CN117603659B - Preparation method of liquid metal/graphene three-dimensional heat conduction material and heat conduction polymer composite material - Google Patents
Preparation method of liquid metal/graphene three-dimensional heat conduction material and heat conduction polymer composite material Download PDFInfo
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- CN117603659B CN117603659B CN202410073128.4A CN202410073128A CN117603659B CN 117603659 B CN117603659 B CN 117603659B CN 202410073128 A CN202410073128 A CN 202410073128A CN 117603659 B CN117603659 B CN 117603659B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 171
- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 157
- 239000000463 material Substances 0.000 title claims abstract description 57
- 229920000642 polymer Polymers 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 43
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 28
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 28
- 229910052738 indium Inorganic materials 0.000 claims abstract description 28
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002135 nanosheet Substances 0.000 claims abstract description 28
- 229910052718 tin Inorganic materials 0.000 claims abstract description 28
- 229920002635 polyurethane Polymers 0.000 claims abstract description 22
- 239000004814 polyurethane Substances 0.000 claims abstract description 22
- 230000001070 adhesive effect Effects 0.000 claims abstract description 14
- 239000000853 adhesive Substances 0.000 claims abstract description 12
- 239000004020 conductor Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- 238000001179 sorption measurement Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 12
- 229920001940 conductive polymer Polymers 0.000 claims description 7
- 239000002322 conducting polymer Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000005336 cracking Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 abstract description 11
- 238000003763 carbonization Methods 0.000 abstract 1
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- 239000006260 foam Substances 0.000 description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 239000000945 filler Substances 0.000 description 19
- 239000002390 adhesive tape Substances 0.000 description 15
- 239000004925 Acrylic resin Substances 0.000 description 13
- 229920000178 Acrylic resin Polymers 0.000 description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 11
- 229920005830 Polyurethane Foam Polymers 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- 239000011496 polyurethane foam Substances 0.000 description 11
- 239000006262 metallic foam Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 3
- 239000002064 nanoplatelet Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
- C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Cooling Or The Like Of Semiconductors Or Solid State Devices (AREA)
Abstract
The invention discloses a preparation method of a liquid metal/graphene three-dimensional heat conduction material, which is characterized in that polyurethane sponge is immersed in a liquid metal/graphene mixture, heated and cracked under a protective atmosphere after being extruded and adsorbed to be saturated, so that the liquid metal/graphene three-dimensional heat conduction material with an independent carbon skeleton is obtained through complete carbonization of the polyurethane sponge, wherein the liquid metal in the liquid metal/graphene mixture consists of gallium, indium and tin, and graphene in the liquid metal/graphene mixture is graphene nano-sheets. Further soaking the liquid metal/graphene three-dimensional heat conduction material in an adhesive, vacuumizing and mixing to obtain the liquid metal/graphene three-dimensional heat conduction polymer composite material, wherein the volume ratio of the liquid metal/graphene three-dimensional heat conduction polymer composite material in the liquid metal/graphene three-dimensional heat conduction polymer composite material is 5% -20%. The heat conducting material obtained by the invention has high heat conducting property and can reduce the influence on the adhesive property of the adhesive material.
Description
Technical Field
The invention relates to a heat conducting material and a preparation method of a heat conducting polymer composite material, in particular to a preparation method of a liquid metal/graphene three-dimensional heat conducting material and a preparation method of a heat conducting polymer composite material.
Background
The heat conducting polymer material has the characteristics of light weight, low cost, good mechanical property, strong corrosion resistance, good processability and the like, and is widely applied to thermal interface materials. Since the intrinsic thermal conductivity of the polymer matrix in the thermally conductive polymer material is very low, the introduction of highly thermally conductive fillers is a conventional and viable method of increasing the thermal conductivity of the composite. However, while thermally conductive fillers can be effective in improving the thermal conductivity of the polymer, formation of a thermally conductive network generally occurs at higher filler loading levels. The presence of high loadings and second phases can affect the properties of the composite, making it difficult to meet the design requirements of the thermal interface material.
The graphene is very suitable for being used as a filler to prepare a heat-conducting polymer material due to the two-dimensional plane structure and the high transverse-longitudinal ratio of the graphene, and the material has the advantages of good processability, corrosion resistance, low production cost and the like. In the prior art, graphene is typically dispersed in a polymer matrix in the form of a powder. In order to form a continuous heat conduction channel, the loading amount of graphene is generally more than 20wt%, however, the powder dispersion type graphene/polymer composite material has higher viscosity and poorer mechanical property, and certain obstruction is brought to industrialized development. In addition, a large number of two-phase interfaces exist between graphene sheets and polymers dispersed in a matrix, so that serious phonon scattering is caused, the dispersion effect of graphene powder in the matrix is influenced by conjugation, and the heat conduction performance of the composite material is reduced due to the factors.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of a liquid metal/graphene three-dimensional heat conduction material and a preparation method of a heat conduction polymer composite material using the liquid metal/graphene three-dimensional heat conduction material, which solve the problem that the traditional adhesive has to rely on high heat conduction filler content (> 40%) to obtain high heat conduction performance but can cause the great reduction of bonding strength (< 10N), namely solve the problem of contradiction between the heat conduction performance and the bonding performance.
The technical scheme of the invention is as follows: the preparation method of the liquid metal/graphene three-dimensional heat conduction material comprises the steps of immersing polyurethane sponge into a liquid metal/graphene mixture, heating and cracking the polyurethane sponge under a protective atmosphere after extrusion and adsorption saturation to obtain the liquid metal/graphene three-dimensional heat conduction material with an independent carbon skeleton, wherein the liquid metal in the liquid metal/graphene mixture consists of gallium, indium and tin, and the graphene in the liquid metal/graphene mixture is graphene nano sheets.
The other technical scheme of the invention is as follows: the preparation method of the liquid metal/graphene three-dimensional heat conduction polymer composite material comprises the steps of infiltrating an adhesive into the liquid metal/graphene three-dimensional heat conduction material, vacuumizing and mixing to obtain the liquid metal/graphene three-dimensional heat conduction polymer composite material, wherein the volume ratio of the liquid metal/graphene three-dimensional heat conduction polymer composite material to the liquid metal/graphene three-dimensional heat conduction polymer composite material is 5% -20%, preferably 10% -20%.
Further, the pore diameter of the polyurethane sponge is 50-200 mu m.
Further, the mass ratio of the liquid metal to the graphene nanoplatelets in the liquid metal/graphene mixture is 1:1-1:3.
Further, the mass percentages of gallium, indium and tin in the liquid metal are respectively 20% -40%, 40% -50% and 20% -40%.
Further, the heating temperature during the heating and cracking is 400-600 ℃.
Compared with the prior art, the technical scheme provided by the invention has the advantages that:
The graphene nano sheet skeleton is matched with carbonized polyurethane to provide a continuous three-dimensional heat conduction path for the composite material, so that the phonon scattering in the composite material is greatly reduced, and the heat conduction performance of the adhesive material can be effectively improved even under the condition of lower filling content.
The interface thermal resistance between the fillers, namely the contact thermal resistance between the fillers is different from the interface thermal resistance between the fillers and the adhesive, when the fraction of the fillers is low, the main factor influencing the thermal conductivity of the adhesive is the interface thermal resistance between the fillers and the adhesive, when the fraction of the fillers is increased, the fillers are overlapped with each other, and the contact thermal resistance between the fillers is shown and often takes the dominant role. The bridging of the fillers involves the formation of a thermally conductive network, and the magnitude of the thermal contact resistance between the fillers (i.e., the ease with which heat is transferred from the filler to the adjacent filler) becomes a critical factor affecting the thermally conductive network. According to the invention, the liquid metal forms connection between graphene sheets, so that the interface thermal resistance between fillers can be greatly reduced, and the network interconnectivity and the thermal conductivity are greatly improved.
In addition, the liquid metal/graphene three-dimensional heat conduction material directly forms a heat conduction network structure, so that the heat conductivity of the glue material can be improved under the condition of lower filler content, and the problem of the reduction of the adhesive property of the glue material caused by high filler content is avoided.
Detailed Description
The present application is further described below with reference to examples, which are to be construed as merely illustrative of the present application and not limiting of its scope, and various modifications to the equivalent arrangements of the present application will become apparent to those skilled in the art upon reading the present description, which are within the scope of the application as defined in the appended claims.
Example 1a polyurethane sponge (pore size 100 μm) was cut into the original foam skeleton, then immersed in a liquid metal/graphene mixture and repeatedly extruded to adsorption saturation. The liquid metal In the liquid metal/graphene mixture is formed by fusing gallium (Ga), indium (In) and tin (Sn), wherein the mass ratio of gallium is 24%, the mass ratio of indium is 40%, and the mass ratio of tin is 36%. The graphene in the liquid metal/graphene mixture is a graphene nano sheet with the size of 5 mu m and the thickness of about 40nm, and the liquid metal and the graphene nano sheet are mixed according to the mass ratio of 1:2.
The liquid metal/graphene is assembled on the surface of the polyurethane foam skeleton through the extrusion adsorption process, the assembled foam is heated at a high temperature of 500 ℃ under the protection of nitrogen, the coated foam is thermally cracked rapidly, and the polymer is fully carbonized, so that the liquid metal/graphene three-dimensional heat conduction material with the independent carbon skeleton is obtained. And then, soaking the liquid metal/graphene three-dimensional heat conduction material in acrylic resin, and vacuumizing to prepare the liquid metal foam/acrylic acid high heat conduction adhesive tape, wherein the volume fraction of the liquid metal/graphene three-dimensional heat conduction material is 15%.
Example 2a polyurethane sponge (pore size 100 μm) was cut into the original foam skeleton, then immersed in a liquid metal/graphene mixture and repeatedly extruded to adsorption saturation. The liquid metal In the liquid metal/graphene mixture is formed by fusing gallium (Ga), indium (In) and tin (Sn), wherein the mass ratio of gallium is 24%, the mass ratio of indium is 40%, and the mass ratio of tin is 36%. The graphene in the liquid metal/graphene mixture is a graphene nano sheet with the size of 5 mu m and the thickness of about 40nm, and the liquid metal and the graphene nano sheet are mixed according to the mass ratio of 1:2.
The liquid metal/graphene is assembled on the surface of the polyurethane foam skeleton through the extrusion adsorption process, the assembled foam is heated at a high temperature of 500 ℃ under the protection of nitrogen, the coated foam is thermally cracked rapidly, and the polymer is fully carbonized, so that the liquid metal/graphene three-dimensional heat conduction material with the independent carbon skeleton is obtained. And then, soaking the liquid metal/graphene three-dimensional heat conduction material in acrylic resin, and vacuumizing to prepare the liquid metal foam/acrylic acid high heat conduction adhesive tape, wherein the volume fraction of the liquid metal/graphene three-dimensional heat conduction material is 20%.
Example 3 a polyurethane sponge (pore size 100 μm) was cut into the original foam skeleton, then immersed in a liquid metal/graphene mixture and repeatedly extruded to adsorption saturation. The liquid metal In the liquid metal/graphene mixture is formed by fusing gallium (Ga), indium (In) and tin (Sn), wherein the mass ratio of gallium is 24%, the mass ratio of indium is 40%, and the mass ratio of tin is 36%. The graphene in the liquid metal/graphene mixture is a graphene nano sheet with the size of 5 mu m and the thickness of about 40nm, and the liquid metal and the graphene nano sheet are mixed according to the mass ratio of 1:2.
The liquid metal/graphene is assembled on the surface of the polyurethane foam skeleton through the extrusion adsorption process, the assembled foam is heated at a high temperature of 500 ℃ under the protection of nitrogen, the coated foam is thermally cracked rapidly, and the polymer is fully carbonized, so that the liquid metal/graphene three-dimensional heat conduction material with the independent carbon skeleton is obtained. And then, soaking the liquid metal/graphene three-dimensional heat conduction material in acrylic resin, and vacuumizing to prepare the liquid metal foam/acrylic acid high heat conduction adhesive tape, wherein the volume fraction of the liquid metal/graphene three-dimensional heat conduction material is 10%.
Example 4a polyurethane sponge (pore size 100 μm) was cut into the original foam skeleton, then immersed in a liquid metal/graphene mixture and repeatedly extruded to adsorption saturation. The liquid metal In the liquid metal/graphene mixture is formed by fusing gallium (Ga), indium (In) and tin (Sn), wherein the mass ratio of gallium is 24%, the mass ratio of indium is 40%, and the mass ratio of tin is 36%. The graphene in the liquid metal/graphene mixture is a graphene nano sheet with the size of 5 mu m and the thickness of about 40nm, and the liquid metal and the graphene nano sheet are mixed according to the mass ratio of 1:2.
The liquid metal/graphene is assembled on the surface of the polyurethane foam skeleton through the extrusion adsorption process, the assembled foam is heated at a high temperature of 500 ℃ under the protection of nitrogen, the coated foam is thermally cracked rapidly, and the polymer is fully carbonized, so that the liquid metal/graphene three-dimensional heat conduction material with the independent carbon skeleton is obtained. And then, soaking the liquid metal/graphene three-dimensional heat conduction material in acrylic resin, and vacuumizing to prepare the liquid metal foam/acrylic acid high heat conduction adhesive tape, wherein the volume fraction of the liquid metal/graphene three-dimensional heat conduction material is 5%.
Example 5a polyurethane sponge (pore size 100 μm) was cut into the original foam skeleton, then immersed in a liquid metal/graphene mixture and repeatedly extruded to adsorption saturation. The liquid metal In the liquid metal/graphene mixture is formed by fusing gallium (Ga), indium (In) and tin (Sn), wherein the mass ratio of gallium is 24%, the mass ratio of indium is 40%, and the mass ratio of tin is 36%. The graphene in the liquid metal/graphene mixture is a graphene nano sheet with the size of 5 mu m and the thickness of about 40nm, and the liquid metal and the graphene nano sheet are mixed according to the mass ratio of 1:1.
The liquid metal/graphene is assembled on the surface of the polyurethane foam skeleton through the extrusion adsorption process, the assembled foam is heated at a high temperature of 500 ℃ under the protection of nitrogen, the coated foam is thermally cracked rapidly, and the polymer is fully carbonized, so that the liquid metal/graphene three-dimensional heat conduction material with the independent carbon skeleton is obtained. And then, soaking the liquid metal/graphene three-dimensional heat conduction material in acrylic resin, and vacuumizing to prepare the liquid metal foam/acrylic acid high heat conduction adhesive tape, wherein the volume fraction of the liquid metal/graphene three-dimensional heat conduction material is 15%.
Example 6a polyurethane sponge (pore size 100 μm) was cut into the original foam skeleton, then immersed in a liquid metal/graphene mixture and repeatedly extruded to adsorption saturation. The liquid metal In the liquid metal/graphene mixture is formed by fusing gallium (Ga), indium (In) and tin (Sn), wherein the mass ratio of gallium is 24%, the mass ratio of indium is 40%, and the mass ratio of tin is 36%. The graphene in the liquid metal/graphene mixture is a graphene nano sheet with the size of 5 mu m and the thickness of about 40nm, and the liquid metal and the graphene nano sheet are mixed according to the mass ratio of 1:3.
The liquid metal/graphene is assembled on the surface of the polyurethane foam skeleton through the extrusion adsorption process, the assembled foam is heated at a high temperature of 500 ℃ under the protection of nitrogen, the coated foam is thermally cracked rapidly, and the polymer is fully carbonized, so that the liquid metal/graphene three-dimensional heat conduction material with the independent carbon skeleton is obtained. And then, soaking the liquid metal/graphene three-dimensional heat conduction material in acrylic resin, and vacuumizing to prepare the liquid metal foam/acrylic acid high heat conduction adhesive tape, wherein the volume fraction of the liquid metal/graphene three-dimensional heat conduction material is 15%.
Example 7a polyurethane sponge (pore size 100 μm) was cut into the original foam skeleton, then immersed in a liquid metal/graphene mixture and repeatedly extruded to adsorption saturation. The liquid metal In the liquid metal/graphene mixture is formed by fusing gallium (Ga), indium (In) and tin (Sn), wherein the mass ratio of gallium is 30%, the mass ratio of indium is 50%, and the mass ratio of tin is 20%. The graphene in the liquid metal/graphene mixture is a graphene nano sheet with the size of 5 mu m and the thickness of about 40nm, and the liquid metal and the graphene nano sheet are mixed according to the mass ratio of 1:2.
The liquid metal/graphene is assembled on the surface of the polyurethane foam skeleton through the extrusion adsorption process, the assembled foam is heated at a high temperature of 500 ℃ under the protection of nitrogen, the coated foam is thermally cracked rapidly, and the polymer is fully carbonized, so that the liquid metal/graphene three-dimensional heat conduction material with the independent carbon skeleton is obtained. And then, soaking the liquid metal/graphene three-dimensional heat conduction material in acrylic resin, and vacuumizing to prepare the liquid metal foam/acrylic acid high heat conduction adhesive tape, wherein the volume fraction of the liquid metal/graphene three-dimensional heat conduction material is 15%.
Example 8a polyurethane sponge (pore size 100 μm) was cut into the original foam skeleton, then immersed in a liquid metal/graphene mixture and repeatedly extruded to adsorption saturation. The liquid metal In the liquid metal/graphene mixture is formed by fusing gallium (Ga), indium (In) and tin (Sn), wherein the mass ratio of gallium is 40%, the mass ratio of indium is 40%, and the mass ratio of tin is 20%. The graphene in the liquid metal/graphene mixture is a graphene nano sheet with the size of 5 mu m and the thickness of about 40nm, and the liquid metal and the graphene nano sheet are mixed according to the mass ratio of 1:2.
The liquid metal/graphene is assembled on the surface of the polyurethane foam skeleton through the extrusion adsorption process, the assembled foam is heated at a high temperature of 500 ℃ under the protection of nitrogen, the coated foam is thermally cracked rapidly, and the polymer is fully carbonized, so that the liquid metal/graphene three-dimensional heat conduction material with the independent carbon skeleton is obtained. And then, soaking the liquid metal/graphene three-dimensional heat conduction material in acrylic resin, and vacuumizing to prepare the liquid metal foam/acrylic acid high heat conduction adhesive tape, wherein the volume fraction of the liquid metal/graphene three-dimensional heat conduction material is 15%.
Example 9 a polyurethane sponge (pore size 200 μm) was cut into the original foam skeleton, then immersed in a liquid metal/graphene mixture and repeatedly extruded to adsorption saturation. The liquid metal In the liquid metal/graphene mixture is formed by fusing gallium (Ga), indium (In) and tin (Sn), wherein the mass ratio of gallium is 24%, the mass ratio of indium is 40%, and the mass ratio of tin is 36%. The graphene in the liquid metal/graphene mixture is a graphene nano sheet with the size of 5 mu m and the thickness of about 40nm, and the liquid metal and the graphene nano sheet are mixed according to the mass ratio of 1:2.
The liquid metal/graphene is assembled on the surface of the polyurethane foam skeleton through the extrusion adsorption process, the assembled foam is heated at a high temperature of 400 ℃ under the protection of nitrogen, the coated foam is thermally cracked rapidly, and the polymer is fully carbonized, so that the liquid metal/graphene three-dimensional heat conduction material with the independent carbon skeleton is obtained. And then, soaking the liquid metal/graphene three-dimensional heat conduction material in acrylic resin, and vacuumizing to prepare the liquid metal foam/acrylic acid high heat conduction adhesive tape, wherein the volume fraction of the liquid metal/graphene three-dimensional heat conduction material is 15%.
Example 10 a polyurethane sponge (pore size 50 μm) was cut into the original foam skeleton, then immersed in a liquid metal/graphene mixture and repeatedly extruded to adsorption saturation. The liquid metal In the liquid metal/graphene mixture is formed by fusing gallium (Ga), indium (In) and tin (Sn), wherein the mass ratio of gallium is 24%, the mass ratio of indium is 40%, and the mass ratio of tin is 36%. The graphene in the liquid metal/graphene mixture is a graphene nano sheet with the size of 5 mu m and the thickness of about 40nm, and the liquid metal and the graphene nano sheet are mixed according to the mass ratio of 1:2.
The liquid metal/graphene is assembled on the surface of the polyurethane foam skeleton through the extrusion adsorption process, the assembled foam is heated at a high temperature of 600 ℃ under the protection of nitrogen, the coated foam is thermally cracked rapidly, and the polymer is fully carbonized, so that the liquid metal/graphene three-dimensional heat conduction material with the independent carbon skeleton is obtained. And then, soaking the liquid metal/graphene three-dimensional heat conduction material in acrylic resin, and vacuumizing to prepare the liquid metal foam/acrylic acid high heat conduction adhesive tape, wherein the volume fraction of the liquid metal/graphene three-dimensional heat conduction material is 15%.
Comparative example 1 is an adhesive tape made of pure acrylic acid.
Comparative example 2a heat conductive tape was prepared by mixing liquid metal/graphene In an amount of 15% by volume directly with an acrylic resin by mechanical stirring, wherein the liquid metal In the liquid metal/graphene mixture was formed by fusing gallium (Ga), indium (In) and tin (Sn), wherein the mass ratio of gallium was 24%, the mass ratio of indium was 40% and the mass ratio of tin was 36%. The graphene in the liquid metal/graphene mixture is a graphene nano sheet with the size of 5 mu m and the thickness of about 40nm, and the liquid metal and the graphene nano sheet are mixed according to the mass ratio of 1:2.
Comparative example 3 a polyurethane sponge (pore size 100 μm) was cut into an original foam skeleton, then immersed in a graphene nanoplatelet solution, and repeatedly extruded to adsorption saturation, the graphene nanoplatelets having a size of 5 μm and a thickness of about 40nm. And assembling graphene on the surface of the polyurethane foam skeleton, heating the assembled foam at a high temperature of 500 ℃ under the protection of nitrogen, and rapidly thermally cracking the coated foam to completely carbonize the polymer, so as to obtain the graphene heat-conducting material with the independent carbon skeleton. And then immersing the graphene heat conduction material into acrylic resin and vacuumizing to prepare the acrylic heat conduction adhesive tape, wherein the volume fraction of the liquid metal/graphene three-dimensional heat conduction material is 15%.
The thermal conductivity of the tapes of each of the above examples and comparative examples was tested, and the thermal conductivity test method was performed with reference to astm e1461 standard, and the results are shown in table 1.
Table 1 shows the results of the thermal conductivity tests for each example and each comparative example.
180 ° Peel force of the thermally conductive tape measured according to GB 2792-2014 standard. Specifically, the heat conductive tape was cut into a standard tape of 25mmx200mm, which was then adhered to a stainless steel plate which was wiped with acetone, and then rolled back and forth three times with a rubber roller of 2kg weight to remove air bubbles which may exist between the steel plate and the tape. After 15min of standing, it was tested for 180℃peel force by an electronic peel tester at a peel speed of 300 mm/min. The peel force obtained for each sample was the result of three measurements on average of the peel force, and the results are shown in Table 2.
Table 2 shows the peel force test results of each example and each comparative example.
From the test results, compared with the method that the heat-conducting adhesive tape is prepared by directly mixing liquid metal and graphene nano sheets as heat-conducting fillers into acrylic resin, the heat-conducting material obtained by carbonizing the polyurethane sponge serving as a foam skeleton can exert better heat-conducting effect in the adhesive tape, and the adhesive tape adhesive force is less affected.
Claims (6)
1. The preparation method of the liquid metal/graphene three-dimensional heat conduction material is characterized in that polyurethane sponge is immersed in a liquid metal/graphene mixture, extrusion adsorption is carried out, then the polyurethane sponge is heated and cracked under a protective atmosphere to be fully carbonized to obtain the liquid metal/graphene three-dimensional heat conduction material with an independent carbon skeleton, the liquid metal in the liquid metal/graphene mixture consists of gallium, indium and tin, graphene in the liquid metal/graphene mixture is a graphene nano sheet, the mass ratio of the liquid metal in the liquid metal/graphene mixture to the graphene nano sheet is 1:1-1:3, and the heating temperature during heating and cracking is 400-600 ℃.
2. The method for preparing the liquid metal/graphene three-dimensional heat conducting material according to claim 1, wherein the pore diameter of the polyurethane sponge is 50-200 μm.
3. The preparation method of the liquid metal/graphene three-dimensional heat conduction material according to claim 1, wherein the mass percentages of gallium, indium and tin in the liquid metal are 20% -40%, 40% -50% and 20% -40%, respectively.
4. The preparation method of the liquid metal/graphene three-dimensional heat conduction polymer composite material is characterized by comprising the steps of infiltrating the liquid metal/graphene three-dimensional heat conduction material in the adhesive, vacuumizing and mixing to obtain the liquid metal/graphene three-dimensional heat conduction adhesive, wherein the volume ratio of the liquid metal/graphene three-dimensional heat conduction material in the liquid metal/graphene three-dimensional heat conduction adhesive is 5% -20%.
5. The method for preparing the liquid metal/graphene three-dimensional heat-conducting polymer composite material according to claim 4, wherein the pore diameter of the polyurethane sponge is 50-200 μm.
6. The preparation method of the liquid metal/graphene three-dimensional heat-conducting polymer composite material according to claim 4, wherein the mass percentages of gallium, indium and tin in the liquid metal are 20% -40%, 40% -50% and 20% -40%, respectively.
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