CN104830248B - A kind of high-termal conductivity heat-conducting glue and preparation method thereof - Google Patents
A kind of high-termal conductivity heat-conducting glue and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of high-termal conductivity heat-conducting glue, including：(1) graphene oxide solution is prepared；(2) the first reducing agent is added in graphene oxide solution, so that it is reduced into graphene particles；(3) graphene particles are dispersed in the aqueous solution for being mixed with surfactant, so that graphene solution is made；(4) add polymer monomer in graphene solution and crosslinking agent is reacted, to form polymer coating in the outer surface of graphene particles；(5) add metal salt, ammonium, acid-base modifier and the second reducing agent in the graphene solution for be formed with polymer coating to be reacted, to obtain the graphene particles of metal cladding；(6) mixed after adding metallic particles in the graphene solution of metal cladding, and evaporation solvent is to obtain solid particle；(7) after being ground to solid particle, it is mixed with heat-conducting glue matrix material and heat-conducting glue is made.Heat-conducting glue prepared according to the methods of the invention has high-termal conductivity.
Description
Technical field
The present invention relates to interface heat sink material field, more particularly to a kind of high-termal conductivity heat-conducting glue and preparation method thereof.
Background technology
With microelectronic component integration density more and more higher, therefore the radiating requirements of microelectronic component also more and more higher, is opened
Sending out a kind of has the interface heat sink material of high thermal conductivity significant.Due to heat-conducting glue possess environment friendly and it is low into
This feature, gradually replaces conventional tin-lead solders interconnection material.However, the evolution of conventional pilot hot glue also runs into some bottlenecks,
As heat conductivility is not high, density is big, the problems such as stability is not high.
The content of the invention
It is an object of the invention to provide a kind of heat-conducting glue with high-conductivity energy and preparation method thereof.
To achieve these goals, a kind of preparation method of high-termal conductivity heat-conducting glue of one aspect of the present invention offer, including with
Lower step：
(1) graphene oxide solution is prepared；
(2) the first reducing agent is added in the graphene oxide solution, so that it is reduced into graphene particles；
(3) graphene particles of reduction are dispersed in the aqueous solution for being mixed with surfactant, so that graphene solution is made；
(4) add polymer monomer in the graphene solution and crosslinking agent is reacted, with the graphene
The outer surface of grain forms polymer coating；
(5) metal salt, ammonium, acid-base modifier and the second reduction are added in the graphene solution for be formed with polymer coating
Agent is reacted, to obtain the graphene particles of metal cladding；
(6) mixed after adding metallic particles in the graphene solution of metal cladding, and evaporation solvent is to be consolidated
Body particle；
(7) after being ground to the solid particle, it is mixed with heat-conducting glue matrix material and heat-conducting glue is made.
Preferably, first reducing agent is selected from hydrazine, gallic acid, glucose and NH3 mixture, ascorbic acid, Portugal
One or more in glycan and NH3 mixture, methanol, ethanol and lewis acid.
Preferably, the surfactant is PVP and/or polyvinyl ethanol.
Further, the one kind of the polymer monomer in Dopamine hydrochloride, ethylene glycol and glycol oligomer
Or it is several.
Preferably, the crosslinking agent is selected from mixture, the Yi Jisan of boric acid, calcium carbonate, potassium and trishydroxymethylaminomethane
One or more in hydroxymethyl aminomethane.
Further, the reaction temperature in the step (4) is room temperature, and the reaction time is 24~30 hours.
Preferably, the material of the metal level is one kind in platinum, palladium, silver and gold.
Preferably, the metal salt is one kind in metal nitrate, metal sulphite and metal chlorination salt.
Further, the acid-base modifier is sodium hydroxide or potassium hydroxide.
Preferably, second reducing agent is glucose or glucan.
Another aspect of the present invention provides a kind of high-termal conductivity heat-conducting glue, and the heat-conducting glue is prepared from according to the above method.
In summary, the present invention has area load the metal composite graphene nano material of high-thermal conductive metal nano particle
Add in heat-conducting glue matrix material, because metal nanoparticle can be greatly enhanced point of metal composite graphene nano material
Property is dissipated, and the metal nanoparticle has low-melting characteristic, thus sintering can be melted under relatively low solidification temperature, with
The formation of micron-scale Argent grain is in close contact, so as to improve the thermal conductivity and conductivity of heat-conducting glue.In addition, using this
Metal composite graphene nano material also has many advantages, such as heat conduction glue additive, such as reduces cost, the increase of heat-conducting glue
Thermal conducting path etc..Between the enhancing heat-conducting glue of the present invention can be used for electronic device and be heat sink, solved as interface heat sink material
Chip cooling problem.
Brief description of the drawings
Figure 1A is the transmission electron microscope photo of the graphene particles of the present invention；
Figure 1B is the transmission electron microscope photo of the graphene particles of the metal cladding of the present invention；
Fig. 1 C be Figure 1B in a part of metal cladding graphene particles enlarged drawing；
Fig. 1 D be Figure 1B in another part metal cladding graphene particles enlarged drawing；
Fig. 2 is the weight in wet base analysis graph of the heat-conducting glue of the present invention；
Fig. 3 varies with temperature curve for the thermal conductivity of the heat-conducting glue of present invention addition different content metal cladding graphene
Figure；
Fig. 4 is the thermal conductivity of the heat-conducting glue of the present invention and the graph of relation of metal cladding graphene content.
Embodiment
It is careful to coordinate accompanying drawing to give citing further specific again to make the technological means and feature that give farther insight into the present invention
After being illustrated in：
The heat-conducting glue preparation method of the present invention comprises the following steps：
1st step, prepares graphene oxide solution：Natural flaky graphite powder is aoxidized in strong acid and strong oxidizer first
Graphene oxide is obtained with peeling off；Then graphene oxide is put into deionized water, carries out ultrasonic disperse, then centrifuge removal not
The graphite particle of stripping, reclaims supernatant, supernatant is graphene oxide solution.
2nd step, graphene oxide reduction：The first reducing agent is added in graphene oxide solution, in 90-98 DEG C of environment
Reduction reaction 1 hour, so that it is reduced into graphene particles.
3rd step, by the graphene particles ultrasonic disperse after reduction in the aqueous solution of surfactant is mixed with, so as to obtain
Graphene solution.
4th step, graphenic surface adhesion pretreatment：In order to improve adhesiveness of the metallic particles in graphenic surface, graphite
Alkene surface is by the polymer coating of functionalization one layer of ten following thickness of nanometer of formation, and the polymer coating is by graphite
Certain polymer monomer and crosslinking agent are added in alkene solution and is obtained for stirring reaction 24-30 hours under room temperature environment；So
The graphene particles of the area load polymer of acquisition are subjected to long-time deionized water eccentric cleaning afterwards.Above-mentioned area load gathers
The graphene particles of compound can be evenly dispersed in deionized water under conditions of not by surfactant.
5th step, metallic particles coating：Metal salt, ammonium, soda acid are added in the graphene solution for be formed with polymer coating
Conditioning agent and the second reducing agent, and reacted 2-12 hours under room temperature environment；After reaction terminates, obtain gold-plated by eccentric cleaning
Belong to the graphene particles of layer.
6th step, takes the graphene particles solution of above-mentioned metal cladding, is mixed with metallic particles, and heated solution is arrived
100-200 DEG C, evaporation solvent obtains solid particle.
7th step, after being ground to solid particle, makes it fully be mixed with heat-conducting glue matrix material by shear mixer
Close, to prepare high hot heat-conducting glue.
Wherein, the first reducing agent in the 2nd step be selected from hydrazine, gallic acid, glucose and NH3 mixture, ascorbic acid,
One or more in glucan and NH3 mixture, methanol, ethanol and lewis acid.Surfactant in 3rd step
For PVP and/or polyvinyl ethanol.Polymer monomer in 4th step is selected from Dopamine hydrochloride, ethylene glycol
And the one or more in glycol oligomer.Crosslinking agent in 4th step is selected from boric acid, calcium carbonate, potassium and trihydroxy methyl ammonia
One or more in the mixture and trishydroxymethylaminomethane of methylmethane.Metal salt in 5th step is metal nitrate
One kind in salt, metal sulphite and metal chlorination salt, described metal refers to one kind in platinum, palladium, silver and gold.5th
Acid-base modifier in step is sodium hydroxide or potassium hydroxide.The second reducing agent in 5th step is glucose or glucan.6th
Metallic particles in step also refers to one kind in platinum, palladium, silver and gold.
The transmission electron microscope photo of single graphene particles is as shown in Figure 1A.After metallic particles is applied, as shown in Figure 1B,
It can clearly see that metallic particles is coated in graphene film layer surface, form graphenic surface metal coating.As shown in Figure 1 C,
The graphene smooth surface of preparation becomes rough due to large area adsorbing metal particle, and metal particle size is typically in 2nm
Left and right.The lap graphene number of plies is probably 5 layers or so, as shown in figure iD.
Another aspect of the present invention, which is provided in a kind of heat-conducting glue prepared according to preceding method, the heat-conducting glue, contains metal composite
Graphene nano material.
The thermogravimetric interpretation of result of heat-conducting glue of the present invention is as shown in Fig. 2 thermogravimetric analysis is used for the proportion for assessing graphene, as a result
Display is about 14%.
Meanwhile, the present invention has also carried out the thermal conductivity detection of heat-conducting glue under different temperatures, and the unit type used is Nano-
Flash, as a result as shown in figure 3, it can be found that when the plating metal graphene content in heat-conducting glue sample reaches 11.5%, glue
Thermal conductivity is significantly improved, and thermal conductivity reaches 7.6W/m K.
Fig. 4 shows heat-conducting glue sample thermal conductivity and plating metal graphene relation with contents, it is seen then that when in heat-conducting glue sample
When plating metal graphene content reaches 6%, the thermal conductivity of glue is about 3W/m K；When the plating metal graphene in heat-conducting glue sample contains
When amount reaches 8%, the thermal conductivity of glue reaches 4W/m K；When the plating metal graphene content in heat-conducting glue sample reaches 11.5%
When, the thermal conductivity of glue reaches about 7.6W/m K.In addition, viscosity test results show, reached in plating metal graphene content
When 11.5%, viscosity is 21Pa.S..
Above-described, only presently preferred embodiments of the present invention is not intended to limit the scope of the present invention, of the invention is upper
Stating embodiment can also make a variety of changes.What i.e. every claims and description according to the present patent application were done
Simply, equivalent changes and modifications, falls within the claims of patent of the present invention.The not detailed description of the present invention it is equal
For routine techniques content.
Claims (11)
1. a kind of preparation method of high-termal conductivity heat-conducting glue, it is characterised in that comprise the following steps：
(1) graphene oxide solution is prepared；
(2) the first reducing agent is added in the graphene oxide solution, so that it is reduced into graphene particles；
(3) graphene particles of reduction are dispersed in the aqueous solution for being mixed with surfactant, so that graphene solution is made；
(4) add polymer monomer in the graphene solution and crosslinking agent is reacted, with the graphene particles
Outer surface forms polymer coating；
(5) metal salt, ammonium, acid-base modifier and the second reducing agent is added in the graphene solution for be formed with polymer coating to enter
Row reaction, to obtain the graphene particles of metal cladding；
(6) mixed after adding metallic particles in the graphene solution of metal cladding, and evaporation solvent is to obtain solid
Grain；
(7) after being ground to the solid particle, it is mixed with heat-conducting glue matrix material and heat-conducting glue is made.
2. the preparation method of high-termal conductivity heat-conducting glue according to claim 1, it is characterised in that the first reducing agent choosing
From hydrazine, gallic acid, glucose and NH3Mixture, ascorbic acid, glucan and NH3Mixture, methanol, ethanol and
One or more in lewis acid.
3. the preparation method of high-termal conductivity heat-conducting glue according to claim 1, it is characterised in that the surfactant is
PVP.
4. the preparation method of high-termal conductivity heat-conducting glue according to claim 1, it is characterised in that the polymer monomer choosing
From the one or more in Dopamine hydrochloride and ethylene glycol.
5. the preparation method of high-termal conductivity heat-conducting glue according to claim 1, it is characterised in that the crosslinking agent is selected from boron
One or more in acid, calcium carbonate and trishydroxymethylaminomethane.
6. the preparation method of high-termal conductivity heat-conducting glue according to claim 1, it is characterised in that in the step (4)
Reaction temperature is room temperature, and the reaction time is 24~30 hours.
7. the preparation method of high-termal conductivity heat-conducting glue according to claim 1, it is characterised in that the material of the metal level
For one kind in platinum, palladium, silver and gold.
8. the preparation method of high-termal conductivity heat-conducting glue according to claim 1, it is characterised in that the metal salt is metal
One kind in nitrate, metal sulphite and metal chlorination salt.
9. the preparation method of high-termal conductivity heat-conducting glue according to claim 1, it is characterised in that the acid-base modifier is
Sodium hydroxide or potassium hydroxide.
10. the preparation method of high-termal conductivity heat-conducting glue according to claim 1, it is characterised in that second reducing agent
For glucose or glucan.
11. a kind of high-termal conductivity heat-conducting glue, it is characterised in that its method according to claim any one of 1-10 prepare and
Into.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105950025A (en) * | 2016-05-22 | 2016-09-21 | 周淑华 | High-conductivity thermally conductive glue |
| 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 |
| 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 |
| 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 |
| 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 |
| CN110041065A (en) * | 2019-03-11 | 2019-07-23 | 江苏华友装饰工程有限公司 | Light brick and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153976A (en) * | 2011-03-01 | 2011-08-17 | 华南理工大学 | Preparation method of graphene/nano silver epoxy conductive adhesive |
| CN102433098A (en) * | 2011-09-19 | 2012-05-02 | 常州合润新材料科技有限公司 | Graphene-filled isotropic high-performance heat-conducting adhesive and preparation method |
| CN103194165A (en) * | 2013-04-26 | 2013-07-10 | 中国电子科技集团公司第三十八研究所 | Method for preparing high-heat-conductivity conductive adhesive containing graphene |
| CN103212711A (en) * | 2013-04-07 | 2013-07-24 | 北京化工大学 | Method for preparing highly conductive graphene oxide |
| CN103614098A (en) * | 2013-11-20 | 2014-03-05 | 常州大学 | Functional graphene-doped epoxy resin conductive adhesive and preparation method thereof |
| CN104099050A (en) * | 2014-07-17 | 2014-10-15 | 深圳市华星光电技术有限公司 | Conductive adhesive preparation method and conductive adhesive |
| CN104130719A (en) * | 2014-08-12 | 2014-11-05 | 哈尔滨工业大学 | Graphene oxide conductive adhesive and preparation and using method of graphene oxide conductive adhesive |
-
2015
- 2015-04-27 CN CN201510204929.0A patent/CN104830248B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153976A (en) * | 2011-03-01 | 2011-08-17 | 华南理工大学 | Preparation method of graphene/nano silver epoxy conductive adhesive |
| CN102433098A (en) * | 2011-09-19 | 2012-05-02 | 常州合润新材料科技有限公司 | Graphene-filled isotropic high-performance heat-conducting adhesive and preparation method |
| CN103212711A (en) * | 2013-04-07 | 2013-07-24 | 北京化工大学 | Method for preparing highly conductive graphene oxide |
| CN103194165A (en) * | 2013-04-26 | 2013-07-10 | 中国电子科技集团公司第三十八研究所 | Method for preparing high-heat-conductivity conductive adhesive containing graphene |
| CN103614098A (en) * | 2013-11-20 | 2014-03-05 | 常州大学 | Functional graphene-doped epoxy resin conductive adhesive and preparation method thereof |
| CN104099050A (en) * | 2014-07-17 | 2014-10-15 | 深圳市华星光电技术有限公司 | Conductive adhesive preparation method and conductive adhesive |
| CN104130719A (en) * | 2014-08-12 | 2014-11-05 | 哈尔滨工业大学 | Graphene oxide conductive adhesive and preparation and using method of graphene oxide conductive adhesive |
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