CN109943023A - A kind of thermally conductive electromagnetic shielding composite material and its preparation method and application - Google Patents
A kind of thermally conductive electromagnetic shielding composite material and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of thermally conductive electromagnetic shielding composite material and its preparation method and application, the thermally conductive electromagnetic shielding composite material includes foam metal and is filled in the intraskeletal polymer matrix composite of foam metal；Wherein, the polymer matrix composite includes polymer and insulating heat-conductive filler.In the present invention, polymer matrix composite containing insulating heat-conductive filler is filled in the three-dimensional grid pore structure of foam metal, there is excellent heating conduction using insulating heat-conductive filler, along with the preferable thermal diffusivity of foam metal itself and electromagnetic shielding performance, so that composite material provided by the invention has both electromagnetic shielding performance while having more excellent heating conduction.
Description
Technical field
The invention belongs to technical field of electromagnetic shielding, it is related to a kind of thermally conductive electromagnetic shielding composite material and its preparation side
Method and application.
Background technique
With the fast development of electronic technology, various electronic device quantity sharply increase and to intelligent, integrated, frivolous
The directions such as change, multifunction are developed.On the one hand, the miniaturization and highly denseization of electronic device, so that leaned between electronic component
It is increasingly closer, the length of signal propagation path is substantially reduced, but increase the chance of interference simultaneously, thus leads to electromagnetic interference
Phenomenon is increasingly severe, can not only damage to the physical and mental health of the mankind, but also will affect the normal work of other sophisticated electronics
Make.Therefore, the importance of electromagnetic shielding is increasingly prominent.Currently, electromagnetic shielding main method first is that using shielding material pair
Electromagnetic radiation carries out effectively barrier and loss.Traditional method is using the higher metal material of shielding properties as shield material
Material, such as nickel, copper, aluminium etc., can be used foam metal or metal mesh, the smaller more intensive screen of mesh size to reduce density
It is better to cover effect.However since the corrosion resistance of metal is poor, its use is limited in some acid or alkali environments.In addition,
For foam metal, since its surface smoothness is usually poor, it is difficult to effectively be bonded, cause in reality with the realization of device heat source surface
Its heat dissipation and electromagnetic shielding performance are had a greatly reduced quality in the application of border.Composite conducting polymer material and eigenstate conductive polymer material
The shortcomings that overcoming metal material processing difficulty, not acid and alkali-resistance, has preferable comprehensive performance, but the shielding of this kind of material is steady
Qualitative poor, shielding wavelength band is relatively narrow.
CN101050284A discloses a kind of electromagnetic shielding macromolecule composite material, is sheet material either coiled material, feature
Be: the electromagnetic shielding macromolecule composite material is mainly combined by foam metal and high molecular material；The foam gold
Category is selected as nickel foam, foam copper, foamed iron, has through-hole structure, and aperture is 60-6000 μm, 75% or more porosity, density
In 0.03-1.20g/cm3Between；The high molecular material is thermoplastic resin, thermosetting resin or rubber, although obtained material
Expect the shield effectiveness having had, but its polymer composite thermal conductivity is bad, and it is serious to easily lead to electronic product fever.
Currently, the heat that the Highgrade integration due to electronic device generates when electronic product being made to work can not be discharged in time
Cause electronic product fever serious, or even can not work normally.Therefore heat dissipation problem is also that face one of electronic product is important
Problem.Based on the above demand, developing a kind of material with high thermal conductivity and electromagnetic shielding dual function becomes very in need.
CN103213980A discloses a kind of three-dimensional grapheme or the preparation method of its compound system, comprising: takes transition golden
Belong to simple substance and/or the compound containing transition metal element prepares three-dimensional porous metallic catalyst by high temperature reduction for raw material
Template obtains the three-dimensional grapheme for having catalyst backbone using chemical vapour deposition technique growing three-dimensional graphene.Further
, can also etching processing have catalyst backbone three-dimensional grapheme, obtain three-dimensional grapheme powder.Further, will also
Three-dimensional grapheme powder and metal, high molecular material, biomolecule material etc. are compounded to form composite system.
CN107474461A discloses a kind of graphene/polymer three-dimensional foam base plate, preparation method and application.The preparation method
Include: that graphene is grown on foamed metal catalyst using chemical vapour deposition technique, forms three-dimensional grapheme/foam metal and urge
Agent compound；By template replacement method by the foamed metal catalyst in three-dimensional grapheme/foamed metal catalyst compound
Skeleton is replaced into polymer, obtains graphene flexible/polymer three-dimensional foam base plate.Although foregoing invention can accomplish thermally conductive
Heat dissipation and electromagnetic shielding, but preparation method is complicated, and uses the material of the higher costs such as graphene and chemical vapor deposition
With technique, it is unfavorable for business promotion.
Therefore, it is necessary to develop a kind of new thermally conductive electromagnetic shielding composite material, not only thermal coefficient with higher but also had very
Good electromagnetic shielding action, and preparation method is simple, it is low in cost.
Summary of the invention
The purpose of the present invention is to provide a kind of thermally conductive electromagnetic shielding composite materials and its preparation method and application.
In order to achieve that object of the invention, the invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of thermally conductive electromagnetic shielding composite material, the thermally conductive electromagnetic shielding composite wood
Material is including foam metal and is filled in the intraskeletal polymer matrix composite of foam metal.
Wherein, the polymer matrix composite includes polymer and insulating heat-conductive filler.
In the present invention, the polymer matrix composite containing insulating heat-conductive filler is filled in the three dimensional network of foam metal
In hole construction, there is excellent heating conduction using insulating heat-conductive filler, add the preferable thermal diffusivity of foam metal itself
And electromagnetic shielding performance, so that composite material provided by the invention has both electromagnetic screen while having more excellent heating conduction
Cover performance.
Preferably, the insulating heat-conductive filler includes boron nitride, aluminium nitride, aluminium oxide, magnesia, silicon nitride, diamond
In crystalline sillica any one or at least two combination, preferably boron nitride and/or aluminium oxide, further preferably
The composition that boron nitride and aluminium oxide are formed with mass ratio 3:7.
In the present invention, it is preferred to which boron nitride and aluminium oxide are using the composition that mass ratio 3:7 is formed as insulation of the invention
Heat filling, good heat conductivity, at low cost, density is lower, fillable amount is high.
Preferably, the preferred ball-aluminium oxide of aluminium oxide, the preferred platelet boron nitride of boron nitride.
Preferably, in polymer matrix composite, the mass percentage of the insulating heat-conductive filler is 20-95%,
Such as 25%, 30%, 40%, 50%, 60%, 70%, 80%, 90% etc..
When the additive amount of insulating heat-conductive filler within this range when, lead to the thermally conductive electromagnetic shielding composite material that finally obtains
Hot property and electromagnetic shielding performance are more excellent.
Preferably, the polymer includes epoxy resin, phenolic resin, Lauxite, melamine formaldehyde resin, gathers
Butadiene resin, polyurethane, silicon ether resin, silica gel, polyethylene, polypropylene, polyvinyl chloride, polystyrene, polymethylacrylic acid
Methyl esters, polyester, polyformaldehyde, polyamide, polycarbonate, polyphenylene oxide, acrylonitrile-butadiene-styrene copolymer, vulcanized rubber,
Synthetic rubber, ethylene-vinyl acetate copolymer, styrene-isoprene-styrene block copolymer, styrene-butadiene-
Any one in styrene block copolymer or styrene ethylene butadiene-styrene block copolymer or at least two
Combination, preferred epoxy and/or silica gel.
Preferably, the polymer be epoxy resin, the insulating heat-conductive filler be ball-aluminium oxide, the polymer and
The mass ratio of the insulating heat-conduction material is 8:92.
Preferably, the polymer is epoxy resin, and the insulating heat-conductive filler is boron nitride, the polymer and described
The mass ratio of insulating heat-conduction material is 20:80.
Preferably, the polymer is epoxy resin, and the insulating heat-conductive filler is boron nitride and aluminium oxide with mass ratio
The mass ratio of the composition of 3:7 composition, the polymer and the insulating heat-conduction material is 10:90.
Preferably, the foam metal is foam copper, nickel foam, foamed aluminium, foamed iron, titanium foam, Foam silver, foam
In zinc, foam iron-nickel, foam nickel chromium triangle, foam cobalt nickel or stainless steel foam any one or at least two combination.
Preferably, in the thermally conductive electromagnetic shielding composite material, the quality percentage of the polymer matrix composite contains
Measuring is 40-85%, such as 45%, 50%, 60%, 65%, 70%, 75%, 80% etc..
Preferably, the porosity of the foam metal be 60-99%, such as 65%, 70%, 75%, 80%, 85%,
90%, 95% etc..
Preferably, the foam metal with a thickness of 0.1-20mm, such as 0.5mm, 1mm, 2mm, 5mm, 8mm, 10mm,
12mm, 15mm, 18mm etc..
It preferably, further include absorbing material in the polymer matrix composite.
Preferably, the absorbing material includes polyaniline, ferrite, barium ferrite, graphene oxide, silicon carbide, nitridation
In silicon, siderochrome, iron silicochromium, barium titanate, iron sial or ferronickel any one or at least two combination.
Second aspect, the present invention provides the preparation sides of the thermally conductive electromagnetic shielding composite material according to first aspect
Method, the preparation method include: to be filled into polymer matrix composite in a form of slurry in the hole of foam metal, then
Solvent is removed, the thermally conductive electromagnetic shielding composite material is obtained.
Preferably, the method for the filling include pour, in die casting or roll-in any one or at least two combination.
Preferably, the polymeric matrix in the polymer matrix composite is thermosetting resin, the removing solvent
Method is to be heating and curing.
Preferably, the temperature being heating and curing be 25-200 DEG C, such as 50 DEG C, 75 DEG C, 100 DEG C, 125 DEG C, 150 DEG C,
175 DEG C etc., time 10min-24h, such as 0.5h, 1h, 5h, 7h, 10h, 12h, 15h, 17h, 20h, 23h etc..
The third aspect, the present invention provides the thermally conductive electromagnetic shielding composite materials according to first aspect in electronic device
In application.
Compared with the existing technology, the invention has the following advantages:
(1) in the present invention, the polymer matrix composite containing insulating heat-conductive filler is filled in the three of foam metal
It ties up in grid pore structure, there is excellent heating conduction or electromagnetic shielding and absorbing property using insulating heat-conductive filler, add
The preferable thermal diffusivity of foam metal itself and electromagnetic shielding performance, so that composite material provided by the invention is with more excellent
Electromagnetic shielding performance is had both while heating conduction.
(2) when polymer is epoxy resin, insulating heat-conduction material is the group that boron nitride and aluminium oxide are formed with mass ratio 3:7
Object is closed, when the mass ratio of the polymer and the insulating heat-conduction material is 8:92, thermally conductive electromagnetic screen that the present invention finally obtains
Cover that composite material obtains heating conduction and electromagnetic shielding performance is optimal, wherein when foam metal is foam copper, thermally conductive system
Number is up to more than 5.8W/ (mK), and when foam metal is nickel foam, electromagnet shield effect can reach 85dB or more.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the foam copper in the embodiment of the present invention 11.
Fig. 2 is the scanning electron microscope (SEM) photograph for the thermally conductive electromagnetic shielding composite material that the embodiment of the present invention 11 provides.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
A kind of thermally conductive electromagnetic shielding composite material, by foam copper and the polymer matrix being filled in foam copper metallic framework
Composite material composition.
Wherein, polymer matrix composite is made of epoxy resin and aluminium oxide, the mass ratio of epoxy resin and aluminium oxide
For 8:92.
The preparation method is as follows:
(1) liquid bisphenol A type epoxy resin is uniformly mixed with ethylenediamine curing agent 100:8 in mass ratio, adds spherical shape
Alumina powder is uniformly mixed；
(2) by the foam copper of above-mentioned mixture die casting to 0.2mm thickness, and in 120 DEG C of solidification 4h, thermally conductive electromagnetic screen is obtained
Cover composite material.
Embodiment 2-4
Difference with embodiment 1 is only that, in the present embodiment, aluminium oxide is replaced with boron nitride (embodiment 2), boron nitride
Composition (embodiment 3), the crystalline sillica (embodiment 4) formed with aluminium oxide with mass ratio 3:7.
Embodiment 5-8
Difference with embodiment 1 is only that, in the present embodiment, the mass ratio of epoxy resin and aluminium oxide is that 5:95 (is implemented
Example 5), 80:20 (embodiment 6), 3:97 (embodiment 7), 90:10 (embodiment 8).
Embodiment 9-10
Difference with embodiment 1 is only that, in the present embodiment, epoxy resin is replaced with liquid silica gel and (while being replaced with
Corresponding curing agent, embodiment 9), polyethylene (embodiment 10).
Embodiment 11
A kind of thermally conductive electromagnetic shielding composite material, by foam copper and the polymer matrix being filled in foam copper metallic framework
Composite material composition.
Wherein, polymer matrix composite is made of silica gel and boron nitride, and the mass ratio of silica gel and boron nitride is 20:80.
The preparation method is as follows:
(1) liquid-state silicon gel is uniformly mixed with its curing agent, is added platelet boron nitride and is uniformly mixed；
(2) by the foam copper of above-mentioned mixture die casting to 0.5mm thickness, and in 100 DEG C of solidification 1h, thermally conductive electromagnetic screen is obtained
Cover composite material.
Fig. 1 is the scanning electron microscope (SEM) photograph of foam copper, and Fig. 2 is the scanning electron microscope of the thermally conductive electromagnetic shielding composite material finally obtained
Figure, by the comparison of Fig. 1 and Fig. 2 it is found that polymer matrix composite provided by the invention is filled in the hole of foam copper.
Embodiment 12
A kind of thermally conductive electromagnetic shielding composite material, by foam copper and the polymer matrix being filled in foam copper metallic framework
Composite material composition.
Wherein, the combination that polymer matrix composite is made of epoxy resin and boron nitride and aluminium oxide with mass ratio 3:7
The mass ratio of object composition, epoxy resin and filler is 10:90.
The preparation method is as follows:
(1) liquid bisphenol A type epoxy resin is uniformly mixed with ethylenediamine curing agent 100:8 in mass ratio, adds nitridation
Boron and aluminium oxide are uniformly mixed with the composition that mass ratio 3:7 is formed；
(2) by the foam copper of above-mentioned mixture die casting to 1.0mm thickness, and in 120 DEG C of solidification 4h, thermally conductive electromagnetic screen is obtained
Cover composite material.
Embodiment 13
A kind of thermally conductive electromagnetic shielding composite material, by nickel foam and the polymer matrix being filled in nickel foam metallic framework
Composite material composition.
Wherein, polymer matrix composite is made of epoxy resin and aluminium oxide, the mass ratio of epoxy resin and aluminium oxide
For 8:92.
The preparation method is as follows:
(1) liquid bisphenol A type epoxy resin is uniformly mixed with ethylenediamine curing agent 100:8 in mass ratio, adds spherical shape
Alumina powder is uniformly mixed；
(2) by the nickel foam of above-mentioned mixture die casting to 1.0mm thickness, and in 120 DEG C of solidification 4h, thermally conductive electromagnetic screen is obtained
Cover composite material.
Embodiment 14
A kind of thermally conductive electromagnetic shielding composite material, by nickel foam and the polymer matrix being filled in nickel foam metallic framework
Composite material composition.
Wherein, the composition group that polymer matrix composite is made of silica gel and boron nitride and aluminium oxide with mass ratio 3:7
At the mass ratio of epoxy resin and filler is 10:90.
The preparation method is as follows:
(1) liquid-state silicon gel is uniformly mixed with its curing agent, adds the group that boron nitride and aluminium oxide are formed with mass ratio 3:7
Object is closed to be uniformly mixed；
(2) by the nickel foam of above-mentioned mixture die casting to 2.0mm thickness, and in 120 DEG C of solidification 4h, thermally conductive electromagnetic screen is obtained
Cover composite material.
Embodiment 15
The difference from embodiment 1 is that polymer matrix composite is made of epoxy resin, aluminium oxide and iron sial, ring
The mass ratio of oxygen resin, aluminium oxide and iron sial is 6:92:2.
Comparative example 1
Difference with embodiment 1 is only that, in this comparative example, thermally conductive electromagnetic shielding composite material by foam metal and
It is filled in the intraskeletal epoxy resin composition of foam metal, wherein not including insulating heat-conductive filler.
Comparative example 2
Difference with embodiment 1 is only that, in this comparative example, thermally conductive electromagnetic shielding composite material by foam metal and
It is filled in the intraskeletal insulating heat-conductive filler composition of foam metal, wherein not including polymer.
Comparative example 2 can not form, and can not be tested and be applied.
Performance test
The thermally conductive electromagnetic shielding composite material provided embodiment and comparative example is tested for the property, the method is as follows:
(1) it thermal coefficient: is tested using ASTM D5470 international standard；
(2) it electromagnet shield effect: is tested using network vector analyzer flange coaxial method, frequency range 300MHz-3GHz.
Test result is shown in Table 1:
Table 1
By embodiment and performance test it is found that thermally conductive electromagnetic shielding composite material provided by the invention have it is excellent thermally conductive
Its electromagnetic shielding performance is also preferable while performance, wherein electromagnet shield effect reaches as high as 85dB or more, thermal coefficient highest
Up to more than 5.8W/ (mK).
The present invention preferably boron nitride and/or aluminium oxide, more preferably nitrogenizes known to the comparison of embodiment 1-3 and embodiment 4
The composition that boron and aluminium oxide are formed with mass ratio 3:7, thermally conductive electromagnetic shielding composite material has better heating conduction at this time
And electromagnetic shielding performance.By the comparison of embodiment 1,5-8 it is found that when the mass percentage of insulating heat-conductive filler is 20-95%
When, better performances, wherein the thermal coefficient of embodiment 7 is higher, but since insulating heat-conductive filler additive amount is excessive, leads to reality
Phenomena such as filler is precipitated is easy to appear in operating process.By the comparison of embodiment 1,9-10 it is found that polymer of the invention is preferred
Epoxy resin and silica gel.
By the comparison of embodiment 1 and comparative example 1-2 it is found that polymer and insulating heat-conductive filler Neither of the two can be dispensed.
The Applicant declares that the present invention is explained by the above embodiments thermally conductive electromagnetic shielding composite material of the invention and its
Preparation method and application, but the invention is not limited to above-mentioned processing steps, that is, do not mean that the present invention must rely on above-mentioned work
Skill step could be implemented.It should be clear to those skilled in the art, any improvement in the present invention, to selected by the present invention
With the equivalence replacement of raw material and addition, selection of concrete mode of auxiliary element etc., protection scope of the present invention and public affairs are all fallen within
Within the scope of opening.
Claims (10)
1. a kind of thermally conductive electromagnetic shielding composite material, which is characterized in that the thermally conductive electromagnetic shielding composite material includes foam gold
Belong to and be filled in the intraskeletal polymer matrix composite of foam metal；
Wherein, the polymer matrix composite includes polymer and insulating heat-conductive filler.
2. thermally conductive electromagnetic shielding composite material according to claim 1, which is characterized in that the insulating heat-conductive filler includes
Any one in boron nitride, aluminium nitride, aluminium oxide, magnesia, silicon nitride, diamond or crystalline sillica or at least two
The combination of kind, preferably boron nitride and/or aluminium oxide, the combination that further preferred boron nitride and aluminium oxide are formed with mass ratio 3:7
Object；
Preferably, in the polymer matrix composite, the mass percentage of the insulating heat-conductive filler is 20-95%.
3. thermally conductive electromagnetic shielding composite material according to claim 1 or 2, which is characterized in that the polymer includes ring
Oxygen resin, phenolic resin, Lauxite, melamine formaldehyde resin, polybutadiene, polyurethane, silicon ether resin, silica gel,
Polyethylene, polypropylene, polyvinyl chloride, polystyrene, polymethyl methacrylate, polyester, polyformaldehyde, polyamide, polycarbonate,
Polyphenylene oxide, acrylonitrile-butadiene-styrene copolymer, vulcanized rubber, synthetic rubber, ethylene-vinyl acetate copolymer, benzene
Ethylene-isoprene-styrene block copolymer, Styrene-Butadiene-Styrene Block Copolymer or styrene-ethylene-fourth two
In alkene-styrene block copolymer any one or at least two combination, preferred epoxy and/or silica gel；
Preferably, the polymer is epoxy resin, and the insulating heat-conductive filler is boron nitride and aluminium oxide with mass ratio 3:7 group
At composition, by the gross mass of the polymer and insulating heat-conduction material be 100% in terms of, the quality of the insulating heat-conduction material
Percentage composition is 8-10%, further preferred 8%.
4. thermally conductive electromagnetic shielding composite material described in any one of -3 according to claim 1, which is characterized in that the foam
Metal is foam copper, nickel foam, foamed aluminium, foamed iron, titanium foam, Foam silver, foam zinc, foam iron-nickel, foam nickel chromium triangle, foam
In cobalt nickel or stainless steel foam any one or at least two combination；
Preferably, in the thermally conductive electromagnetic shielding composite material, the mass percentage of the polymer matrix composite is
40-85%.
5. thermally conductive electromagnetic shielding composite material described in any one of -4 according to claim 1, which is characterized in that the foam
The porosity of metal is 60-99%；
Preferably, the foam metal with a thickness of 0.1-20mm.
6. thermally conductive electromagnetic shielding composite material described in any one of -5 according to claim 1, which is characterized in that the polymerization
It further include absorbing material in object based composites；
Preferably, the absorbing material includes polyaniline, ferrite, barium ferrite, graphene oxide, silicon carbide, silicon nitride, iron
In chromium, iron silicochromium, barium titanate, iron sial or ferronickel any one or at least two combination.
7. the preparation method of thermally conductive electromagnetic shielding composite material described in any one of -6, feature exist according to claim 1
In the preparation method includes: to be filled into polymer matrix composite in a form of slurry in the hole of foam metal, then
Solvent is removed, the thermally conductive electromagnetic shielding composite material is obtained.
8. preparation method according to claim 7, which is characterized in that the method for the filling include pour, die casting or roller
In pressure any one or at least two combination.
9. preparation method according to claim 7 or 8, which is characterized in that the polymerization in the polymer matrix composite
Object matrix is thermosetting resin, and the method for removing solvent is to be heating and curing；
Preferably, the temperature being heating and curing is 25-200 DEG C, time 10min-24h.
10. according to claim 1 thermally conductive electromagnetic shielding composite material described in any one of -6 heat-conducting pad, heat-conducting cream or
Application in thermally conductive gel.
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