-04-20 中国科学院深圳先进技术研究院 Self-healing electromagnetic shielding material, preparation method therefor and application thereof

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