CN113337077A - High-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with isolation structure and preparation method and application thereof - Google Patents
High-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with isolation structure and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with an isolation structure, and a preparation method and application thereof, and belongs to the technical field of composite materials. According to the invention, the carbon nano tube and the graphene are used as synergistic hybrid fillers, so that the contact area between the fillers is increased, the establishment of a filler network is facilitated, and the transmission effectiveness is improved; introducing polybenzoxazine with hydrogen bond effect to respectively modify and compound the polyetheretherketone and the hybrid filler to obtain polyetheretherketone composite particles with hybrid filler as a skin layer, polybenzoxazine as an adhesion layer and polyetheretherketone particles as a core, and obtaining the high-thermal-conductivity electromagnetic shielding polyetheretherketone composite material with an isolation structure through crosslinking curing and melting hot pressing. According to the invention, the benzoxazine polymer layer is used for modifying polyether-ether-ketone and constructing an isolation structure, so that a stable and efficient heat conduction and conduction transmission network is formed, the interface compatibility of the filler and the polymer is improved, the interface thermal resistance is reduced, and the heat conduction and electromagnetic shielding performance is good.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with an isolation structure, and a preparation method and application thereof.
Background
With the innovation of advanced wireless communication technology, the application of electronic chips in some industries, particularly in the fields of military, aerospace, machinery, energy and the like, puts higher requirements on densification, integration and light weight of chips. However, miniaturization of electronic devices and circuits is accompanied by a large accumulation of heat energy, heat dissipation has become a critical factor affecting stability, reliability and lifetime, and these micro devices also generate unexpected electromagnetic interference (EMI), which not only affects transmission performance of signal systems, but also seriously harms human health and environmental friendliness. The absorption and conversion of electromagnetic waves into thermal energy is one of the common methods of reducing electromagnetic pollution, but this exacerbates the thermal diffusion problem. Therefore, heat conductive composite materials having electromagnetic shielding properties have been attracting attention. However, the functional composite material using general plastic as the matrix is difficult to meet the application requirements of military and aerospace in high temperature resistance, strong mechanical properties or high electromagnetic shielding requirements under severe conditions.
Polyether ether ketone (PEEK) is a semi-crystalline special engineering plastic, has excellent thermal stability (the long-term use temperature is 260 ℃ and the melting temperature is 340 ℃) and excellent mechanical property and chemical stability compared with common general materials. Therefore, the PEEK-based thermally conductive electromagnetic shielding material is widely used. But because of the low thermal conductivity of polyetheretherketone (about 0.2 W.m)-1·K-1) Its shielding performance is also poor. Meanwhile, due to the characteristic that PEEK is hardly dissolved in a conventional solvent, the difficulty of modification work of covalent bonds or non-covalent bonds is greatly increased. Thus, obtaining PEEK composites with good thermal/electrical conductivity properties remains challenging.
At present, the construction of a good filler transmission network and the selection of a filler system with a synergistic effect are effective methods for improving the heat/electrical conductivity of the composite material. For example, chinese patent CN110527247B discloses that a polyetheretherketone/multiwall carbon nanotube composite material is prepared by an in-situ polymerization method, and is dispersed in a graphene nanosheet network by ball milling and hot-pressed to form a polyetheretherketone thermal conductive composite material with a double-network structure with excellent performance. Chinese patent CN107459770B discloses that a polyetheretherketone composite material with high thermal conductivity and high stability is prepared by using silicon carbide, boron nitride and basalt fiber as synergistic thermal conductive fillers. However, the heat conductivity of the polyetheretherketone composite material prepared by the method is only improved to a certain extent and cannot meet the application requirements on shielding performance.
Disclosure of Invention
In view of this, the present invention provides a high thermal conductivity electromagnetic shielding polyetheretherketone composite material with an isolation structure, and a preparation method and an application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with an isolation structure, which comprises the following steps of:
(1) mixing a multi-walled carbon nanotube, a graphene nanosheet, benzoxazine and a soluble benzoxazine solvent for ultrasonic modification to obtain a modified hybrid filler dispersion liquid;
(2) mixing polyether-ether-ketone, benzoxazine and a soluble benzoxazine solvent for ultrasonic modification to obtain a modified polyether-ether-ketone dispersion liquid;
(3) mixing the modified hybrid filler dispersion liquid and the modified polyether-ether-ketone dispersion liquid, and performing vacuum shearing assisted mixing to obtain polyether-ether-ketone composite particles;
(4) sequentially carrying out curing crosslinking and melting hot pressing on the polyether-ether-ketone composite particles to obtain the high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with the isolation structure;
the step (1) and the step (2) have no chronological sequence.
Preferably, the mass ratio of the multi-walled carbon nanotube to the graphene nanosheet is 1-5: 1.
preferably, the ratio of the total mass of the multi-walled carbon nanotubes and the graphene nanoplatelets to the mass of the benzoxazine is 100: 1 to 10.
Preferably, the particle size of the polyether-ether-ketone is 15-1000 meshes.
Preferably, the mass ratio of the polyether-ether-ketone to the benzoxazine is 10-100: 1.
preferably, the cured crosslinking comprises a first cured crosslinking, a second cured crosslinking and a third cured crosslinking which are sequentially carried out;
the temperature of the first curing crosslinking is 130-150 ℃, and the heat preservation time is 1-2 h;
the temperature of the second curing crosslinking is 170-190 ℃, and the heat preservation time is 2-3 h;
the temperature of the third curing crosslinking is 210-230 ℃, and the heat preservation time is 1-2 h.
Preferably, the temperature of the melting hot pressing is 370-390 ℃, and the pressure is 10-50 MPa.
The invention provides the high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with the isolation structure, which is prepared by the preparation method in the technical scheme.
Preferably, the volume fraction of the hybrid filler in the high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with the isolation structure is 1-20%.
The invention provides the application of the high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with the isolation structure in the automobile industry, the military and the aerospace.
The invention provides a preparation method of a high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with an isolation structure, which comprises the following steps of: (1) mixing a multi-walled carbon nanotube, a graphene nanosheet, benzoxazine and a soluble benzoxazine solvent for ultrasonic modification to obtain a modified hybrid filler dispersion liquid; (2) mixing polyether-ether-ketone, benzoxazine and a soluble benzoxazine solvent for ultrasonic modification to obtain a modified polyether-ether-ketone dispersion liquid; (3) mixing the modified hybrid filler dispersion liquid and the modified polyether-ether-ketone dispersion liquid, and performing vacuum shearing assisted mixing to obtain polyether-ether-ketone composite particles; (4) sequentially carrying out curing crosslinking and melting hot pressing on the polyether-ether-ketone composite particles to obtain the high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with the isolation structure; the step (1) and the step (2) have no chronological sequence. The invention successfully prepares the high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with an isolation structure by using a multi-wall carbon nano tube and a graphene nano sheet as hybrid fillers, using benzoxazine as a modifier of the hybrid fillers and polyether-ether-ketone and adopting a vacuum auxiliary method, a thermal cross-linking polymer modification method and a melting hot-pressing method. In the invention, the hybrid filler is extruded from the polyether-ether-ketone polymer phase in the melting and hot pressing process, is enriched and is continuously lapped, so that a conduction network (namely an isolation structure) which is separated from the polyether-ether-ketone phase and is continuously stacked with the hybrid filler is formed, thereby being beneficial to the rapid transmission of phonons and facilitating the conduction and the diffusion of heat. Compared with the common melt blending method, the preparation method provided by the invention can obtain a special isolation structure, and the isolation structure can form a relatively complete heat transfer network under the condition of low filler content. Meanwhile, the 'nano-microbridge' effect with synergistic effect in the isolation structure increases the contact area (point-line, point-surface, line-surface) between the hybrid fillers, is beneficial to sound heat conduction and heat dissipation, and is very beneficial to improving the heat conduction performance of the material. The polyether-ether-ketone matrix and the hybrid filler are modified by introducing the thermosetting polybenzoxazine polymer, the polybenzoxazine, the hybrid filler and the polyether-ether-ketone are subjected to hydrogen bond interaction, the hydrogen bond interaction can reduce the strong intramolecular pi-pi interaction of the hybrid filler, so that the dispersity of the hybrid filler is improved, and the contact thermal resistance is reduced. Therefore, the high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with the isolation structure has excellent electrical conductivity, thermal conductivity and electromagnetic shielding performance.
The invention provides the high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with the isolation structure, which is prepared by the preparation method in the technical scheme. The high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with the isolation structure has excellent electrical conductivity, thermal conductivity and electromagnetic shielding performance, as shown in an embodiment result, the thermal conductivity of the high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with the isolation structure in the vertical direction is 0.4-3.338W/mK, the thermal conductivity of the high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with the isolation structure in the parallel direction is 0.531-6.27W/mK, the electrical conductivity of the high-thermal-shielding polyether-ether-ketone composite material is 0.12-524S/m, the total shielding performance of the high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with the isolation structure in 8-12 GHz floats within 60-80 dB, and. Has good application prospect in the automobile industry, military and aerospace.
Drawings
Fig. 1 is a schematic view illustrating the improvement of the heat conducting and electromagnetic shielding performance of the high heat conducting electromagnetic shielding polyetheretherketone composite material with an isolation structure according to the present invention; the heat conduction of the high-heat-conductivity electromagnetic shielding polyether-ether-ketone composite material with the isolation structure is improved, and the shielding effectiveness of the high-heat-conductivity electromagnetic shielding polyether-ether-ketone composite material with the isolation structure is improved;
FIG. 2 is a flowchart of a process for preparing a high thermal conductivity electromagnetic shielding polyetheretherketone composite with an isolation structure according to an embodiment;
fig. 3 is scanning electron microscope images of the peek composite particles before and after fusion and hot pressing in example 4, where (a) is the scanning electron microscope image of the peek composite particles before fusion and hot pressing, and (b) is the scanning electron microscope image of the high thermal conductivity electromagnetic shielding peek composite material with the isolation structure obtained after fusion and hot pressing;
fig. 4 is a shielding performance graph of the high thermal conductive electromagnetic shielding polyetheretherketone composite material with an isolation structure prepared in example 6;
fig. 5 is a thermogravimetric analysis graph of the high thermal conductive electromagnetic shielding polyetheretherketone composite material with an isolation structure prepared in example 2.
Detailed Description
The invention provides a preparation method of a high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with an isolation structure, which comprises the following steps of:
(1) mixing a multi-walled carbon nanotube, a graphene nanosheet, benzoxazine and a soluble benzoxazine solvent for ultrasonic modification to obtain a modified hybrid filler dispersion liquid;
(2) mixing polyether-ether-ketone, benzoxazine and a soluble benzoxazine solvent for ultrasonic modification to obtain a modified polyether-ether-ketone dispersion liquid;
(3) mixing the modified hybrid filler dispersion liquid and the modified polyether-ether-ketone dispersion liquid, and performing vacuum shearing assisted mixing to obtain polyether-ether-ketone composite particles;
(4) sequentially carrying out curing crosslinking and melting hot pressing on the polyether-ether-ketone composite particles to obtain the high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with the isolation structure;
the step (1) and the step (2) have no chronological sequence.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
The preparation method comprises the step of mixing a multi-walled carbon nanotube, a graphene nanosheet, benzoxazine and a soluble benzoxazine solvent for ultrasonic modification to obtain a modified hybrid filler dispersion liquid. In the invention, the length of the multi-walled carbon nanotubes (MWCNTs) is preferably 8-15 μm, and the pipe diameter is preferably 45-90 nm; the length of the graphene nano sheets (GnPs) is preferably 7-15 micrometers, and the thickness of the graphene nano sheets (GnPs) is preferably 6-10 nm; the mass ratio of the multi-walled carbon nanotube to the graphene nanosheet is preferably 1-5: 1, more preferably 2 to 4: 1, more preferably 3: 1. in the present invention, the mass ratio of the total mass of the multiwalled carbon nanotubes and graphene nanoplatelets to the benzoxazine (PBZ) is preferably 100: 1-10, more preferably 100: 3 to 8. The mixing is not particularly limited, and the raw materials can be uniformly mixed and dispersed. In the present invention, the mixing order is preferably that benzoxazine is dissolved in a soluble benzoxazine solvent to obtain a benzoxazine solution; and adding a multi-walled carbon nanotube and a graphene nanosheet into the benzoxazine solution for mixing. The type of the soluble benzoxazine solvent is not particularly limited, and the soluble benzoxazine solvent can be used for dissolving benzoxazine, such as a ketone solvent, and the ether solvent preferably comprises acetone and/or butanone; the concentration of the benzoxazine solution is preferably 1.25-10 wt%, more preferably 2-8 wt%, and further preferably 5-6 wt%. In the present invention, the solid content of the modified hybrid filler dispersion (i.e., the content of the modified hybrid filler) is preferably 1 to 8g/L, more preferably 2 to 6g/L, and still more preferably 3 to 5 g/L. The mixing is not particularly limited, and the raw materials can be uniformly mixed and dispersed. In the invention, the frequency of the ultrasonic modification is preferably 40-100 Mpa, more preferably 50-80 Mpa; the ultrasonic time is preferably 3-6 h, and more preferably 4-5 h; the ultrasound is preferably carried out in an ultrasonic oscillator; in the ultrasonic modification process, the crystal fillers which are closely packed and arranged are stripped and dispersed under the action of oscillation, so that the benzoxazine modifier enters the interlayer, the pi-pi interaction between the fillers is reduced, and the interface compatibility when the modified hybrid fillers and the polyether-ether-ketone polymer are compounded is improved.
The invention mixes polyether-ether-ketone, benzoxazine and soluble benzoxazine solvent for ultrasonic modification to obtain modified polyether-ether-ketone dispersion liquid. In the present invention, the polyether ether ketone (PEEK) preferably has a particle size of 15 to 1000 mesh, more preferably 100 to 500 mesh. In the invention, the mass ratio of the polyether-ether-ketone to the benzoxazine is preferably 10-100: 1, more preferably 30 to 80: 1, more preferably 50 to 60: 1; the invention has no special limitation on the mixing, and the raw materials can be uniformly mixed and dispersed; the mixing sequence is preferably that the benzoxazine is dissolved in a soluble benzoxazine solvent to obtain a benzoxazine solution; mixing the benzoxazine solution with polyetheretherketone. The type of the soluble benzoxazine solvent is not particularly limited, and the soluble benzoxazine solvent can be used for dissolving benzoxazine, such as a ketone solvent, and the ether solvent preferably comprises acetone and/or butanone; the concentration of the benzoxazine solution is preferably 1.25-10 wt%, more preferably 2-8 wt%, and further preferably 5-6 wt%, in the invention, the frequency of the ultrasonic modification is preferably 40-100 MHz, and more preferably 50-80 MHz; the ultrasonic time is preferably 1-6 h, and more preferably 3-4 h; the ultrasound is preferably carried out in an ultrasonic oscillator; and in the ultrasonic modification process, the polyether-ether-ketone surface layer is uniformly coated with the benzoxazine polymer modifier.
After the modified hybrid filler dispersion liquid and the modified polyether-ether-ketone dispersion liquid are obtained, the modified hybrid filler dispersion liquid and the modified polyether-ether-ketone dispersion liquid are mixed, and vacuum shearing assisted mixing is carried out to obtain the polyether-ether-ketone composite particles. In the invention, the mass ratio of the modified hybrid filler in the modified hybrid filler dispersion liquid to the modified polyether-ether-ketone in the modified polyether-ether-ketone dispersion liquid is preferably 1-50: 50 to 99, more preferably 10 to 40: 60 to 90, and more preferably 20 to 30: 70-80. The mixing is not particularly limited, and the raw materials can be uniformly mixed and dispersed. In the present invention, the vacuum shear-assisted mixing is preferably performed by slow-release vacuum-assisted filtration; the vacuum shear-assisted mixing is carried out under the action of a certain shear force, the polyetheretherketone composite particles with a more complete structure can be obtained through the vacuum shear-assisted mixing, the skin layer of the polyetheretherketone composite particles is mixed filler, the adhesion layer is polybenzoxazine, and the core is the polyetheretherketone composite particles of the polyetheretherketone particles.
After the polyether-ether-ketone composite particles are obtained, the polyether-ether-ketone composite particles are subjected to melting hot pressing to obtain the high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with the isolation structure. In the present invention, the cured crosslinking preferably includes a first cured crosslinking, a second cured crosslinking, and a third cured crosslinking, which are performed in this order; the temperature of the first curing crosslinking is preferably 130-150 ℃, and more preferably 140 ℃; the heat preservation time of the first curing crosslinking is preferably 1-2 h, and more preferably 1.5 h; the temperature of the second curing crosslinking is preferably 170-190 ℃, and more preferably 180 ℃; the heat preservation time of the second curing crosslinking is preferably 2-3 h, and more preferably 2.5 h; the temperature of the third curing and crosslinking is preferably 210-230 ℃, and more preferably 220 ℃; the heat preservation time of the third curing crosslinking is preferably 1-2 h, and more preferably 1.5 h; the curing and crosslinking are preferably carried out in an oven; in the curing and crosslinking process, part of oxazine ring is subjected to ring opening to generate a phenolic hydroxyl prepolymer (first crosslinking and curing); at a higher temperature (second crosslinking and curing), the oxazine ring is continuously subjected to ring opening and heterolysis to generate a cation active center, and the cation active center is combined with other molecules in a reaction manner to realize chain growth and generate an aromatic ether structure; further raising the temperature (third cross-linking and curing), raising the curing rate, increasing the cross-linking density, obtaining a polymer similar to the phenolic resin, and having strong intermolecular and intramolecular hydrogen bonding; the invention adopts a temperature programming crosslinking curing mode, which is beneficial to controlling the integrity of the whole crosslinking structure and improving the heat conductivity, the electric conductivity and the whole electromagnetic shielding performance of the composite material.
In the invention, the temperature of the melting hot pressing is preferably 370-390 ℃, and more preferably 380 ℃; the pressure of the melting hot pressing is preferably 10-50 MPa, and more preferably 20-40 MPa. In the invention, the polyether-ether-ketone is melted in the melting and hot-pressing process, the mixed filler is coated macroscopically, and the high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with the isolation structure is obtained by further molding.
The invention provides the high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with the isolation structure, which is prepared by the preparation method in the technical scheme.
In the present invention, a schematic diagram of the manufacturing heat conduction and the electromagnetic shielding performance improvement of the high thermal conductivity electromagnetic shielding polyetheretherketone composite material with the isolation structure is shown in fig. 1, wherein (a) is a schematic diagram of the heat conduction improvement of the high thermal conductivity electromagnetic shielding polyetheretherketone composite material with the isolation structure, and (b) is a schematic diagram of the shielding effectiveness improvement of the high thermal conductivity electromagnetic shielding polyetheretherketone composite material with the isolation structure. The isolating structure in the high-thermal-conductivity electromagnetic shielding polyetheretherketone composite material with the isolating structure provided by the invention provides more heat transfer paths and constructs a good heat-conducting network, and meanwhile, the contact area between the fillers is improved under the synergistic effect of the hybrid fillers, so that the scattering of phonons is reduced and the heat transfer performance is improved; therefore, the isolating structure in the high-thermal-conductivity electromagnetic shielding polyetheretherketone composite material with the isolating structure promotes the formation of more conductive interfaces, increases the multiple reflection times in the material, prolongs the propagation path and energy consumption of the material, reduces the transmission of electromagnetic waves, and further improves the shielding performance of the electromagnetic waves.
The invention also provides the application of the high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with the isolation structure in the automobile industry, military and aerospace.
In the present invention, the application of the high thermal conductivity electromagnetic shielding polyetheretherketone composite material with an isolation structure in automobiles preferably comprises the application of the high thermal conductivity electromagnetic shielding polyetheretherketone composite material as an engine inner cover, an ABS brake gasket or a clutch ring gear in automobile bearing transmission, braking and air conditioning systems, and is also preferably applied to the manufacture of turbo compressors, pumps, valves, wire cables, seat adjusting parts or standard parts. In the invention, the application of the high-thermal-conductivity electromagnetic shielding polyetheretherketone composite material with the isolation structure in aerospace preferably comprises the application of the high-thermal-conductivity electromagnetic shielding polyetheretherketone composite material in replacing an aluminum metal pipeline to protect high-voltage cables, main load-bearing members or parts of an air regeneration system. In the invention, the application of the high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with the isolation structure in military affairs preferably comprises the application in airplane parts for preventing electromagnetic interference of fighters.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The process flow chart shown in fig. 2 is adopted, and a vacuum auxiliary method, a thermal cross-linking polymer modification method and a melting hot-pressing method are adopted to prepare the high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with the isolation structure, and the specific steps are as follows:
0.05g of MWCNTs and 0.2g of GnPs are added into 250mL of 1.25 wt% PBZ acetone solution, mixed and dispersed uniformly, and subjected to ultrasonic treatment for 3 hours at room temperature and 60MHz in an ultrasonic oscillator to obtain the modified hybrid filler dispersion liquid. 9.75g of PEEK with the particle size of 200 meshes is added into 450mL of PBZ acetone solution with the concentration of 1.25 wt%, and ultrasonic treatment is carried out for 1h in an ultrasonic oscillator under the conditions of 60MHz and room temperature, so as to obtain the modified polyether-ether-ketone dispersion liquid. And mixing the modified mixed filler dispersion liquid and the modified polyether-ether-ketone dispersion liquid, and performing slow-release vacuum-assisted filtration treatment to obtain the polyether-ether-ketone composite particles. And (2) placing the polyether-ether-ketone composite particles in an oven, preserving heat for 1h at the temperature of 140 ℃, preserving heat for 2h at the temperature of 180 ℃, preserving heat for 2h at the temperature of 210 ℃, and then carrying out fusion hot pressing at the temperature of 380 ℃ and under the pressure of 30Mpa to obtain the high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with an isolation structure.
Example 2
The high-thermal-conductivity electromagnetic shielding polyetheretherketone composite material with an isolation structure is prepared according to the method of the embodiment 1, and the preparation conditions of the embodiments 2 to 6 are shown in table 1.
TABLE 1 preparation conditions for examples 1 to 6
Comparative example 1
0.125g of MWCNTs, 0.125g of GnPs and 9.75g of PEEK (1000 meshes) are mixed and stirred under a high-speed stirrer, and then the mixture is melted and hot-pressed under the conditions of 380 ℃ and 30Mpa to obtain the polyetheretherketone composite material.
The heat conductive performance and the electrical conductivity test results of the composite materials prepared in examples 1 to 6 and comparative example 1 are shown in table 2.
The thermal conductivity tester used for the thermal conductivity test was the flash emission method LFA467, germany. Conductivity test the conductivity tester utilized was a four-probe resistivity tester 2450 SourceMeter, KEITHLEY.
Table 2 results of testing thermal conductivity and electrical conductivity of the composite materials prepared in examples 1 to 6 and comparative example 1
As can be seen from Table 2, the composite material prepared by the present invention has excellent thermal conductivity and electrical conductivity.
Fig. 3 is a scanning electron microscope image of the peek composite particles before and after fusion and hot pressing in example 4, in which (a) is a scanning electron microscope image of the peek composite particles before fusion and hot pressing, and (b) is a scanning electron microscope image of the composite material obtained after fusion and hot pressing. As can be seen in fig. 3, the isolation structure in the composite material provided by the present invention is well established.
Fig. 4 is a shielding performance graph of the composite material prepared in example 6, and as can be seen from fig. 4, the total shielding performance of the composite material floats within 60-80 dB within 8-12 GHz, and the shielding efficiency reaches above 99.996%, which indicates that the composite material prepared in the present invention has excellent electromagnetic shielding performance.
FIG. 5 is a thermogravimetric analysis of the composite material prepared in example 2, T5(5% weight loss) at 550 ℃ C, T10The temperature of (10% weight loss) is 580 ℃, which shows that the composite material prepared by the invention has excellent thermal stability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with an isolation structure comprises the following steps:
(1) mixing a multi-walled carbon nanotube, a graphene nanosheet, benzoxazine and a soluble benzoxazine solvent for ultrasonic modification to obtain a modified hybrid filler dispersion liquid;
(2) mixing polyether-ether-ketone, benzoxazine and a soluble benzoxazine solvent for ultrasonic modification to obtain a modified polyether-ether-ketone dispersion liquid;
(3) mixing the modified hybrid filler dispersion liquid and the modified polyether-ether-ketone dispersion liquid, and performing vacuum shearing assisted mixing to obtain polyether-ether-ketone composite particles;
(4) sequentially carrying out curing crosslinking and melting hot pressing on the polyether-ether-ketone composite particles to obtain the high-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with the isolation structure;
the step (1) and the step (2) have no chronological sequence.
2. The preparation method of claim 1, wherein the mass ratio of the multi-walled carbon nanotube to the graphene nanosheet is 1-5: 1.
3. the method according to claim 1, wherein the ratio of the total mass of the multi-walled carbon nanotubes and graphene nanoplatelets to the mass of benzoxazine is 100: 1 to 10.
4. The preparation method according to claim 1, wherein the particle size of the polyetheretherketone is 15-1000 mesh.
5. A preparation method according to claim 1 or 4, wherein the mass ratio of the polyether-ether-ketone to the benzoxazine is 10-100: 1.
6. the production method according to claim 1, wherein the cured crosslinking includes a first cured crosslinking, a second cured crosslinking, and a third cured crosslinking that are performed in this order;
the temperature of the first curing crosslinking is 130-150 ℃, and the heat preservation time is 1-2 h;
the temperature of the second curing crosslinking is 170-190 ℃, and the heat preservation time is 2-3 h;
the temperature of the third curing crosslinking is 210-230 ℃, and the heat preservation time is 1-2 h.
7. The method according to claim 1, wherein the temperature of the melt hot pressing is 370 to 390 ℃ and the pressure is 10 to 50 MPa.
8. The high-thermal-conductivity electromagnetic shielding polyetheretherketone composite material with an isolation structure, which is obtained by the preparation method of any one of claims 1 to 7.
9. The high-thermal-conductivity electromagnetic shielding polyetheretherketone composite material with an isolation structure according to claim 8, wherein the volume fraction of the hybrid filler in the high-thermal-conductivity electromagnetic shielding polyetheretherketone composite material with an isolation structure is 1-20%.
10. Use of the high thermal conductivity electromagnetic shielding polyetheretherketone composite with an insulation structure according to any of claims 8 to 9 in the automotive industry, military and aerospace.
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| CN202110861525.4A CN113337077B (en) | 2021-07-29 | 2021-07-29 | High-thermal-conductivity electromagnetic shielding polyether-ether-ketone composite material with isolation structure and preparation method and application thereof |
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