CN112961452B - Preparation method of polymer-based nanocomposite material with high thermal conductivity and low dielectric loss for microwave communication - Google Patents
Preparation method of polymer-based nanocomposite material with high thermal conductivity and low dielectric loss for microwave communication Download PDFInfo
- Publication number
- CN112961452B CN112961452B CN202110168544.9A CN202110168544A CN112961452B CN 112961452 B CN112961452 B CN 112961452B CN 202110168544 A CN202110168544 A CN 202110168544A CN 112961452 B CN112961452 B CN 112961452B
- Authority
- CN
- China
- Prior art keywords
- nano
- mixing
- dielectric loss
- melting
- filler
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000004891 communication Methods 0.000 title claims abstract description 20
- 239000000463 material Substances 0.000 title claims abstract description 18
- 239000013339 polymer-based nanocomposite Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 57
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 30
- 239000000945 filler Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 23
- 229920000642 polymer Polymers 0.000 claims abstract description 23
- 238000002844 melting Methods 0.000 claims abstract description 21
- 230000008018 melting Effects 0.000 claims abstract description 21
- 239000000919 ceramic Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000002114 nanocomposite Substances 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 239000004793 Polystyrene Substances 0.000 claims description 25
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 21
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 20
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 20
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 19
- 239000005543 nano-size silicon particle Substances 0.000 claims description 18
- 239000002041 carbon nanotube Substances 0.000 claims description 12
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 229920005992 thermoplastic resin Polymers 0.000 claims description 7
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002042 Silver nanowire Substances 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 44
- 238000012545 processing Methods 0.000 abstract description 9
- 239000000758 substrate Substances 0.000 abstract description 4
- 230000033228 biological regulation Effects 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000012767 functional filler Substances 0.000 abstract 1
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 239000011347 resin Substances 0.000 description 22
- 229920005989 resin Polymers 0.000 description 22
- 238000012360 testing method Methods 0.000 description 18
- 238000005259 measurement Methods 0.000 description 12
- 238000000465 moulding Methods 0.000 description 10
- 239000002048 multi walled nanotube Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000523 sample Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 239000011231 conductive filler Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 229920013657 polymer matrix composite Polymers 0.000 description 1
- 239000011160 polymer matrix composite Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/201—Pre-melted polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/223—Packed additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/02—Homopolymers or copolymers of hydrocarbons
- C08J2325/04—Homopolymers or copolymers of styrene
- C08J2325/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/16—Homopolymers or copolymers of vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2425/02—Homopolymers or copolymers of hydrocarbons
- C08J2425/04—Homopolymers or copolymers of styrene
- C08J2425/06—Polystyrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/16—Homopolymers or copolymers of vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2433/12—Homopolymers or copolymers of methyl methacrylate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention relates to a preparation method of a polymer-based nanocomposite with high thermal conductivity and low dielectric loss for microwave communication, which is used for obtaining the polymer-based nanocomposite with excellent thermal conductivity and low dielectric loss under microwave communication based on the distribution regulation of functional nano-fillers in an incompatible polymer system, and belongs to the field of composite material preparation. The invention prepares the composite material with the 'double-communication' structure by a master batch melting and mixing process, utilizes the driving force of the functional filler to migrate from a thermodynamic nonequilibrium state to an equilibrium state, and from the aspect of mechanics, controls the distribution of the conductive nano-filler and the heat-conducting insulating nano-ceramic filler by the adjustment of a processing process, exerts the structural advantages of an incompatible system and the synergistic effect of the two fillers, prepares the nano-composite material which simultaneously considers higher heat conductivity coefficient and low dielectric loss, and provides a material preparation method with higher application significance for the requirements of packaging, substrate materials and the like of modern electronic equipment.
Description
Technical Field
The invention relates to a preparation method of a polymer-based nano composite material with high thermal conductivity and low dielectric loss for microwave communication, belonging to the field of composite materials.
Background
In recent years, with the rapid development of science and technology and the arrival of the 5G and higher frequency communication era, the product performance in the electronic and electrical fields has higher requirements. Due to the recent upgrading of assembly technology and integration technology, electronic equipment is required to have higher integration density and faster signal transmission speed, and heat dissipation of devices becomes an important issue, which has a great influence on the performance and service life of the devices, so that it is currently important to improve the thermal conductivity of substrates and packaging materials used for manufacturing the devices.
At present, most of metal materials with extremely high heat conductivity coefficient are applied in the aspects of heat conduction and heat dissipation, but the metal materials are expensive, poor in corrosion resistance and difficult to machine and form; ceramic materials with very good heat conductivity are not easy to process due to high brittleness, and have poor mechanical properties, and particularly, when the ceramic materials are applied to small parts of fast-updating electronic products, the requirements of high-precision forming technology cannot be met, and the defects limit the application and development of the ceramic materials to a great extent. The heat conductive filler has been widely studied in recent years to improve the thermal conductivity of polymer matrix composites, and because of its high electrical insulation, good processability and excellent mechanical properties, it can be applied to electronic device substrates and packaging materials if its thermal conductivity can be sufficiently improved. The heat transfer mechanism of such composites can be explained by phonon scattering, which can be greatly reduced if a network of thermally conductive particles can be formed in the composite, resulting in a significant increase in the thermal conductivity of the composite. The conventional method for forming the heat conducting network is to use a filler with a high volume fraction, however, the filler content higher than 50 vol% can cause the reduction of the processing performance and the remarkable reduction of the mechanical performance, and the addition of a carbon material with extremely excellent heat conducting performance, such as carbon nanotubes, graphene and the like, can effectively reduce the filler content, but simultaneously, the composite material forms the heat conducting network, so that higher dielectric loss is generated, signal delay is caused, and signal attenuation is increased. Patent cn201710201149.x provides a high thermal conductivity coefficient composite material compounded by graphene nanosheets and polystyrene mixed by using a solution, but the method for mixing by using the solution has the advantages of low efficiency, high cost, large environmental pollution and incapability of solving the problem of large dielectric loss. It is therefore necessary to develop polymer-based nanocomposites with lower filler loading to maintain low dielectric loss, but at the same time achieve higher thermal conductivity.
Disclosure of Invention
The invention aims to provide a preparation method of a polymer-based nanocomposite material with high thermal conductivity and low dielectric loss for microwave communication, which has simple process, is easy to control and is expected to be industrially generated aiming at the defects of the prior art. The method starts from the angle of dynamic regulation and control of the nano-filler, and realizes the polymer-based nano-composite material with high thermal conductivity and low dielectric loss based on an incompatible polymer system, a substrate and an encapsulation material of an electronic device facing microwave communication and the like through a processing technology probe.
The technical scheme adopted by the invention is as follows:
a nanometer composite material with high heat conductivity coefficient and low dielectric loss based on an incompatible polymer system and a preparation method thereof comprise the following steps:
s1: melting and mixing the thermoplastic resin A in the fully dried incompatible polymer system A/B and the conductive nano filler, wherein the technological parameters of melting and mixing are that the rotating speed is 40-80 r/min, the temperature is 180-210 ℃, and the melting and mixing are carried out for 10-20 minutes, so as to obtain a master batch I;
s2: melting and mixing the thermoplastic resin B in the fully dried incompatible polymer system A/B and the insulating nano ceramic filler, wherein the technological parameters of melting and mixing are that the rotating speed is 40-80 r/min, the temperature is 180-210 ℃, and the melting and mixing are carried out for 10-20 minutes, so as to obtain a master batch II;
s3: and (3) melting and mixing the master batch I and the master batch II obtained in the S1 and the S2, wherein the technological parameters of melting and mixing are that the rotating speed is 40-80 r/min, the temperature is 180-210 ℃, and the melting and mixing are carried out for 2-5 minutes, so that the nano composite material with high thermal conductivity and low dielectric loss is obtained.
Preferably, the thermoplastic resin system of steps S1, S2 comprises one of the typically incompatible polymer systems PMMA/PS system, PE/EVA system, PVDF/PS system or PVDF/PA6 system.
Preferably, the conductive nanofiller component of step S1 comprises one of carbon nanotubes, graphene, having a high aspect ratio.
Preferably, the insulating nanoceramic filler component of step S2 includes one of nano silicon carbide, nano boron nitride, nano alumina or nano aluminum nitride.
Preferably, the PMMA and PS resins of steps S1 and S2 should be dried sufficiently before melt-mixing.
Preferably, the volume fraction of the conductive nano filler in the master batch I in the step S1 is 1-2 vol%; in the step S2, the volume fraction of the insulating heat-conducting ceramic filler in the master batch II is 1-6 vol%; in the step S3, the volume ratio of the master batch I to the master batch II is 40/60-60/40.
Preferably, the nanofiller and the polymer are pre-mixed by sufficient milling before melt mixing in steps S1 and S2.
The invention has the beneficial effects that:
1) the invention prepares the composite material with the 'double-communication' structure by a master batch method melt mixing process, and realizes the construction of the connection network of the nano filler with lower percolation threshold by using the structural advantages of an incompatible polymer system, particularly the communication of a system interface.
2) According to the invention, through the introduction of the insulating heat-conducting nano ceramic filler and the conductive nano carbon material and the regulation and control of the processing technology, a three-dimensional heat-conducting network is formed at the interface of two-phase polymers of the matrix. Meanwhile, the synergistic effect of the two is exerted, the conductive filler serves as a heat transfer bridge of the ceramic filler, the phonon transmission efficiency is improved, and the heat conductivity coefficient of the composite material is improved.
3) In the invention, the conductive network of the conductive nano filler is blocked because of the introduction of the insulating ceramic filler, and the ceramic filler is used as the open circuit of the conductive path to form a discontinuous conductive network, so that the leakage conduction loss part of the system is greatly reduced, and the dielectric loss is greatly reduced.
Drawings
FIG. 1 is a scanning electron micrograph of the composite material obtained in example 1.
FIG. 2 is a transmission electron microscope image of the composite material obtained in example 1.
FIG. 3 is a graph showing the dielectric properties of the composite materials prepared in example 1, example 2, example 3, comparative example 1 and comparative example 2.
Fig. 4 is a graph showing the thermal conductivity of the composite materials prepared in example 1, example 2, example 3, comparative example 1 and comparative example 2.
Detailed Description
The invention will be further elucidated and described with reference to the drawings and the detailed description.
Example 1
(1) The PS resin and PMMA resin were dried in an oven at 60 ℃ for 24 hours for use.
(2) Before melt-mixing processing, 1 vol% of carbon nanotubes (MWCNT) and the dried PMMA resin were weighed out and sufficiently ground and premixed, and 1 vol% of nano silicon carbide (SiC) and the PS resin were weighed out and sufficiently ground and premixed.
(3) And (2) carrying out melt mixing by using a miniature high-performance composite material mixing and molding system (HAAKE Minilab II), setting the temperature at 200 ℃, rotating the screw at 60 r/min, and carrying out melt mixing for 10 minutes to fully and uniformly mix the carbon nanotube and the PMMA resin to obtain a master batch I (PMMA-MWCNT).
(4) And (3) carrying out melt mixing by using a miniature high-performance composite material mixing and molding system (HAAKE Minilab II), setting the temperature at 200 ℃, rotating the screw at 60 r/min, and carrying out melt mixing for 10 minutes to fully and uniformly mix the nano silicon carbide and the PS resin to obtain a master batch II (PS-SiC).
(5) Melting and mixing by using a miniature high-performance composite material mixing and molding system (HAAKE Minilab II), setting the temperature at 200 ℃ and the screw rotating speed at 60 r/min, mixing the master batch I and the master batch II at the volume ratio of 50/50 to construct a double-communication form, and controlling the melting and mixing time to be 2.5 minutes to ensure that the carbon nano tube and the nano silicon carbide are not completely migrated, the cross-linking is generated at the interface of the two-phase polymer, which plays a role of mutual synergy, the communication of the carbon tubes is blocked by the insulated nanometer silicon carbide, the leakage loss generated by the carbon tube network is reduced, meanwhile, the heat-conducting phonon conduction network constructed by the silicon carbide at the interface is more complete through the connection of the carbon tube, thereby realizing the polymer-based nano composite material (PMMA-MWCNT/PS-SiC) with high coefficient of thermal conductivity and low dielectric loss.
Measurement of thermal conductivity coefficient:
the thermal conductivity of the composite sample prepared in example 1 was measured using a thermal conductivity tester (TPS 2500S) from Hot Disk, Switzerland. Before testing, a sample is subjected to hot press molding to form an original sheet with the thickness of 3-5 mm and the diameter of 30-50 mm, measurement is carried out in a block mode, measurement is repeated for three times, 30 minutes is waited before each measurement, so that the internal thermal field of the sample is fully released, and the average value is taken as the final result.
And (3) measuring results: the thermal conductivity of the composite material (PMMA-MWCNT/PS-SiC) obtained by the test is 0.4678W/mK, which is obviously higher than that of the matrix PS/PMMA.
Measurement of dielectric Properties:
the scattering parameters (S parameters) at 8.2-12.4GHz were measured using a vector network analyzer (R & S, ZNB20), the samples were thermoformed into waveguide test dimensions of 22.86mm by 10.16mm by 5mm, the vector network analyzer was calibrated using the open-short-load-thru method prior to the test, the complex dielectric constant was calculated using the Nicolson-Ross-Weir method, and the loss tangent value was obtained as the magnitude of the dielectric loss.
And (3) testing results: the dielectric loss tangent value of the composite material (PMMA-MWCNT/PS-SiC) obtained by the test is 0.31, and the value is obviously lower compared with the composite material without the insulating nano silicon carbide.
As shown in fig. 1, after the PMMA phase is etched away, it can be clearly observed that the "double-connected" morphology can be successfully constructed by controlling the volume ratio of the matrix polymer to 50/50, and the interface has a bar-shaped carbon tube and spherical silicon carbide, which have protruding parts not falling off along with the PMMA phase in the PS phase. Fig. 2 is a transmission electron microscope photograph, and a composite material sheet with a thickness of 40 nm is prepared by freezing and slicing, wherein a bright phase is PMMA resin, a dark phase is PS resin, it can be obviously observed that the carbon tubes premixed into the PMMA phase in the master batch i have higher affinity with the PS phase, and the nano silicon carbide in the master batch ii has higher affinity with the PMMA phase, so that when the two master batches are blended again, the driving force for the transformation to the thermodynamic equilibrium state is reduced due to the reduction of the free energy of the system, the carbon tubes will migrate to the PS phase through the interface of the two-phase polymer during the mixing process, and the nano silicon carbide will migrate to the PMMA phase, so that spherical silicon carbide particles can be observed in the bright PMMA phase in the photograph, and rod-shaped carbon tubes are distributed in the dark PS phase. Further enlarging the observation of the interface, it can be clearly observed in fig. 2 that the migration of the carbon nanotubes and the nano-silicon carbide across the interface is not completely performed at the processing time selected in this example, and a large amount of the carbon nanotubes and the nano-silicon carbide are cross-linked at the interface as shown in the figure, which is consistent with the phenomenon observed at the interface in the scanning electron microscope. The construction of the structure successfully realizes the polymer-based nano composite material with higher heat conductivity coefficient and lower dielectric loss.
Example 2
(1) The PVDF resin and the PS resin were dried in an oven at 60 ℃ for 24 hours for use.
(2) Before melt-mixing processing, 1 vol% of Graphene (GN) and dried PVDF were weighed out and fully ground and premixed, and 1 vol% of nano-silicon carbide and dried PS were weighed out and fully ground and premixed.
(3) And (3) carrying out melt mixing by using a miniature high-performance composite material mixing and molding system (HAAKE Minilab II), setting the temperature at 200 ℃, rotating the screw at 60 r/min, and carrying out melt mixing for 10 minutes to fully and uniformly mix the carbon nanotube and the PVDF resin to obtain a master batch I (PVDF-GN).
(4) And (3) carrying out melt mixing by using a miniature high-performance composite material mixing and molding system (HAAKE Minilab II), setting the temperature at 200 ℃, rotating the screw at 60 r/min for 10 minutes, and fully and uniformly mixing the nano silicon carbide and the PS resin to obtain a master batch II (PS-SiC).
(5) And (2) carrying out melt mixing by using a miniature high-performance composite material mixed molding system (HAAKE Minilab II), setting the temperature at 200 ℃, rotating the screw at 60 r/min, controlling the volume ratio of the master batch I to the master batch II to be 50/50, constructing a double-communication form, and controlling the melt mixing time to be 2.5 minutes to obtain the composite material (PVDF-GN)/(PS-SiC).
Measurement of thermal conductivity coefficient:
the thermal conductivity of the composite sample prepared in example 1 was measured using a thermal conductivity tester (TPS 2500S) from Hot Disk, Switzerland. Before testing, a sample is hot-pressed and molded into an original sheet with the thickness of 3-5 mm and the diameter of 30-50 mm, the measurement is repeated for three times before the measurement and the test are carried out by using a block mode, 30 minutes are waited before each measurement, so that the internal thermal field of the sample is fully released, and the average value is taken as the final result.
And (3) measuring results: the thermal conductivity of the composite material (PVDF-GN)/(PS-SiC) is 0.4337W/mK and is obviously higher than that of the matrix.
Measurement of dielectric Properties:
the scattering parameter (S parameter) at 8.2-12.4GHz was measured using a vector network analyzer (R & S, ZNB20), the samples were thermoformed to a waveguide test size of 22.86mm by 10.16mm by 5mm, the vector network analyzer was calibrated using the open-short-load-thru method prior to testing, the complex dielectric constant was calculated using the Nicolson-Ross-Weir method, and the magnitude of the dielectric loss was expressed as the loss tangent.
And (3) testing results: the dielectric loss tangent value of the composite material (PVDF-GN)/(PS-SiC) obtained by the test is 0.28, and compared with the composite material without the insulating nano silicon carbide, the dielectric loss tangent value is obviously lower.
The embodiment has the same 'double-communication' structure as the embodiment 1, regulates and controls the migration and distribution of the nano-filler, and adopts different incompatible polymer systems and conductive fillers to realize the nano-composite material with high thermal conductivity and low dielectric loss.
Example 3
The difference between this example and example 1 is only that the content of the added nano filler is different, the content of the carbon nano tube is 1 vol%, the content of the nano silicon carbide is 6 vol%, and the preparation process of the composite material is consistent with that of example 1.
Measurement of thermal conductivity coefficient:
the thermal conductivity of the composite sample prepared in example 3 was measured using a thermal conductivity tester (TPS 2500S) from Hot Disk corporation, switzerland, the test method was identical to that of example 1.
And (3) measuring results: the thermal conductivity of the composite material (PMMA-MWCNT/PS-SiC2) is 0.8317W/mK and is obviously higher than that of the matrix PS/PMMA.
Measurement of dielectric Properties:
the scattering parameters (S parameters) at 8.2-12.4GHz were measured using a vector network analyzer (R & S, ZNB20), the samples were thermoformed into waveguide test dimensions of 22.86mm by 10.16mm by 5mm, the vector network analyzer was calibrated using the open-short-load-thru method prior to the test, the complex dielectric constant was calculated using the Nicolson-Ross-Weir method, and the loss tangent value was obtained as the magnitude of the dielectric loss.
And (3) testing results: the dielectric loss tangent value of the composite material (PMMA-MWCNT/PS-SiC) obtained by the test is 0.32, and the value is obviously lower compared with the composite material without the insulating nano silicon carbide.
After the content of the insulating nano silicon carbide is increased in embodiment 3, the value of the dielectric loss is further reduced, and meanwhile, due to the increase of the content, the heat conductivity coefficient is also greatly improved, and the construction of the heat conducting network is more complete.
Comparative example 1
(1) The PS resin and PMMA resin were dried in an oven at 60 ℃ for 24 hours for use.
(2) A miniature high-performance composite material mixing and molding system (HAAKE Minilab II) is used for carrying out melt mixing, the temperature is set to be 200 ℃, the rotating speed of a screw is 60 r/min, two resin matrix materials are mixed, the volume ratio of the two resin matrix materials is 50/50, a 'double-communication' form is constructed, and the melt mixing time is controlled to be 10 min.
Comparative example 2
(1) The PS resin and PMMA resin were dried in an oven at 60 ℃ for 24 hours for use.
(2) Before melt-mixing processing, 1 vol% of carbon nanotubes was weighed and thoroughly ground and premixed with the dried PMMA resin.
(3) And (2) carrying out melt mixing by using a miniature high-performance composite material mixing and molding system (HAAKE Minilab II), setting the temperature at 200 ℃, rotating the screw at 60 r/min, and carrying out melt mixing for 10 minutes to fully and uniformly mix the carbon nanotube and the PMMA resin to obtain a master batch I (PMMA-MWCNT).
(4) And (2) carrying out melt mixing by using a miniature high-performance composite material mixing and molding system (HAAKE Minilab II), setting the temperature at 200 ℃ and the screw rotation speed at 60 rpm, mixing the master batch 1 with the dried PS resin at the volume ratio of 50/50 to construct a 'double-communication' form, and controlling the melt mixing time to be 2.5 minutes to obtain the composite material without the addition of the insulating nano silicon carbide.
In order to verify the performance of the polymer-based nanocomposite obtained by the preparation method, the dielectric properties and the thermal conductivity of the materials in the examples and the comparative examples are measured by using a vector network analyzer and an instantaneous flat plate heat source measurement method, wherein the polymer-based nanocomposites prepared in the examples 1 and 2 and the comparative examples 1 and 2 are respectively marked as PMMA-MWCNT/PS-SiC, PVDF-GN/PS-SiC, PMMA/PS, PMMA-MWCNT/PS. The dielectric property test result is shown in fig. 3, compared with the comparative example 2, after the insulating nano silicon carbide is added, the dielectric loss of the composite material is greatly reduced, and meanwhile, the heat conductivity test result is shown in fig. 4, the heat conductivity coefficient of the composite material of the embodiment 1 is greatly improved, and the design of the polymer-based composite material with high heat conductivity coefficient and low dielectric loss is realized.
In addition, in the present invention, the specific parameters and materials of each step can be reasonably adjusted according to the needs. For example, the matrix of the composite material may be made of other materials, but it needs to satisfy the requirement that the processing temperature of the two polymers is in the same range and the two polymers are incompatible polymers, so as to form a "double-communication" structure, such as a system of PE/EVA, PVDF/PS and the like, and the form can form a communication interface structure, and simultaneously exert a volume exclusion effect and reduce the content of the filler. In addition, the added conductive material with extremely high thermal conductivity can be other materials with larger long diameter (>500), such as graphene and silver nanowires, and the added insulating and heat conducting material can be selected from boron nitride, aluminum nitride and the like.
Claims (8)
1. A preparation method of a polymer-based nanocomposite material with high thermal conductivity and low dielectric loss for microwave communication is characterized by comprising the following steps:
s1: melting and mixing the thermoplastic resin A and the conductive nano filler in the fully dried incompatible polymer system A/B, wherein the technological parameters of melting and mixing are that the rotating speed is 40-80 r/min, the temperature is 180-210 ℃, and the melting and mixing are carried out for 10-20 minutes, so as to obtain a master batch I;
s2: melting and mixing the thermoplastic resin B in the fully dried incompatible polymer system A/B and the insulating nano ceramic filler, wherein the technological parameters of melting and mixing are that the rotating speed is 40-80 r/min, the temperature is 180-210 ℃, and the melting and mixing are carried out for 10-20 minutes, so as to obtain a master batch II;
s3: and (3) melting and mixing the master batch I and the master batch II obtained in the S1 and the S2 to form a three-dimensional heat conduction network at the interface of the two-phase polymers of the matrix, wherein the process parameters of melting and mixing are that the rotating speed is 40-80 rpm, the temperature is 180-210 ℃, and the melting and mixing are carried out for 2-5 minutes to obtain the polymer-based nanocomposite with high heat conductivity coefficient and low dielectric loss.
2. The method of claim 1, wherein the incompatible polymer system A/B of steps S1 and S2 is one of PMMA/PS system, PVDF/PS system or PVDF/PA6 system.
3. The method of claim 1, wherein the conductive nano-filler in step S2 is one or more of carbon nanotube, graphene, carbon nanofiber, and silver nanowire with aspect ratio > 500.
4. The method according to claim 1, wherein the insulating nanoceramic filler in step S3 is one or more of nano silicon carbide, nano boron nitride, nano aluminum oxide, nano aluminum nitride, and nano titanium carbide.
5. The method of claim 1, wherein the thermoplastic resin A and the thermoplastic resin B are fully dried before melt-mixing in steps S1 and S2.
6. The method of claim 1, wherein in the masterbatch I of step S1, the conductive nanofiller is present in an amount of 1 to 2 vol%; in the master batch II of the step S2, the volume fraction of the insulating heat-conducting ceramic filler is 1-6 vol%; in step S3, the volume ratio of the master batch I to the master batch II is 40/60-60/40.
7. The method of claim 1, wherein the conductive nano-filler, the insulating nano-ceramic filler and the polymers A and B are fully ground and pre-mixed before melt-mixing in steps S1 and S2.
8. A nanocomposite with high thermal conductivity and low dielectric loss based on an incompatible polymer system prepared by the process according to any of claims 1 to 7, characterized in that its thermal conductivity is greater than 0.8 and its dielectric loss in the X-band is less than 0.32.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110168544.9A CN112961452B (en) | 2021-02-07 | 2021-02-07 | Preparation method of polymer-based nanocomposite material with high thermal conductivity and low dielectric loss for microwave communication |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110168544.9A CN112961452B (en) | 2021-02-07 | 2021-02-07 | Preparation method of polymer-based nanocomposite material with high thermal conductivity and low dielectric loss for microwave communication |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112961452A CN112961452A (en) | 2021-06-15 |
| CN112961452B true CN112961452B (en) | 2021-12-10 |
Family
ID=76275149
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110168544.9A Active CN112961452B (en) | 2021-02-07 | 2021-02-07 | Preparation method of polymer-based nanocomposite material with high thermal conductivity and low dielectric loss for microwave communication |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112961452B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116102947A (en) * | 2022-09-09 | 2023-05-12 | 江苏合和阖新材料科技有限公司 | Insulating heat dissipation coating and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3981889B2 (en) * | 2005-06-15 | 2007-09-26 | 東洋紡績株式会社 | High frequency electronic components |
| JP2008222955A (en) * | 2007-03-15 | 2008-09-25 | Nec Corp | Thermoconductive resin composition and thermoconductive resin molded article |
| JP2010155953A (en) * | 2009-01-05 | 2010-07-15 | National Institute Of Advanced Industrial Science & Technology | Structure composed of filler and non-compatible resin or elastomer, method for producing the same, and use of the same |
| CN102286207B (en) * | 2011-06-22 | 2015-12-02 | 四川大学 | A kind of thermoplastic polymer based thermal conductive composite and preparation method thereof |
| CN106977830B (en) * | 2017-04-24 | 2019-01-25 | 四川大学 | Thermal conductive polymer composite material and preparation method with isolation dual network structure |
-
2021
- 2021-02-07 CN CN202110168544.9A patent/CN112961452B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112961452A (en) | 2021-06-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113150541B (en) | High-strength high-thermal-conductivity nylon composite material and preparation method thereof | |
| Xiao et al. | Preparation of highly thermally conductive epoxy resin composites via hollow boron nitride microbeads with segregated structure | |
| CN110128792B (en) | Thermal interface composite material and preparation method and application thereof | |
| CN110951254A (en) | Boron nitride composite high-thermal-conductivity insulating polymer composite material and preparation method thereof | |
| Zhang et al. | Improved thermal and electrical properties of epoxy resin composites by dopamine and silane coupling agent modified hexagonal BN | |
| CN113150544B (en) | Oriented boron nitride @ polydopamine @ silver hybrid nanosheet flexible thermal interface material and preparation method thereof | |
| CN110016205B (en) | Epoxy resin heat-conducting insulating material and preparation method thereof | |
| CN111534016B (en) | Electronic packaging material with heat conduction and electromagnetic shielding performance and preparation method thereof | |
| Weng et al. | Preparation and properties of boron nitride/epoxy composites with high thermal conductivity and electrical insulation | |
| CN112961452B (en) | Preparation method of polymer-based nanocomposite material with high thermal conductivity and low dielectric loss for microwave communication | |
| CN113214583A (en) | Thermal interface material with vertical sandwich structure and preparation method thereof | |
| CN111471299B (en) | Heat-conducting and insulating polyimide nano composite film and preparation method thereof | |
| Li et al. | High-performance epoxy resin/silica coated flake graphite composites for thermal conductivity and electrical insulation | |
| Wang et al. | Achieving high thermal conductivity in epoxy resin composites by synergistically utilizing Al2O3 framework and BN sheet as fillers | |
| Xie et al. | Spherical boron nitride/pitch‐based carbon fiber/silicone rubber composites for high thermal conductivity and excellent electromagnetic interference shielding performance | |
| Wang et al. | High electromagnetic interference shielding effectiveness in MgO composites reinforced by aligned graphene platelets | |
| CN110607161A (en) | Preparation method of diamond-filled silicone rubber heat-conducting adhesive | |
| Guo et al. | Magnetically assisted construction of Al2O3 platelets dual network and its excellent thermal conductivity in epoxy resin composites | |
| Hu et al. | Polyhedral oligosilsesquioxane-modified alumina/aluminum nitride/silicone rubber composites to enhance dielectric properties and thermal conductivity | |
| Yan et al. | Multi-scale hybrid spherical graphite composites: a light weight thermal interface material with high thermal conductivity and simple processing technology | |
| CN114196186B (en) | Multi-scale insulating heat conduction PC composite material based on nano regulation and control and preparation method thereof | |
| WO2021039477A1 (en) | Electromagnetic wave absorbing material | |
| CN115491009A (en) | Anisotropic composite material and preparation method thereof | |
| CN115785864A (en) | PI-Al 2 O 3 Preparation method of PI-BN codoped high-thermal-conductivity epoxy resin composite material | |
| Yakubu et al. | The effect of ZnO nanoparticle filler on the attenuation of ZnO/PCL nanocomposites using microstrip line at microwave frequency |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |