CN101029219B - Heat-transferring solution containing nano-carbon ball - Google Patents
Heat-transferring solution containing nano-carbon ball Download PDFInfo
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- CN101029219B CN101029219B CN2006100198554A CN200610019855A CN101029219B CN 101029219 B CN101029219 B CN 101029219B CN 2006100198554 A CN2006100198554 A CN 2006100198554A CN 200610019855 A CN200610019855 A CN 200610019855A CN 101029219 B CN101029219 B CN 101029219B
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Abstract
A heat-conductive solution contains multiple nano-carbon balls 0.05-10wt% which are dispersed into the fluid as solvent, the nano-carbon ball surface is modified by functional radical. It has better heat conduction, dispersion and radiation.
Description
Technical field
The present invention relates to the fluid of the required use of a kind of liquid-cooling heat radiator, particularly a kind of solution that contains nano carbon microsphere is as the application of heat-transfer fluid in the heat conducting module of heat pipe (heat pipe) or the fine stream pipe of tool.
Background technology
Products such as general computer, electronics, electrical equipment, communication and machinery, behind operation process after a while, can continue consumption of electric power and produce heat energy, this heat energy is quite big to the influence stable and usefulness of equipment itself, in order to make every electronic package normal running of electronic product, must guarantee that this electronic product ties up to operation in the default temperature range, therefore the diffusing function of heat is one of problem very important when the every electronic product of design.But along with improvement is constantly innovated in product design, make that the duration of service of product is longer, relatively also cause more thermal energy to produce, and along with the size of electronic product is more and more littler, and make heat energy also more and more concentrate (being so-called focus), and tradition is used the simple heat dissipation design of air cooling (radiator element or radiator fan), except having shortcomings such as the volume that increases product and the noise of deriving, also can't derive or disperse heat energy effectively fast.
With the mobile computer is example, because the restriction of its congenital upper volume reduces use temperature to become main flow gradually with the water-cooled cooling method.In traditional water-cooled power converter (radiating module that contains heat pipe), generally be as cooling fluid with pure water, yet, the thermal conduction degree of pure water is not good, along with the arithmetic speed quickening of mobile computer and the trend of processing procedure microminiaturization, need to rely on add high heat conduction material in fluid,, promote the total system heat dissipation with the fluid of high-heat conductive efficency more heat-conducting fluid as liquid-cooling heat radiator.
Summary of the invention
In view of this, the present invention's purpose is to provide a kind of heat-transferring solution that comprises nano carbon microsphere, with the cooling fluid as heat abstractor.The characteristic that relies on the high thermal conduction degree of nano carbon microsphere (greater than 1600W/mK), high surface area and light weight, the heat conduction efficiency of increase cooling fluid, the heat-sinking capability of lifting heat abstractor.In addition, the diameter of nano carbon microsphere is less than 100nm, and have heat-resistant quality (in the presence of oxygen, can bear 630 ℃ and be not destroyed) and easily be scattered in characteristic in the liquid, in be highly suitable for having micron runner heat abstractor of (caliber approximately several to dozens of μ m).
For reaching above-mentioned purpose, the heat-transferring solution that contains nano carbon microsphere of the present invention comprises fluid, and a plurality of nano carbon microspheres are scattered in this fluid, wherein the weight percent of this nano carbon microsphere is between 0.05～10wt%, and is preferable between 0.1～4wt%, is benchmark with this solution gross weight that contains nano carbon microsphere.
One of feature of the present invention is, the characteristic of utilizing the many insatiable hungers on the nano carbon microsphere graphite linings to close two keys, its surface be easy to rely on chemically modified make its graphite linings surface further with specific functional group's bond, make nano carbon microsphere rely on these functional groups and have the characteristic that easier dispersion is dissolved in liquid phase, for example but upgrading is for having alcohol radical, aldehyde radical, amino or its radical ion, sulfate or its radical ion, alkane fat base, nitroxyl or its radical ion, the nano carbon microsphere of carboxylic acid group or its radical ion, (for example: water increase nano carbon microsphere and fluid, organic solvents such as alcohols) therefore the reactive force between does not need additionally to use any interfacial agent promptly to have splendid dispersiveness.In addition, nano carbon microsphere is because its particle diameter (between most about 30～40nm), has extraordinary flowing property between 1～100nm in the heat abstractor that uses the fluid channel design.
Nano carbon microsphere of the present invention can be added in the heat-conducting fluid that known any liquid-cooling heat radiator or heat pipe (heat pipe) used, to form the solution that comprises nano carbon microsphere of the present invention.In the present invention's preferred embodiment, this heat-conducting fluid can be water, oil or organic solution, for example: alcohols, ethers, ketone, acid, alkali, ester class or aromatic solvent similarly are: water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, t-butanols, t-amylalcohol, ethylene glycol, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, propylene glycol list ethyl ether, vinylbenzene, ethyl acetate, toluene, dimethylbenzene, methylethylketone, acetone or its mixing.
Below relying on several embodiment and comparing embodiment and cooperate appended graphicly, with method, feature and the advantage that illustrates further the present invention, but is not the scope that is used for limiting the present invention, and the present invention's scope should be as the criterion with appended claim.
Description of drawings
Fig. 1 be show the embodiment of the invention 1 described among high resolution electron microscope (HREM) (HRTEM) photo of empty nano carbon microsphere (HCNC).
Fig. 2 is high resolution electron microscope (HREM) (HRTEM) photo of the filling terbium nano carbon microsphere (Tb@CNC) that shows that the embodiment of the invention 1 is described.
Fig. 3 is the nano carbon microsphere heat-conducting fluid outward appearance of homodisperse.
Fig. 4 is the nano carbon microsphere of demonstration after the functional group modifies, and relies on capillarity to see through copper screen cloth with the aqueous solution and diffuses in another empty bottle.
Fig. 5 is nano carbon microsphere solution dried sweep electron microscope (SEM) photo of demonstration after the functional group modifies.
Embodiment
Nano carbon microsphere of the present invention is a kind of polyhedron carbon of being organized by the multilayer graphite linings structure of sealing bunch (carbon cluster).The graphite linings of nano carbon microsphere shell, middle all is six membered ring partly, in the corner and turnover partly then form by five annulus, each carbon atom is all SP
2Structure, the special layers graphite-structure of nano carbon microsphere makes it have advantages such as high heat conductivity, electroconductibility, structural strength, stability.The graphite linings of nano carbon microsphere can be pure carbon, or the heteroatoms of the 3rd or five families of mixing, and for example boron, phosphorus, sulphur, nitrogen make it have the characteristic in polyelectrons or hole.
The shell of nano carbon microsphere is the multilayer graphite-structure, inside can be hollow (hollow), or the metal of filling agent magnetic, metal oxide, metallic carbide, metallic sulfide, metal nitride, metal boride or metal alloy be in its inside, and the content of metal can be 0.1wt% to 80wt%.This metal or its compound can comprise atoms metal or its combinations such as Sc, V, Cr, Fe, Co, Ni, Y, Zr, Mo, Ru, Rh, Pd, La, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Tm, Lu, Ta, Os, Ir, Pt, Th or U.The nano carbon microsphere that contains magneticmetal with inside is scattered in the solution, can make heat-conducting fluid have magnetic fluid character concurrently, can be applicable in the heat pipe system of externally-applied magnetic field or electric field, relies on the electromagnetic field functions such as liquid motion or vaporization of tending to act.Please refer to Fig. 1, is high resolution electron microscope (HREM) (HRTEM) photo of this hollow nano carbon microsphere (HCNC), in addition, please refer to Fig. 2, is depicted as electron microscope (HRTEM) photo of the filling terbium nano carbon microsphere (Tb@CNC) of amplification.
For making nano carbon microsphere be easier to be dispersed in uniformly in this fluid, the present invention further relies on the mode of chemically modified, two key bonds are closed in insatiable hunger on specific functional group and the nano carbon microsphere graphite linings, make nano carbon microsphere can rely on the easier liquid phase that is scattered in of functional group of its surfaction, for example but upgrading is for having alcohol radical, aldehyde radical, amino or its radical ion, sulfate or its radical ion, alkane fat base, nitroxyl or its radical ion, the nano carbon microsphere of carboxylic acid group or its radical ion, (for example: water increase nano carbon microsphere and fluid, organic solvents such as alcohols) reactive force between, so the present invention does not need to use any extra interfacial agent promptly to have splendid dispersiveness.
The preparation of water-soluble nano carbon ball
Surface tool carboxylic acid group (nano carbon microsphere COOH):
Get hollow nano carbon microsphere (HCNC) 2g, be scattered in 100ml by sulfuric acid and nitric acid (sulfuric acid: nitric acid=1: 1) in the solution of forming, heat back and heat up in a steamer three hours.After reaction was finished, centrifugal, washing and filtering was removed solution, obtains the surface and has carboxylic acid group's (hollow nano carbon microsphere COOH).
Contain the preparation of the solution of nano carbon microsphere
Disperse to be dissolved in the water of 100g with stating carboxylic acid group's nano carbon microsphere on 0.5g and the 2g respectively, be mixed with the nano carbon microsphere aqueous solution of 0.5wt% and 2wt%, please refer to the 3rd figure.
The nano carbon microsphere fluid properties is identified
Please refer to Fig. 4, this nano carbon microsphere after the carboxylic acid group modifies can rely on the capillarity and the aqueous solution to see through copper screen cloth, diffuses to together in another empty bottle (among Fig. 4 right bottle), and this intermiscibility of representing this nano carbon microsphere after the carboxylic acid group modifies and water is splendid.In addition, please refer to Fig. 5, after 0.1ml is contained the solution of nano carbon microsphere and makes its drying, utilize sweep electron microscope (SEM) photo to observe its distribution, its result as shown in Figure 5, this nano carbon microsphere system is the state of many homodisperse.
Get the nano carbon microsphere aqueous solution of above-mentioned 0.5wt% and 2wt%, and measure its conductivity and thermal conduction degree, measuring result is as shown in table 1 below:
Table 1
| Pure water | The 0.5wt% carboxylic acid group nano carbon microsphere aqueous solution | The 2wt% carboxylic acid group nano carbon microsphere aqueous solution | |
| Conductivity (mV) | 2.1 | 76.4 | 270.5 |
| Thermal conduction degree (W/mk) | 0.64 | 2.92 | 8.12 |
As shown in Table 1, the thermal conduction degree that adds the aqueous solution of nano carbon microsphere is not have 4.5～12.5 times that add the nano carbon microsphere pure water, therefore with nano carbon microsphere as additive, can significantly promote the thermal conduction degree of original solution (for example water) really.
Being scattered in the solution with nano material, is the main application mode of present little heat abstractor with the thermal conduction capability of lifting fluid.Traditional little heat abstractor is mainly with cupric oxide (CuO), metallics (gold and silver) or CNT (carbon nano-tube) (CNT) additive as heat-transferring solution, yet these known additives have its inborn restriction in the use.With the CNT (carbon nano-tube) is example, because the runner caliber of the circulation line of heat abstractor is more and more little, the high fineness ratio of CNT (carbon nano-tube) is limited its motion at circulation line, and easily causes the runner blocking problem.In addition, cupric oxide and metallics because of not good with heat radiation fluidic solubleness, are assembled easily each other, need the extra interfacial agent that adds to help disperse, but thus, can cause the problem of thermal impedance, reduce thermal conduction capability.
Review finishing functional group nano carbon microsphere of the present invention, its particle diameter is fit to be applied in heat pipe or the little heat abstractor between 1～100nm very much.Nano carbon microsphere of the present invention relies on the compatibility of surfaction increase and water or organic solvent, can directly be scattered in water or the organic solvent, therefore need not add any interfacial agent.
For further verifying the advantage that contains the nano carbon microsphere heat-transferring solution of the present invention, following series is lifted several can increase the additive of fluid thermal conductivity in known techniques, and indicate its relatively hot conductivity, to do one relatively, please refer to table 2 with the nano carbon microsphere aqueous solution that contains of the present invention:
Table 2
| Heat-conducting fluid and additive | Relative Heat conductivity | The data source |
| 0.5wt% hollow nano carbon microsphere is scattered in the pure water | 478％ | The embodiment of the invention is prepared contains nano carbon microsphere solution |
| 1vol％Al 2O 3Be scattered in the pure water | 102％ | Lee S et.al(Lee S，Choi SUS，Li S，Eastman JA.1999.Measuring thermal conductivity of fluids containingoxide nanoparticles.J.Heat Trans.121：280) |
| 0.4vol%CuO is scattered in the ethylene glycol | 155％ | Eaetman JA et.al(Eastman JA，Choi SUS，Li S，Yu W，Thompson LJ.200 1.Anomalously increased effectivethermal conductivities of ethylene glycol-basednanofluids containing copper nanop articles.Appl.Phys.Lett.78：718-20) |
| 0.011% silver medal gold particle is scattered in water/toluene | 121％ | Patel et.al(Patel HE，Das SK，Sundararajan T，Nair AS，George B.Pradeep T.2003.Thermal conductivities ofnaked and monolayer protected metal nanoparticlebased nanofluids：manifestation of anomalousenhancement and chemical efffects.Appl. Phys.Lett.83：2931-33) |
| The 0.16vol% CNT (carbon nano-tube) is scattered in the oil | 150％ | Choi SUS et.al(Choi SUS，Zhang ZG，Yu W，Lockwood FE，Grulke EA.2001.Anomalous thermalconductivity enhancement in nano-tube suspensions.Appl.Phys.Lett.79：2252-54) |
Though the present invention discloses as above with preferred embodiment; right its is not in order to limit the present invention; anyly have the knack of this skill person; without departing from the spirit and scope of the invention; when can doing various changes and retouching, so the present invention's protection domain attached claim person of defining after looking is as the criterion.
Claims (8)
1. heat-transferring solution that contains nano carbon microsphere comprises:
Fluid; And
A plurality of nano carbon microspheres are scattered in this fluid,
Wherein this nanoparticle surface cording has the functional group, is scattered in this fluid to promote it;
Wherein the weight percent of this nano carbon microsphere is benchmark between 0.05～10wt% with this heat-transferring solution gross weight that contains nano carbon microsphere;
Wherein this fluid comprises water, organic solvent or its mixture;
Wherein this functional group is selected from alcohol radical, aldehyde radical, amino, sulfate, nitroxyl, alkane fat base, carboxylic acid group and radical ion thereof.
2. according to the heat-transferring solution that contains nano carbon microsphere of claim 1, wherein this nano carbon microsphere is a kind of nano-sized carbon of being made up of with the structure of ball in the ball the sealing graphite linings bunch.
3. according to the heat-transferring solution that contains nano carbon microsphere of claim 2, wherein the sealing graphite linings of this nano carbon microsphere is doped with nitrogen-atoms, phosphorus atom, sulphur atom or boron atom.
4. according to the heat-transferring solution that contains nano carbon microsphere of claim 1, wherein this nano carbon microsphere is the hollow nano carbon microsphere.
5. according to the heat-transferring solution that contains nano carbon microsphere of claim 1, wherein the inside of this nano carbon microsphere is filled with metal, metal oxide, metallic carbide, metallic sulfide, metal nitride, metal boride or metal alloy.
6. according to the heat-transferring solution that contains nano carbon microsphere of claim 1, wherein the diameter of this nano carbon microsphere is between 1～100nm.
7. according to the heat-transferring solution that contains nano carbon microsphere of claim 1, wherein this organic solvent comprises alcohol.
8. according to the heat-transferring solution that contains nano carbon microsphere of claim 1, wherein this fluid is water, methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, t-butanols, t-amylalcohol, ethylene glycol, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, propylene glycol list ethyl ether, vinylbenzene, ethyl acetate, toluene, dimethylbenzene, methylethylketone, acetone or its mixing.
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| CN103421470B (en) * | 2012-05-24 | 2016-01-20 | 中国科学院理化技术研究所 | A kind of cooling fluid comprising rigid hollow particle |
| CN103159982B (en) * | 2013-03-18 | 2014-07-30 | 中国石油大学(华东) | Preparation method of nano carbon particles having core-shell structure for field of dielectric materials |
| CN105086946B (en) * | 2015-09-01 | 2018-06-29 | 胡祥卿 | Microgravity molecule heat transfer medium |
| CN110079278B (en) * | 2019-04-30 | 2020-12-08 | 国电南瑞科技股份有限公司 | High-thermal-conductivity composite hydrated salt phase-change heat storage material and preparation method thereof |
| CN110117483B (en) * | 2019-06-17 | 2021-03-16 | 广东工业大学 | Composite material, preparation method thereof and nanofluid |
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| US6432320B1 (en) * | 1998-11-02 | 2002-08-13 | Patrick Bonsignore | Refrigerant and heat transfer fluid additive |
| CN1626612A (en) * | 2003-12-13 | 2005-06-15 | 鸿富锦精密工业（深圳）有限公司 | Heat sink and phase change conducting strip |
| CN1241979C (en) * | 2004-10-11 | 2006-02-15 | 东华大学 | Composite material fiber based on carbon nano-tube and its preparation method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6432320B1 (en) * | 1998-11-02 | 2002-08-13 | Patrick Bonsignore | Refrigerant and heat transfer fluid additive |
| CN1626612A (en) * | 2003-12-13 | 2005-06-15 | 鸿富锦精密工业（深圳）有限公司 | Heat sink and phase change conducting strip |
| CN1241979C (en) * | 2004-10-11 | 2006-02-15 | 东华大学 | Composite material fiber based on carbon nano-tube and its preparation method |
Non-Patent Citations (2)
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| 吕瑞涛 等.高导热炭基功能材料研究进展.《材料导报》.2005,69-72. * |
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