CN114075386A - Liquid metal resin composite material with bicontinuous structure and preparation method thereof - Google Patents
Liquid metal resin composite material with bicontinuous structure and preparation method thereof Download PDFInfo
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- CN114075386A CN114075386A CN202110995778.0A CN202110995778A CN114075386A CN 114075386 A CN114075386 A CN 114075386A CN 202110995778 A CN202110995778 A CN 202110995778A CN 114075386 A CN114075386 A CN 114075386A
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- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 104
- 239000000463 material Substances 0.000 title claims abstract description 78
- 239000000805 composite resin Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 35
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 6
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005751 Copper oxide Substances 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 3
- 229910000431 copper oxide Inorganic materials 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 229920000098 polyolefin Polymers 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 229910001923 silver oxide Inorganic materials 0.000 claims description 3
- 239000011787 zinc oxide Substances 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 20
- 229910052802 copper Inorganic materials 0.000 abstract description 20
- 239000010949 copper Substances 0.000 abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 13
- 238000012360 testing method Methods 0.000 description 44
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 12
- 230000007797 corrosion Effects 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 12
- 229910052733 gallium Inorganic materials 0.000 description 12
- 235000011837 pasties Nutrition 0.000 description 10
- 239000000945 filler Substances 0.000 description 7
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- -1 aluminum metals Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910001152 Bi alloy Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- AMTWCFIAVKBGOD-UHFFFAOYSA-N dioxosilane;methoxy-dimethyl-trimethylsilyloxysilane Chemical compound O=[Si]=O.CO[Si](C)(C)O[Si](C)(C)C AMTWCFIAVKBGOD-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000004200 microcrystalline wax Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229940083037 simethicone Drugs 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Images
Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- 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
Abstract
The invention discloses a liquid metal resin composite material with a bicontinuous structure and a preparation method thereof, wherein the liquid metal resin composite material comprises the following components in percentage by weight: 30-99% of liquid metal, 0.01-5% of powder for modifying the liquid metal and 1-70% of resin; and a microcosmic bicontinuous structure is formed between the liquid metal modified by the powder and the resin, and the resin is wrapped on the surface of the liquid metal. The invention utilizes the powder to modify the liquid metal, effectively improves the affinity of the liquid metal and the resin, and the prepared liquid metal resin composite material has compressibility and self-lubricity, can passivate the fluidity, conductivity and corrosivity of the liquid metal, can be directly printed on the surfaces of copper and aluminum, and has the functions of a thermal interface material, convenient application and low application cost.
Description
Technical Field
The invention relates to the field of liquid metal, in particular to a liquid metal resin composite material with a bicontinuous structure and a preparation method thereof, which can obviously passivate the fluidity, the conductivity and the corrosivity to metal of the liquid metal and are applied to the fields of thermal interface materials, printed electronics and the like.
Background
The liquid metal refers to a low-melting-point alloy with a melting point lower than 200 ℃, wherein the liquid metal has a lower melting point at room temperature and is liquid at room temperature, and typical liquid metals include mercury, gallium and alloys thereof, bismuth alloy and the like. Liquid metal is widely researched and applied in the fields of thermal interface materials, flexible electronics, intelligent electronics and the like due to the characteristic of high thermal conductivity.
Liquid metal has conductivity and good fluidity, for example, gallium-based liquid metal has the characteristics of low melting point, high boiling point, low vapor pressure and the like, and once leakage to an integrated circuit occurs, the risk of short circuit exists. In addition, liquid metals, such as gallium-based liquid metals, once infiltrated inside copper and aluminum metals to form intermetallic compounds, reduce the mechanical properties of the copper and aluminum metals, and the intermetallic compounds formed also form additional interfacial thermal resistance, resulting in a significant reduction in the thermal conductivity of copper and aluminum.
In the prior art, the heat conduction performance is further enhanced by adding heat conduction enhanced particles and the liquid metal is bonded by adding a viscosity regulator, the liquid metal paste obtained by the method is still in direct contact with the surface of the radiator, the self electrical conductivity and corrosivity still exist, and the liquid metal paste cannot be directly applied to the surfaces of copper and aluminum.
In the prior art, liquid metal is made into liquid metal heat-conducting filler and then processed into heat-conducting products such as films, adhesives and the like. The liquid metal heat-conducting filler is usually prepared by directly adding some organic resin, aerogel and the like, and is used as the filler and also needs to be doped with micro-wax powder, spherical graphite, a dispersing agent, a foaming agent, a leveling agent and other auxiliary agents to promote the dispersion of the filler in matrixes such as films, glue and the like. This technique has the following disadvantages: 1. the liquid metal does not have wrapping property and lubricating property, is directly mixed with organic resin and aerogel and has poor dispersibility; 2. then mixing with supplementary heat-conducting fillers of larger particles such as spherical graphite and the like, and adding a large amount of additives, so that the actual compression interface thickness of the product is larger, the thermal resistance is also larger, and the heat-conducting effect is not obvious; 3. the liquid metal heat-conducting filler is prepared from liquid metal firstly, and then the liquid metal heat-conducting filler is processed into heat-conducting products such as films, glue and the like to realize the use of the liquid metal on the surfaces of copper and aluminum or under other application conditions.
Disclosure of Invention
The invention solves the defects of two processing application methods of liquid metal in the prior art by providing the liquid metal resin composite material with the bicontinuous structure and the preparation method thereof.
In order to solve the technical problems, the invention provides a liquid metal resin composite material with a bicontinuous structure, which comprises the following components in percentage by weight: 30-99% of liquid metal, 0.01-5% of powder for modifying the liquid metal and 1-70% of resin; and a microcosmic bicontinuous structure is formed between the liquid metal modified by the powder and the resin, and the surface of the liquid metal is wrapped by the resin.
In a preferred embodiment of the present invention, the liquid metal is a liquid metal having a melting point of-40 to 150 ℃.
In a preferred embodiment of the present invention, the liquid metal is a liquid metal having a melting point of-40 to 70 ℃.
In a preferred embodiment of the present invention, the powder includes at least one of aluminum oxide, zinc oxide, magnesium oxide, silicon oxide, boron nitride, aluminum nitride, tungsten oxide, chromium oxide, manganese oxide, copper oxide, silver oxide, molybdenum sulfide, or silver powder.
In a preferred embodiment of the present invention, the powder has a particle size of 0.05 to 100 μm and a specific surface area of 10 to 1000m2/g。
In a preferred embodiment of the present invention, the powder is in a spherical shape, a one-dimensional whisker, a two-dimensional sheet structure, or a three-dimensional parting structure.
In a preferred embodiment of the present invention, the viscosity of the resin is 50 to 5000 mPas.
In a preferred embodiment of the present invention, the resin includes at least one of dimethylsilicone oil, polyolefin, or polyethylene oxide.
In order to solve the technical problems, the invention also provides a preparation method of the liquid metal resin composite material, which comprises the following steps:
adding the liquid metal and the powder in a formula amount into a stirring and mixing device for first stirring and mixing to obtain liquid metal modified by the powder, adding the resin in a formula amount, and stirring and mixing for a second time to obtain the state metal resin composite material.
In a preferred embodiment of the present invention, the process conditions of the first stirring and mixing and the second stirring and mixing are as follows: the rotating speed is 10-2000 r/min, the temperature is 20-80 ℃, the time is 5-60 min, and the vacuum degree is 30-100 Pa.
The invention has the beneficial effects that: according to the liquid metal resin composite material with the bicontinuous structure and the preparation method thereof, the liquid metal is modified and modified by using the powder, the affinity between the liquid metal and the resin is effectively improved, the liquid metal is wrapped by the resin to form the bicontinuous structure, the prepared liquid metal resin composite material has compressibility and self-lubricating property, the bicontinuous structure increases the stability of the liquid metal resin composite material and keeps the high thermal conductivity of the liquid metal, the fluidity, the electrical conductivity and the corrosivity of the liquid metal are passivated after the resin is wrapped, the liquid metal resin composite material can be directly printed on the surfaces of copper and aluminum, the function of a thermal interface material is born, the application is convenient, and the application cost is low.
Drawings
FIG. 1 is a scanning electron microscope photograph of a liquid metal resin composite prepared in example 1 of the present invention;
FIG. 2 is a graph showing the effect of printing a liquid metal-resin composite material prepared in example 2 of the present invention on a copper plate;
FIG. 3 is a graph showing the compression effect of the continuous and smooth interface layer formed after a pressure of 1Kg is applied to the liquid metal-resin composite prepared in example 2 of the present invention;
FIG. 4 is a diagram illustrating the corrosion of the liquid metal-resin composite material prepared in example 4 of the present invention on an aluminum plate at a high temperature of 125 ℃;
FIG. 5 is a graph of corrosion of liquid gallium metal on an aluminum plate at a high temperature of 125 ℃;
FIG. 6 is a diagram showing the corrosion of the liquid metal-resin composite material prepared in example 4 of the present invention on a copper plate at a high temperature of 125 ℃;
FIG. 7 is a diagram showing the corrosion of liquid gallium metal on a copper plate at a high temperature of 125 ℃.
Detailed Description
The following detailed description of the preferred embodiments of the present invention, taken in conjunction with the accompanying drawings, will make the advantages and features of the invention easier to understand by those skilled in the art, and thus will clearly and clearly define the scope of the invention.
A liquid metal resin composite material with a bicontinuous structure comprises the following components in percentage by weight:
30-99% of liquid metal, wherein the liquid metal is liquid metal with a melting point of-40-150 ℃, preferably liquid metal with a melting point of-40-70 ℃, and comprises mercury, gallium, alloy thereof, bismuth alloy and the like;
0.01-5% of powder, wherein the powder comprises at least one of aluminum oxide, zinc oxide, magnesium oxide, silicon oxide, boron nitride, aluminum nitride, tungsten oxide, chromium oxide, manganese oxide, copper oxide, silver oxide, molybdenum sulfide or silver powder; specifically, the particle size of the powder is 0.05-100 mu m, and the specific surface area is 10-1000 m2(ii)/g; the powder is in a spherical shape, a one-dimensional whisker, a two-dimensional sheet structure or a three-dimensional parting structure. The powder is used for modifying the surface of the liquid metal, specifically, hydrogen bonds can be formed between oxygen, nitrogen and sulfur atoms introduced by the powder and resin molecular chains, and the acting force between the liquid metal and the resin is obviously improved, so that the acting force between the liquid metal and the resin is enhancedThe affinity between the resins helps to stabilize the liquid metal microstructure.
1-70% of resin, wherein the resin comprises at least one of simethicone, polyolefin or polyethylene oxide, and the viscosity of the resin is 50-5000 mPa & s.
The preparation method of the liquid metal resin composite material comprises the following steps:
adding the liquid metal and the powder in a formula amount into planetary defoaming mixing equipment, and stirring and mixing for 5-60 min under the conditions that the temperature is 20-80 ℃ and the rotating speed is 10-2000 r/min, so that the powder is in full contact with the liquid metal, and modification of the surface of the liquid metal is realized;
and then adding the resin with the formula amount into the planetary defoaming mixing equipment, and continuously stirring and mixing for 5-60 min under the conditions that the temperature is 20-80 ℃ and the rotating speed is 10-2000 r/min, so that the modified liquid metal and the resin are fully contacted to form a microscopic bicontinuous structure between the modified liquid metal and the resin, the resin is completely wrapped on the surface of the liquid metal, the liquid metal is not exposed, the corrosion to metal copper or aluminum can be effectively prevented, and the resin can be directly printed on the surfaces of copper and aluminum to take the function of a thermal interface material.
Example 1
1g of a polymer having a particle diameter of 1 μm and a specific surface area of 50m2Putting the alumina powder per gram and 30 grams of gallium indium tin alloy (7:2:1) into a mixing tank, mixing for 10 minutes in a planetary defoaming mixer at the mixing speed of 500r/min and the vacuum degree of 50Pa to obtain a silvery white pasty material, namely the liquid metal modified by the powder.
5 g of dimethylsilicone oil with the viscosity of 1000 mPa.s is added into the silver white pasty material, and the mixture is mixed for 10min in a planetary defoaming mixer, the mixing speed is 500r/min, and the vacuum degree is 50Pa, so that the gray pasty material is obtained.
And observing the microstructure of the gray paste material obtained by the method under a scanning electron microscope to obtain the mutually wrapped liquid metal resin composite material. The scanning electron micrograph is shown in FIG. 1.
The gray paste material was tested on a thermal resistance testerThe test pressure is 200N, the cold electrode temperature is 20 ℃, the hot electrode temperature is 80 ℃, the heat conductivity is 8W/mK, and the thermal resistance is 0.02 ℃ cm2/W。
Example 2
0.3g of tungsten oxide powder having a particle size of 200nm and 30g of gallium-indium alloy (7.5:2.5) were put into a planetary defoaming mixer and mixed for 10 minutes at a mixing speed of 800r/min and a vacuum degree of 50Pa to obtain a silver-white paste material.
10g of polyalphaolefin having a viscosity of 800 mPas was added to the above silver white paste material, and mixed in a planetary defoaming mixer for 20min at a mixing speed of 800r/min and a vacuum degree of 50Pa to obtain a gray paste material.
Performance testing
(1) Thermal conductivity and thermal resistance: the gray paste material prepared by the method is tested for heat conductivity and thermal resistance on a thermal resistance instrument, the test pressure is 200N, the cold electrode temperature is 20 ℃, the hot electrode temperature is 80 ℃, the heat conductivity is 7.8W/mK, and the thermal resistance is 0.03 ℃ cm2/W。
(2) The above gray paste material was printed on a copper plate in the form of steel mesh printing with a thickness of 0.1mm, and a complete pattern was obtained as shown in fig. 2.
(3) The slide was placed over the printed pattern and a 1Kg pressure was applied to form a continuous smooth interface layer. As shown in fig. 3.
Example 3
1g of aluminum nitride powder with the grain diameter of 5 mu m and 30g of gallium are put into a planetary defoaming mixer and mixed for 10min in the planetary defoaming machine, the mixing speed is 500r/min, the vacuum degree is 50Pa, and a silvery white pasty material, namely the powder modified liquid metal, is obtained.
15 g of polydimethylsiloxane oil with the viscosity of 1000mPa & s is added into the silver white pasty material, and the mixture is mixed for 30min in a planetary defoaming mixer, the mixing speed is 500r/min, and the vacuum degree is 50Pa, so that the gray pasty material is obtained. The mixing temperature was controlled to 30 ℃ throughout the mixing process.
Performance testing
(1) Thermal conductivity and thermal resistance: the gray paste material prepared by the method is tested for heat conductivity and thermal resistance on a thermal resistance instrument, the test pressure is 200N, the cold electrode temperature is 20 ℃, the hot electrode temperature is 80 ℃, the heat conductivity is 8.2W/mK, and the thermal resistance is 0.02 ℃ cm2/W。
(2) Testing thermal resistance stability at high temperature: the gray paste material prepared by the method is coated on a stability test jig, and is tested in a forced air drying oven after being assembled under pressure, wherein the test temperature is 125 ℃, and the test time is 1000 hours. The percent change in thermal resistance data obtained from the test is shown in table 1 below.
TABLE 1
As can be seen from the above Table 1, the interface thermal resistance of the gray paste material is reduced after 250 hours of testing, which is due to the reason that the wettability between the material and the heat sink and the heat source is gradually improved, and the interface thermal resistance is maintained in a lower thermal resistance range and has smaller fluctuation within 1000 hours of testing, so that the liquid metal resin composite material provided by the invention is used as a thermal interface material and can maintain low thermal resistance under long-term high-temperature operation.
(3) Testing thermal resistance stability at high and low temperatures: the gray paste material prepared by the method is coated on a stability test jig, and after pressure assembly, the percentage of change of the interface thermal resistance is tested in a high-low temperature environment test box, wherein the test temperature is-40-125 ℃, and the test time is 1000 hours. The percent change in thermal resistance data obtained from the test is shown in table 2 below.
TABLE 2
From the above table, it can be seen that the interface thermal resistance of the gray paste material is reduced after 250 hours of testing, which is due to the reason that the wettability between the material and the heat sink and the heat source is gradually improved, and the interface thermal resistance is maintained in a lower thermal resistance range and has smaller fluctuation within 1000 hours of testing, which indicates that the liquid metal resin composite material of the present invention is used as a thermal interface material, and can maintain low thermal resistance under long-time high-low temperature cold and hot shock operation.
Example 4
0.5 g of alumina powder with the grain diameter of 1 micron, 0.5 g of aluminum nitride powder with the grain diameter of 5 microns and 30g of gallium are put into a mixing tank and mixed for 10 minutes in a planetary defoaming mixer at the mixing speed of 500 revolutions per minute and the vacuum degree of 50Pa to obtain a silvery white pasty material, namely the liquid metal after powder modification.
5 g of dimethylsilicone oil having a viscosity of 1000 mPas was added to the above silver white paste material, and the mixture was mixed in a planetary defoaming mixer at a mixing speed of 500 rpm and a vacuum degree of 50Pa to obtain a gray paste material.
Performance testing
(1) Thermal conductivity and thermal resistance: the gray paste material prepared by the method is tested for heat conductivity and thermal resistance on a thermal resistance instrument, the test pressure is 200N, the cold electrode temperature is 20 ℃, the hot electrode temperature is 80 ℃, the heat conductivity is 8.3W/mK, and the thermal resistance is 0.02 ℃ cm2/W。
(2) And (3) resistivity testing: the resistivity of the gray paste material prepared by the method is tested by using a volume resistivity tester, the testing voltage is 200V, and the testing volume resistivity is 30000 ohm per centimeter.
(3) And (3) testing the corrosion of the aluminum plate: and (3) coating the heat-conducting paste on an aluminum plate for corrosivity test, wherein the test condition is that the heat-conducting paste is placed in an oven at 125 ℃ for 1000 hours, and no obvious corrosion is found after the test for 1000 hours. The test results are shown in FIG. 4.
And (3) comparison test: the liquid metal gallium is used for aluminum surface corrosion behavior research, and the test result is as follows: in a baking oven at 125 ℃, the corrosion of the copper surface is obvious after 168 hours, the copper surface presents obvious silvery white marks, and CuGa is formed2An alloy phase. See figure 5.
(4) And (3) testing the corrosivity of the copper plate: and (3) coating the heat-conducting paste on a copper plate for corrosion test, wherein the test condition is that the heat-conducting paste is placed in an oven at 125 ℃ for 1000 hours, and no obvious corrosion is found after the test for 1000 hours. The test results are shown in FIG. 6.
And (3) comparison test: the liquid metal gallium is used for researching the corrosion behavior of the surface of the copper plate, and the test result is as follows: in an oven at 125 ℃, the copper surface is obviously corroded after 168 hours. See fig. 7.
Example 5
0.5 g of zinc oxide powder with the grain diameter of 1 micron, 0.5 g of silver powder with the grain diameter of 1 micron and 30g of gallium are put into a mixing tank and mixed in a planetary defoaming mixer for 10 minutes at the mixing speed of 500 revolutions per minute and the vacuum degree of 50Pa, and a silver white pasty material is obtained.
5 g of dimethyl silicone oil with the viscosity of 100 is added into the silver white pasty material, and the mixture is mixed in a planetary defoaming machine for 10 minutes, the mixing speed is 500 rpm, and the vacuum degree is 50Pa, so that the gray pasty material is obtained.
Performance testing
(1) Thermal conductivity and thermal resistance: the gray paste material prepared by the method is tested for the heat conductivity coefficient and the thermal resistance value on a thermal resistance instrument, and the test conditions are as follows: the pressure is 200N, the cold electrode temperature is 20 ℃, the hot electrode temperature is 80 ℃, and the test result is as follows: the thermal conductivity coefficient is 8.5W/mK, and the thermal resistance is 0.018 ℃ cm2/W。
(2) The gray paste material prepared by the method is smeared on the surface of a bare belt chip of a notebook computer, and after a heat pipe is assembled, a start-up test is carried out. The test conditions are that the working efficiency of the central processing unit is 100%, the power is 45W, and the temperature of the central processing unit is 82 ℃.
And (3) comparison test: the temperature drop experiment comparison of the notebook computer is carried out by using 6W commercial silicone grease, and the test result shows that the temperature of the central processing unit is 92 ℃ which is higher than the temperature drop effect of the gray paste material.
The liquid metal resin composite material prepared by the method has the following advantages:
(1) the liquid metal is modified by the powder and then mixed with the resin, so that the acting force between the liquid metal and the resin is effectively improved, the microstructure of the liquid metal is stabilized, and the obtained liquid metal resin composite material can remarkably passivate the fluidity, the conductivity and the corrosivity of the liquid metal;
(2) the prepared liquid metal resin composite material has good compressibility, can be compressed to about 10 mu m under the pressurization condition, and has obvious effect of reducing the interface thermal resistance;
(3) the prepared liquid metal resin composite material can be directly applied to the surfaces of copper and aluminum radiators, no additional surface treatment is needed, metal is not corroded, and the application cost is obviously reduced;
(4) the prepared liquid metal resin composite material can be used as a thermal interface material and has excellent stability under the conditions of high temperature, long term and high humidity;
(5) the prepared liquid metal resin composite material can be used as a thermal interface material, the working temperature of the chip is obviously reduced, and the working efficiency and the service life of the chip are improved.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present specification and drawings, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. The liquid metal resin composite material with the bicontinuous structure is characterized by comprising the following components in percentage by weight: 30-99% of liquid metal, 0.01-5% of powder for modifying the liquid metal and 1-70% of resin; and a microcosmic bicontinuous structure is formed between the liquid metal modified by the powder and the resin, and the surface of the liquid metal is wrapped by the resin.
2. The liquid metal-resin composite material with a bicontinuous structure of claim 1, wherein said liquid metal is a liquid metal having a melting point of-40 to 150 ℃.
3. The liquid metal-resin composite material with a bicontinuous structure of claim 2, wherein said liquid metal is a liquid metal having a melting point of-40 to 70 ℃.
4. The liquid metal-resin composite material with a bicontinuous structure of claim 1, characterized in that said powder comprises at least one of aluminum oxide, zinc oxide, magnesium oxide, silicon oxide, boron nitride, aluminum nitride, tungsten oxide, chromium oxide, manganese oxide, copper oxide, silver oxide, molybdenum sulfide, or silver powder.
5. The liquid metal-resin composite material with a bicontinuous structure of claim 4, wherein the powder has a particle size of 0.05 to 100 μm and a specific surface area of 10 to 1000m2/g。
6. The liquid metal-resin composite material with a bicontinuous structure of claim 5, wherein the powder is spherical, one-dimensional whisker, two-dimensional sheet structure, or three-dimensional parting structure.
7. The liquid metal-resin composite material with a bicontinuous structure of claim 1, characterized in that the viscosity of said resin is 50 to 5000 mPa-s.
8. The liquid metal-resin composite with a bicontinuous structure of claim 7, characterized in that said resin comprises at least one of dimethylsilicone oil, polyolefin or polyethylene oxide.
9. A method for preparing a liquid metal-resin composite material having a bicontinuous structure as defined in any one of claims 1 to 8, comprising the steps of:
adding the liquid metal and the powder in a formula amount into a stirring and mixing device for first stirring and mixing to obtain liquid metal modified by the powder, adding the resin in a formula amount, and stirring and mixing for a second time to obtain the state metal resin composite material.
10. The method for preparing a liquid metal-resin composite material with a bicontinuous structure of claim 9, wherein the process conditions of the first stirring and mixing and the second stirring and mixing are as follows: the rotating speed is 10-2000 r/min, the temperature is 20-80 ℃, the time is 5-60 min, and the vacuum degree is 30-100 Pa.
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