CN116117130A - Liquid metal with reduced surface tension and preparation method and application thereof - Google Patents
Liquid metal with reduced surface tension and preparation method and application thereof Download PDFInfo
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- CN116117130A CN116117130A CN202310217719.XA CN202310217719A CN116117130A CN 116117130 A CN116117130 A CN 116117130A CN 202310217719 A CN202310217719 A CN 202310217719A CN 116117130 A CN116117130 A CN 116117130A
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- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title abstract description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 32
- 239000010937 tungsten Substances 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 25
- 239000002105 nanoparticle Substances 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 12
- 229910052582 BN Inorganic materials 0.000 claims description 14
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 12
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052733 gallium Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 5
- 239000004917 carbon fiber Substances 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 9
- 238000002156 mixing Methods 0.000 description 12
- 229910001128 Sn alloy Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 6
- 239000002905 metal composite material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 3
- 229910000846 In alloy Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- -1 boron nitride compound Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- 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
- C09K5/10—Liquid materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a liquid metal with reduced surface tension, a preparation method and application thereof. The weight portion comprises: 75-96.5 parts of liquid metal, 0.5-5 parts of spherical tungsten particles and 3-20 parts of heat conducting powder; wherein, the metal tungsten nano particles play a role in reducing the surface tension of the liquid metal; after stirring and defoaming, the liquid metal and the heat conducting powder form a continuous heat conducting path, the viscosity of the composite material is greatly increased, the risk of leakage and short circuit of the liquid metal is reduced, and the stability of the liquid metal heat conducting paste is improved. The invention successfully reduces the surface tension of the liquid metal by utilizing the metal tungsten nano particles, improves the wettability and affinity of the liquid metal and other heat conducting powder, can be combined with other heat conducting powder, and expands the application of the liquid metal.
Description
Technical Field
The invention relates to the field of thermal interface materials, in particular to a liquid metal with reduced surface tension, a preparation method and application thereof, which can obviously reduce the surface tension of the liquid metal and improve the wettability to heat conducting powder and solid surfaces, thereby improving the interface of a liquid metal composite heat conducting paste, reducing the risk of short circuit and the like of electronic equipment caused by liquid metal exudation, improving the heat conducting coefficient of the composite heat conducting paste, and being applied to the fields of thermal interface materials, printed electronics and the like.
Background
The rapid development of technology has led to faster, smaller, higher power densities for electronic devices, but higher and higher heating values, due to incomplete surface contact, air gaps always occur at the interface of the heat source and the heat sink, with a thermal conductivity of only 0.026W m -1 K -1 Efficient heat transfer from the heat source to the heat sink is hindered. By filling the air gap with the thermal interface material, the contact resistance of the interface can be reduced and the thermal conductivity can be improved.
Gallium-based liquid metals are of great interest as thermal interface materials for thermal management due to their high thermal conductivity and flow state at room temperature. However, gallium has too high a surface tension to wet the surfaces of the heat source and heat sink, and there is great difficulty and risk of direct application of liquid metal, including device shorting due to leakage of liquid metal.
Filling the liquid metal with high thermal conductivity enhancing particles not only can further enhance thermal conductivity, but can also reduce fluidity to reduce the risk of leakage of the liquid metal. However, the high surface tension of the liquid metal also makes it difficult to well contact the liquid metal with the thermally conductive reinforcing particles to produce a composite thermal interface material.
Researchers are currently exploring the use of metal particles, such as copper, iron, nickel, magnesium, silver, tungsten, as a second phase to reduce the surface tension of liquid metals, and also as a thermal conductivity enhancing particle to reduce leakage and increase the thermal conductivity of liquid metals. This technique has the following drawbacks: 1. most of the metal particles reported to date form intermetallic compounds, create additional interfacial thermal resistance, and over time can lead to failure. 2. The metal-to-metal mixing also results in conductivity still present, causing shorting of the electronic device. 3. The metal material used as the heat conducting filler is likely to be used in a large quantity, so that the cost is raised greatly, and the large-scale industrial production is not facilitated. Therefore, a stable and low-cost method is needed to reduce the surface tension of the liquid metal, and a foundation is laid for developing the liquid metal heat conduction paste.
Disclosure of Invention
The invention provides the liquid metal with reduced surface tension, the preparation method and the application thereof, and solves the problems of difficult infiltration of solid heat conduction powder on the low surface and leakage caused by high surface tension of the liquid metal in the prior art.
In order to solve the technical problems, the liquid metal with reduced surface tension comprises the following raw materials in parts by mass: 75-96.5 parts of liquid metal, 0.5-5 parts of metal tungsten nano particles and 3-20 parts of heat conducting powder. The metal tungsten nano particles can reduce the surface tension of the liquid metal, further increase the affinity of the liquid metal and the heat conducting powder, and strengthen the heat conducting performance of the liquid metal composite material.
In a preferred embodiment of the present invention, the liquid metal is a liquid metal having a melting point of-40 to 60 ℃.
The liquid metal is gallium metal or an alloy thereof. Preferably, the liquid metal is selected from gallium-based alloys.
Further, the liquid metal is at least one selected from gallium indium alloy and gallium indium tin alloy.
Wherein, the particle diameter of the metal tungsten nano particles is 10-100 nanometers, preferably 20 nanometers.
The heat conducting powder comprises at least one of boron nitride, carbon fiber, graphene, aluminum oxide, aluminum nitride, zinc oxide and silicon carbide.
In order to solve the technical problems, the invention also provides a preparation method of the liquid metal with reduced surface tension, which comprises the following steps:
firstly stirring the formula amount of the metal tungsten nano particles and the high-surface-tension liquid metal for the first time to obtain the liquid metal with the surface tension reduced by the nano tungsten, and stirring the liquid metal and the heat conducting powder for the second time to form a liquid metal compound embedded into the heat conducting powder, wherein the compound is the high-performance liquid metal heat conducting paste.
The technological conditions of stirring and mixing are as follows: the stirring speed is 1000 rpm and the stirring time is 5 minutes by adopting a planetary stirring deaerator.
The product obtained by the invention is used as a heat conducting material.
The beneficial effects of the invention are as follows: according to the liquid metal with reduced surface tension, the micro/nano interface is formed in the liquid metal matrix by utilizing the metal tungsten nano particles, so that the surface tension of the liquid metal is reduced, the affinity between the liquid metal and the heat conducting powder is effectively improved, the heat conducting path and the viscosity of the composite material are increased, oil precipitation and liquid metal exudation are avoided, the product is easy to store, the quality guarantee period is prolonged, the good heat conducting coefficient is shown in a heat conducting property test, and the application scene of the liquid metal is expanded.
Drawings
FIG. 1 is a graph showing the contact angle of liquid metal mixed with metal tungsten nanoparticles and boron nitride tablets as described in example 1 of the present invention;
FIG. 2 is a graph showing the contact angle of liquid metal with boron nitride compacts as described in example 1 of the invention;
FIG. 3 is a digital photograph of a liquid metal boron nitride composite thermal paste mixed with metal tungsten nanoparticles as described in example 1 of the present invention;
FIG. 4 is a scanning electron micrograph of a liquid metal boron nitride composite thermal paste mixed with metal tungsten nanoparticles as described in example 1 of the present invention;
fig. 5 is a digital photograph of powder prepared by mixing the liquid metal obtained in comparative example 1 with boron nitride.
Detailed Description
The preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings so that the advantages and features of the present invention can be more easily understood by those skilled in the art, thereby making clear and defining the scope of the present invention.
The liquid metal with reduced surface tension comprises the following components in parts by weight:
75-96.5 parts of liquid metal, wherein the liquid metal is liquid metal with a melting point of-40-60 ℃, preferably liquid metal with a melting point of-40-30 ℃, and comprises gallium-indium alloy, gallium-indium-tin alloy and the like;
0.5 to 5 parts of tungsten, wherein the tungsten is one of nanoscale and micron-sized tungsten, preferably nanoscale spherical tungsten, and particularly the tungsten particle size is 10 to 100 nanometers.
3-20 parts of heat conducting powder, wherein the heat conducting powder comprises at least one of boron nitride, carbon fiber and graphene; specifically, in order to obtain a higher thermal conductivity, the particle size of the thermal conductive powder is 5 to 50 micrometers.
The preparation method of the liquid metal with reduced surface tension comprises the following steps:
adding the liquid metal and the nano tungsten with the formula amount into defoaming mixing equipment, and stirring and mixing at a high speed, wherein the stirring time is 5 minutes at 1000 revolutions per minute.
And then adding the formula amount of the heat conducting powder into the planetary defoaming mixing equipment, fully soaking the liquid metal and the heat conducting powder after the surface tension of the tungsten is reduced under the same stirring condition, embedding the powder into the liquid metal, and controlling the proportion of the powder and the liquid metal to ensure that the composite material still has good fluidity.
Example 1
0.1 g of metal tungsten nanoparticles with the particle size of 20 nanometers and 9.3 g of liquid metal gallium indium tin alloy are placed into a planetary stirring deaerator, the mixing speed is 1000 revolutions per minute, and the mixing time is 5 minutes, so that the liquid metal mixed with the metal tungsten nanoparticles is obtained.
To confirm that the liquid metal mixed with metal tungsten nanoparticles was able to improve contact with the solid surface, liquid metal gallium indium tin alloy was dropped onto the surface of the boron nitride wafer using a microsyringe, and the contact angle of both was calculated using a sessile drop contact angle meter, the contact angle was recorded as 105 °, as shown in fig. 1.
Correspondingly, the contact angle between the liquid metal without the metal tungsten nano-particles and the boron nitride tablet is 133 degrees, as shown in fig. 2, which shows that the contact between the liquid metal and the solid surface is obviously improved after the metal tungsten nano-particles are mixed.
Further, 0.6 g of 5 μm boron nitride was added to the above-mentioned liquid metal heat conductive substrate with reduced surface tension, placed in a stirring cup, stirred in a planetary stirring deaerator at a stirring speed of 1500 rpm for 10 minutes, to obtain a liquid metal composite heat conductive paste as shown in the figure. The scanning electron microscope image is shown in fig. 4.
The liquid metal boron nitride compound heat conduction paste obtained by the method is smeared on a heat conduction instrument, the heat conduction coefficient is tested, the test pressure is 50N, the cold electrode temperature is 20 ℃, the hot electrode temperature is 70 ℃, and the heat conduction coefficient is 14.5W m -1 K -1 。
Example 2
0.1 g of metal tungsten nano particles with the particle size of 20 nanometers and 8.3 g of liquid metal gallium indium tin alloy are placed into a planetary stirring deaerator, the mixing speed is 1000 revolutions per minute, and the mixing time is 5 minutes, so that the liquid metal mixed with the metal tungsten nano particles is obtained.
Further, 1.6 g of graphene with the particle size of 10 microns is added into the liquid metal heat conduction matrix with the surface tension reduced, the mixture is placed into a stirring cup and stirred in a planetary stirring deaerator at the stirring speed of 2000 rpm for 15 minutes, and the liquid metal graphene composite heat conduction paste is obtained.
The liquid metal composite heat conduction paste obtained by the method is smeared on a heat conduction instrument, and the heat conduction coefficient of the gray paste material is tested, the test pressure is 50N, the cold electrode temperature is 20 ℃, the hot electrode temperature is 70 ℃, and the heat conduction coefficient is 17.3W m -1 K -1 。
Example 3
0.1 g of metal tungsten nanoparticles with the particle size of 20 nanometers and 8.7 g of liquid metal gallium indium tin alloy are placed into a planetary stirring deaerator, the mixing speed is 1000 revolutions per minute, and the mixing time is 5 minutes, so that the liquid metal mixed with the metal tungsten nanoparticles is obtained.
Further, 1.2 g of carbon fiber with the length of 50 micrometers is added into the liquid metal heat conduction matrix with the surface tension reduced, and the mixture is placed into a stirring cup and stirred in a planetary stirring deaerator at the stirring speed of 1000 revolutions per minute for 10 minutes, so as to obtain the liquid metal carbon fiber composite heat conduction paste.
The liquid metal composite heat conduction paste obtained by the method is smeared on a heat conduction instrument, and the heat conduction coefficient of the gray paste material is tested, the test pressure is 50N, the cold electrode temperature is 20 ℃, the hot electrode temperature is 70 ℃, and the heat conduction coefficient is 23.8W m -1 K -1 。
Comparative example 1
0.6 g of boron nitride with the grain diameter of 5 microns and 9.4 g of liquid metal gallium indium tin alloy are placed into a stirring cup, the stirring speed is 1500 revolutions per minute, the stirring time is 5 minutes, a pasty liquid metal boron nitride compound cannot be obtained, the product is black powder, and the real object is shown in figure 5.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related technical fields are included in the scope of the present invention.
Claims (8)
1. The liquid metal with reduced surface tension is characterized by comprising the following raw materials in parts by mass: 75-96.5 parts of liquid metal, 0.5-5 parts of metal tungsten nano particles and 3-20 parts of heat conducting powder.
2. A liquid metal with reduced surface tension according to claim 1, wherein the melting point of the liquid metal is 10-60 ℃.
3. A reduced surface tension liquid metal according to claim 2, wherein the liquid metal is gallium metal or an alloy thereof.
4. A reduced surface tension liquid metal according to claim 1, wherein the metal tungsten nanoparticles have a particle size of 10 to 100 nanometers.
5. The reduced surface tension liquid metal of claim 1, wherein the thermally conductive powder comprises at least one of boron nitride, carbon fiber, graphene, aluminum oxide, aluminum nitride, zinc oxide, silicon carbide.
6. The method of preparing a liquid metal with reduced surface tension according to any one of claims 1 to 5, wherein the metal tungsten nanoparticles and the liquid metal are mixed and stirred for the first time, and then added and stirred with the heat conducting powder for the second time to form a liquid metal compound embedded in the heat conducting powder.
7. The method for producing a liquid metal having a reduced surface tension as defined in claim 6, wherein the raw materials are mixed by stirring, and the raw materials are mixed at a high speed by using a planetary stirring deaerator, wherein the stirring speed is 500 to 2000 rpm, and the stirring time is 3 to 20 minutes.
8. Use of a liquid metal with reduced surface tension according to any of claims 1 to 5 as a heat conducting material.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310217719.XA CN116117130A (en) | 2023-03-08 | 2023-03-08 | Liquid metal with reduced surface tension and preparation method and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202310217719.XA CN116117130A (en) | 2023-03-08 | 2023-03-08 | Liquid metal with reduced surface tension and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117866484A (en) * | 2024-03-12 | 2024-04-12 | 成都先进金属材料产业技术研究院股份有限公司 | Liquid metal printing ink and preparation method thereof |
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| CN117866484B (en) * | 2024-03-12 | 2024-06-04 | 成都先进金属材料产业技术研究院股份有限公司 | Liquid metal printing ink and preparation method thereof |
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