CN104830248A - Heat-conducting glue with high thermal conductivity and preparation method thereof - Google Patents
Heat-conducting glue with high thermal conductivity and preparation method thereof Download PDFInfo
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- CN104830248A CN104830248A CN201510204929.0A CN201510204929A CN104830248A CN 104830248 A CN104830248 A CN 104830248A CN 201510204929 A CN201510204929 A CN 201510204929A CN 104830248 A CN104830248 A CN 104830248A
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Abstract
The invention provides a preparation method of a heat-conducting glue with high thermal conductivity. The preparation method comprises the following steps: (1) preparing an oxidized graphene solution; (2) adding a first reducing agent into the oxidized graphene solution to reduce the oxidized graphene so as to obtain graphene particles; (3) dispersing graphene particles into a water solution containing surfactant to prepare a graphene solution; (4) adding polymer monomers and a crosslinking agent into the graphene solution to carry out reactions so as to form a polymer layer on the external surface of the graphene particles; (5) then adding metal salts, ammonium, a pH adjusting agent, and a second reducing agent into the polymer-coated graphene solution to carry out reactions so as to obtain metal-plated graphene particles; (6) adding metal particles into the metal-plated graphene solution, mixing, and evaporating the solvent to obtain solid particles; (7) grinding the solid particles, and finally mixing the grinded solid particles with a base material of heat-conducting glue to prepare the heat-conducting glue, which has high thermal conductivity.
Description
Technical field
The present invention relates to heat sink material field, interface, particularly relate to a kind of high thermal conductivity heat-conducting glue and preparation method thereof.
Background technology
Along with microelectronic device integration density is more and more higher, the radiating requirements of microelectronic device is also more and more higher, therefore, develops a kind of interface heat sink material with high thermal conductivity significant.Because heat-conducting glue possesses environment friendly and low cost feature, replace conventional tin-lead solders interconnection material gradually.But the evolution of conventional thermal conductive glue also runs into some bottlenecks, as not high in heat conductivility, density is large, the problems such as stability is not high.
Summary of the invention
The object of the present invention is to provide a kind of have high-conductivity can heat-conducting glue and preparation method thereof.
To achieve these goals, one aspect of the present invention provides a kind of preparation method of high thermal conductivity heat-conducting glue, comprises the following steps:
(1) graphene oxide solution is prepared;
(2) in described graphene oxide solution, add the first reductive agent, be reduced into Graphene particle to make it;
(3) by the Graphene Granular composite of reduction in the aqueous solution being mixed with tensio-active agent, to make graphene solution;
(4) in described graphene solution, add polymer monomer and linking agent reacts, form polymeric coating with the outside surface at described Graphene particle;
(5) in the graphene solution being formed with polymeric coating, add metal-salt, ammonium, acid-base modifier and the second reductive agent to react, to obtain the Graphene particle of metal cladding;
(6) mix after adding metallic particles in the graphene solution of metal cladding, and evaporating solvent is to obtain solid particulate;
(7), after grinding described solid particulate, it is made to mix with heat-conducting glue body material and make heat-conducting glue.
Preferably, described first reductive agent is selected from one or more in the mixture of the mixture of hydrazine, gallic acid, glucose and NH3, xitix, dextran and NH3, methyl alcohol, ethanol and Lewis acid.
Preferably, described tensio-active agent is Polyvinylpyrolidone (PVP) and/or polyvinyl ethanol.
Further, described polymer monomer is selected from one or more in dopamine hydrochloride, ethylene glycol and glycol oligomer.
Preferably, described linking agent is selected from one or more in the mixture of boric acid, calcium carbonate, potassium and Tutofusin tris and Tutofusin tris.
Further, the temperature of reaction in described step (4) is room temperature, and the reaction times is 24 ~ 30 hours.
Preferably, the material of described metal level is the one in platinum, palladium, silver and gold.
Preferably, described metal-salt is the one in metal nitrate, metal sulphite and metal chlorination salt.
Further, described acid-base modifier is sodium hydroxide or potassium hydroxide.
Preferably, described second reductive agent is glucose or dextran.
The present invention provides a kind of high thermal conductivity heat-conducting glue on the other hand, and this heat-conducting glue is prepared from according to aforesaid method.
In sum, area load has the metal composite graphene nano material of high-thermal conductive metal nano particle to add in heat-conducting glue body material by the present invention, because metal nanoparticle greatly can improve the dispersiveness of metal composite graphene nano material, and this metal nanoparticle has low-melting characteristic, thus sintering can be melted under lower solidification value, form close contact with micron-scale Argent grain, thus improve thermal conductivity and the conductivity of heat-conducting glue.In addition, this metal composite graphene nano material is used also to have plurality of advantages as heat-conducting glue additive, as reduced the cost, increase thermal conducting path etc. of heat-conducting glue.Enhancing heat-conducting glue of the present invention can be used for electron device and heat sink between, solve chip cooling problem as interface heat sink material.
Accompanying drawing explanation
Figure 1A is the transmission electron microscope photo of Graphene particle of the present invention;
Figure 1B is the transmission electron microscope photo of the Graphene particle of metal cladding of the present invention;
Fig. 1 C is the enlarged view of the Graphene particle of a part of metal cladding in Figure 1B;
Fig. 1 D is the enlarged view of the Graphene particle of another part metal cladding in Figure 1B;
Fig. 2 is the weight in wet base analysis graph of heat-conducting glue of the present invention;
Fig. 3 is that the thermal conductivity that the present invention adds the heat-conducting glue of different content metal cladding Graphene varies with temperature graphic representation;
Fig. 4 is the thermal conductivity of heat-conducting glue of the present invention and the graph of relation of metal cladding Graphene content.
Embodiment
For making to understand technique means of the present invention and feature further in depth, careful cooperation accompanying drawing gives citing again and illustrates in rear further:
Heat-conducting glue preparation method of the present invention comprises the steps:
1st step, preparation graphene oxide solution: be first oxidized natural flaky graphite powder in strong acid and strong oxidizer and peel off acquisition graphene oxide; Then graphene oxide is put into deionized water, carry out ultrasonic disperse, then the graphite granule that centrifugal segregation is unstripped, reclaim supernatant liquor, supernatant liquor and graphene oxide solution.
2nd step, graphene oxide reduces: in graphene oxide solution, add the first reductive agent, reduction reaction 1 hour in 90-98 DEG C of environment, is reduced into Graphene particle to make it.
3rd step, by the Graphene particle ultrasonic disperse after reduction in the aqueous solution being mixed with tensio-active agent, thus obtains graphene solution.
4th step, graphenic surface adheres to pre-treatment: in order to improve the adhesivity of metallic particles at graphenic surface, graphenic surface forms the polymeric coating of one deck ten following thickness of nanometer by functionalization, and this polymeric coating by adding certain polymer monomer and linking agent and obtaining for stirring reaction 24-30 hour under room temperature environment in graphene solution; Then the Graphene particle of the area load polymkeric substance of acquisition is carried out long-time deionized water eccentric cleaning.The Graphene particle of above-mentioned area load polymkeric substance can be evenly dispersed in deionized water under not by the condition of tensio-active agent.
5th step, metallic particles applies: in the graphene solution being formed with polymeric coating, add metal-salt, ammonium, acid-base modifier and the second reductive agent, and react 2-12 hour under room temperature environment; After reaction terminates, obtained the Graphene particle of metal cladding by eccentric cleaning.
6th step, gets the Graphene particle solution of above-mentioned metal cladding, mix, and heated solution is to 100-200 DEG C with metallic particles, evaporating solvent, obtains solid particulate.
7th step, after grinding, makes it fully mix with heat-conducting glue body material by shear mixer to solid particulate, to prepare high hot heat-conducting glue.
Wherein, the first reductive agent in the 2nd step is selected from one or more in the mixture of the mixture of hydrazine, gallic acid, glucose and NH3, xitix, dextran and NH3, methyl alcohol, ethanol and Lewis acid.Tensio-active agent in 3rd step is Polyvinylpyrolidone (PVP) and/or polyvinyl ethanol.Polymer monomer in 4th step is selected from one or more in dopamine hydrochloride, ethylene glycol and glycol oligomer.Linking agent in 4th step is selected from one or more in the mixture of boric acid, calcium carbonate, potassium and Tutofusin tris and Tutofusin tris.Metal-salt in 5th step is the one in metal nitrate, metal sulphite and metal chlorination salt, and described metal refers to the one in platinum, palladium, silver and gold.Acid-base modifier in 5th step is sodium hydroxide or potassium hydroxide.The second reductive agent in 5th step is glucose or dextran.Metallic particles in 6th step also refers to the one in platinum, palladium, silver and gold.
The transmission electron microscope photo of independent Graphene particle as shown in Figure 1A.When after metallizing particle, as shown in Figure 1B, clearly can see that metallic particles is coated in graphene sheet layer surface, form graphenic surface metallic coating.As shown in Figure 1 C, the Graphene smooth surface of preparation becomes coarse injustice due to big area attract metal particles, and metal particle size is generally at about 2nm.The lap Graphene number of plies the chances are about 5 layers, as shown in figure ip.
The present invention provides a kind of heat-conducting glue prepared according to preceding method on the other hand, containing metal composite graphene nano material in this heat-conducting glue.
As shown in Figure 2, thermogravimetric analysis is for assessment of the proportion of Graphene, and result display is probably 14% in the thermogravimetric interpretation of result of heat-conducting glue of the present invention.
Simultaneously, the thermal conductivity that the present invention has also carried out heat-conducting glue under differing temps detects, the unit type adopted is Nano-Flash, result as shown in Figure 3, can find when the metallizing Graphene content in heat-conducting glue sample reaches 11.5%, the thermal conductivity of glue significantly improves, and thermal conductivity reaches 7.6W/m K.
Fig. 4 shows heat-conducting glue sample thermal conductivity and metallizing Graphene relation with contents, visible, and when the metallizing Graphene content in heat-conducting glue sample reaches 6%, the thermal conductivity of glue is about 3W/m K; When the metallizing Graphene content in heat-conducting glue sample reaches 8%, the thermal conductivity of glue reaches 4W/m K; When the metallizing Graphene content in heat-conducting glue sample reaches 11.5%, the thermal conductivity of glue reaches about 7.6W/m K.In addition, viscosity test results shows, when metallizing Graphene content reaches 11.5%, viscosity is 21Pa.S..
Above-described, be only preferred embodiment of the present invention, be not intended to limit scope of the present invention, the above embodiment of the present invention can also make a variety of changes.Namely every claims according to the present patent application and description are done simple, equivalence change and modify, and all fall into the claims of patent of the present invention.The not detailed description of the present invention be routine techniques content.
Claims (11)
1. a preparation method for high thermal conductivity heat-conducting glue, is characterized in that, comprises the following steps:
(1) graphene oxide solution is prepared;
(2) in described graphene oxide solution, add the first reductive agent, be reduced into Graphene particle to make it;
(3) by the Graphene Granular composite of reduction in the aqueous solution being mixed with tensio-active agent, to make graphene solution;
(4) in described graphene solution, add polymer monomer and linking agent reacts, form polymeric coating with the outside surface at described Graphene particle;
(5) in the graphene solution being formed with polymeric coating, add metal-salt, ammonium, acid-base modifier and the second reductive agent to react, to obtain the Graphene particle of metal cladding;
(6) mix after adding metallic particles in the graphene solution of metal cladding, and evaporating solvent is to obtain solid particulate;
(7), after grinding described solid particulate, it is made to mix with heat-conducting glue body material and make heat-conducting glue.
2. the preparation method of high thermal conductivity heat-conducting glue according to claim 1, it is characterized in that, described first reductive agent is selected from one or more in the mixture of the mixture of hydrazine, gallic acid, glucose and NH3, xitix, dextran and NH3, methyl alcohol, ethanol and Lewis acid.
3. the preparation method of high thermal conductivity heat-conducting glue according to claim 1, is characterized in that, described tensio-active agent is Polyvinylpyrolidone (PVP) and/or polyvinyl ethanol.
4. the preparation method of high thermal conductivity heat-conducting glue according to claim 1, is characterized in that, described polymer monomer is selected from one or more in dopamine hydrochloride, ethylene glycol and glycol oligomer.
5. the preparation method of high thermal conductivity heat-conducting glue according to claim 1, is characterized in that, described linking agent is selected from one or more in the mixture of boric acid, calcium carbonate, potassium and Tutofusin tris and Tutofusin tris.
6. the preparation method of high thermal conductivity heat-conducting glue according to claim 1, is characterized in that, the temperature of reaction in described step (4) is room temperature, and the reaction times is 24 ~ 30 hours.
7. the preparation method of high thermal conductivity heat-conducting glue according to claim 1, is characterized in that, the material of described metal level is the one in platinum, palladium, silver and gold.
8. the preparation method of high thermal conductivity heat-conducting glue according to claim 1, is characterized in that, described metal-salt is the one in metal nitrate, metal sulphite and metal chlorination salt.
9. the preparation method of high thermal conductivity heat-conducting glue according to claim 1, is characterized in that, described acid-base modifier is sodium hydroxide or potassium hydroxide.
10. the preparation method of high thermal conductivity heat-conducting glue according to claim 1, is characterized in that, described second reductive agent is glucose or dextran.
11. 1 kinds of high thermal conductivity heat-conducting glues, is characterized in that, its method according to any one of claim 1-10 is prepared from.
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Cited By (6)
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| CN105950025A (en) * | 2016-05-22 | 2016-09-21 | 周淑华 | High-conductivity thermally conductive glue |
| CN106221227A (en) * | 2016-08-18 | 2016-12-14 | 安徽省和翰光电科技有限公司 | A kind of LED high-performance heat-conducting silicon rubber thermal interfacial material and preparation method |
| CN106280470A (en) * | 2016-08-19 | 2017-01-04 | 蚌埠市英路光电有限公司 | A kind of LED heat-conducting silicon rubber thermal interfacial material and preparation method with ultraviolet resistance |
| CN106317883A (en) * | 2016-08-19 | 2017-01-11 | 蚌埠市英路光电有限公司 | Anti-ageing high-heat-conductivity silicone rubber thermal interface material for LED and preparation method |
| CN106349697A (en) * | 2016-08-18 | 2017-01-25 | 安徽省和翰光电科技有限公司 | Glass-fiber-reinforced type high-thermal-conductivity silicone rubber thermal interface material for LEDs and preparation method of glass-fiber-reinforced type high-thermal-conductivity silicone rubber thermal interface material |
| CN110041065A (en) * | 2019-03-11 | 2019-07-23 | 江苏华友装饰工程有限公司 | A kind of light-weight brick and preparation method thereof |
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| CN106349697A (en) * | 2016-08-18 | 2017-01-25 | 安徽省和翰光电科技有限公司 | Glass-fiber-reinforced type high-thermal-conductivity silicone rubber thermal interface material for LEDs and preparation method of glass-fiber-reinforced type high-thermal-conductivity silicone rubber thermal interface material |
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| CN106317883A (en) * | 2016-08-19 | 2017-01-11 | 蚌埠市英路光电有限公司 | Anti-ageing high-heat-conductivity silicone rubber thermal interface material for LED and preparation method |
| CN110041065A (en) * | 2019-03-11 | 2019-07-23 | 江苏华友装饰工程有限公司 | A kind of light-weight brick and preparation method thereof |
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Effective date of registration: 20171127 Address after: 518108 Guangdong city of Shenzhen province Baoan District Shiyan street aucan Industrial Park 1 building room 703 Patentee after: Shenzhen city deep ruimo Technology Co. Ltd. Xi Address before: 200072 new building, No. 149, science and technology building, No. 149, Yanchang Road, Shanghai Patentee before: Shanghai Shang Da Rui Hu Microsystem Integration Technology Co., Ltd. (SMIT Ltd) |