WO2017062697A2 - 2-dimensional thermal conductive materials and their use - Google Patents
2-dimensional thermal conductive materials and their use Download PDFInfo
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- WO2017062697A2 WO2017062697A2 PCT/US2016/055873 US2016055873W WO2017062697A2 WO 2017062697 A2 WO2017062697 A2 WO 2017062697A2 US 2016055873 W US2016055873 W US 2016055873W WO 2017062697 A2 WO2017062697 A2 WO 2017062697A2
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- WIPO (PCT)
- Prior art keywords
- thermal
- thermal interface
- interface material
- graphene
- filler
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- 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
Definitions
- This invention deals with the development and manufacture of graphene based he mal interface jaatsrials including,, among other, greases, pastes, gels, adhesives, pads, sheets, solders and phase change materials,; with good through-plane thermal conductivity for ae si s l i n er face applicat ons,: The good " through- lan th :rmal conductivity is achieved through the formation of a conductive network by the use of the grephane and graphene"-coated. f l l era.
- Therm l interface materials a e used to minimize the contact therma resistance between a heat source and a heat sink. It is widely applied in electronic and other industries where heat removal from chips or processors is critical since operation of inrearahod circuits at elevated temperatores is a major cause: of failure for electronic devisee . Such thermal management is becoming jsors ' and more important wit the rapidly increasing functions and hence oc e > ⁇ densities of advanced electronics. Generated heat needs to be transferred or dissipated: to a heat sink in order to maintain an appropriate operating temperature.
- TIMs include greases, pads, gels, adhesives, solders, and p ase change materials, etc. Hosr. of them are made of a polymer or silicone matrix loaded with thermall conductive filler particles .
- Thermal greases are a form of thick pasts com sed of " thermally conductive filler dispersed in silicone or hydrocarbon oil.
- the filler can be me allic, ceramic, or carbonaceous materials.
- Metal-based the m l greases ofte employ silver., co pe , 3 ⁇ 43 ⁇ 4? alu mim articlesi They usually have good thermal conductivi y, b3 ⁇ 4t ma suffer high cost.
- Ceramic-based thermal pastes typically use conductive ceramic particles, such as beryllium oxide, aluminum nitride, aluminum oxide, sine o3 ⁇ 4ide. and silica as the filler. They usually have good thermal conductivity and low cost. Carbon-based oe rod greases are relatively new.
- Good fi llets include carbon n notube (CiiT) and carbon nano fibers (CPf ⁇ .
- thermal greases have high thermal conductivity, thin bond line thickness ⁇ BLT) with minimal pressure* low viscosity to fill the voids between mating surfaces, and no need to be cured.
- thermal grease is
- the pxa -out is typically caused by mismatched coefficients of thermal expansion (CTE) of the m ting surfaces, which could forc the TIM to flow out of the interface by alternatel squeezing and releasing the system during thermal cycling.
- CTE coefficients of thermal expansion
- Thermal pads are a group of TIMs in the form of pad. They typically consist of an eiastoms.t matrix such as silicone rubber and thermally conductive fillers such as boron nitride, alumina, or tine oxide. The material is often made nto a soft pad that can be conforaable t the mating sur ces 3 ⁇ 4pon compression. ate e sil
- Thermal gels typically consist of silicone (or olefin) polymers with low cross-link density loaded 3 ⁇ 4ith thermally conductive filler, either ceramic or metallic:.
- the silicone has low jaoduiws o
- the m terials are li e greases bnt can he cured. They have relatively de ent thermal conduc ivity, good we ti g c aracteris ics , easy to conform, to mating surfaces, and are lass susceptible to pump out.
- Thermal adhesivea ar a type of thermall edndixctlve glue normally consistin of at adhesiv resin and a thermally conductive filler,
- An example is silver particles dispersed in a cured epoxy matrix.
- Such TI s eliminate the need for mechanical attachment of permanent pressure and are easy to apply. They are not susceptible to pump-out and can conform to the rsating surfaces. However, they need to be cured and there is a risk of del min&tion during usage,
- phase change material is a substance with a high heat of fusion whic is capable of s oring or releasing a large amount of energy upon melting or solidifying.
- the phase change thermal interface materials are typically made of suspended particles of high thermal conductivity and a base material. Exam les include conductive metal oxide particles dispersed in an organic matrix such as fully refined paraffin, a polymer, a co-polymer, or a mixture of the three, At room temperatures, they are similar to thermal pads, hen heated to a certain temperature, normally >50 S, C, they change to semi-soiids o liquids to fill the void between mating surf ces. They solidify again when the temperature drops below the transition temperature,.
- PCM is less susceptible to pump-out and its application is easier than grease. It also does not need to cure and there is no deia ination concern .
- the inv ors herein have d velo d a graphen -bas she product 1Kb 1 Leaf 8 that can be sed £ ⁇ r s readi g eats from a heat source to a heat sink.
- the material has & high in-plane hermal conductivity of >S00 /rah and a low through-plane conductivity of 5 i/ K .
- This m terial utilises the 2-diisen ionai and anisotropic features of graphen n&nopiateiets so that heat is dissipated
- thermal interface material in a LED lighting device.
- silver-based solder paste is used to transfer beat away from LED chip to a heat sink.
- tbis t 3 ⁇ 4r3 ⁇ 43 ⁇ 4i jenagbian soi tiorr- hirst t : pate needs to be: cured at : -eppera u e that can easily cause damage bo the: chips.
- the instant invention has unique
- WO20X5/103435 deals with a rseth d of aligning graphene flakes perpendicular to th mating substrate using magnetic f nctionaiiKstios and magnetic fields , This e ui s x siv specialized equ i. . ⁇ enr. to generate the mag t c f lds, A ditionally, the gra hene alignment may decrease o e time, in a fluid sys em, once the .magnetic field Is no longer pplied.
- qraphe-ne, graph® ⁇ n nopiatelets f or t:chat thermally conductive materials such as boron nitride platelet can be coated or anchored on the surface of fillers.
- the partial qraphene platelet alignment perpendicular to the mating subs ates is an inherent property ⁇ 3 ⁇ 4 I ade with grspheae or another coated tille , and nil! remain stable.
- Such a TIM can be processed using standard I dust y equi ent and methods and still get the benefit of aligned grap ene and other thermally conductive platelets; .
- S2G13/ 22126S describe a thermal paste using graphene latele a in conjunction with other filler materials to create a 3D conductive ne w k.
- Ho eeer by coating the graphene platelets onto the other fillers without significantly amaging their structure the instant i ventio achieves similar thermal conductivity improvement ith greatly reduced viscosit f resulting in a superior product for handling and thermal resistance.
- U.S. 7,866,813 describes a TIM material with filier particles coated w t high thermal conductivity coatings.
- the coatings are met ls and the use of a graphite or a sheet materiel to coat the fillers is not contemplated.
- figure I is an exem la y application illustration of the mal interface ssaterial shoeing a pad an an 3 ⁇ 4I board 1, LED chip 2, thermal interface mat al 3, silicon , board S, the mal
- figure 2 is an illustration of nanoplatelet coated filler particle showing the graphene coating 8 and the filler particles 9 arsd
- Figure 3 is an illustration of a .thermal in e face ma erial ssade with thermally conductive nanoplatsleta and nanoplateiet c a ed fillers shoving the resin matrix 10, the gra me coated filler particle 11, the graphene sheet or grap ene nanoplateiet 2,
- Figure 4 is a microp otograph of g a ene nanoplateiet coated alhmina fillers for t etisa! intetfaen mat ialss,
- Figpre S is grap of thatma i conductivity of loMna o the pr;.o: art compared to coated alumna of the idatant la ⁇ enfida.
- Figure 6 is a graph of thermal resistance of alusana of he prior art compared to coated alumina of the instant inverc:: ;m.
- Figure ? is a graph of thermal conductivity showing dry coated alumina v rsus w coated alumina.
- Figure 8 is a graph showing thermal conductivity for alumina "A" versus iom.ina treated according to this invention B B" and coated al i ft C* f and coated alumina and nanoplateiet blend tt' -" .
- Figure 3 is a graph showing thermal resistance of dry coated alumina versus wet coated alumina
- Figure 10 is a graph showing th. rs3 ⁇ 43 ⁇ 4l resistance of alumina and wet coated aluraina *
- Figure II is a graph s oeing thermal conductivity of alumina and ml coated alumina.
- a t erma interface material containing a jaaterial selected from the group consisting of fillers,, graphene coated fillers, and, fixture of fillers and graphene coated fillers.
- a method o providing a thermal interface composite the method, c m sing - rovidi a irst substrate- that is a heat sink and providing a second substrate tha is a heat sou ce, and placing- a thermal interface ma erial as described herein between the first substrate and the second substrate.
- a further embodiment f which is a composite structure comprising a solid heat source; a solid heat sink, and, a thermal int rface mat al as described hersln contained, between the solid heat source and the solid heat sink.
- a through-plane thermal pathw y can be c ie ed through two approaches:
- nanoplatelet-ooated fille particles F r e am le, ceramic particles can be coated by a highly conductive nanoplatelet material such- s grapheme nanopletele and boron oitride platelet:, :3 ⁇ 4 coating: helps ensure a vertical heat conducting pathway with a
- nano-piatelefc coated spherical filler particles are used together with graphene nanopiatelets to foras a 3-D conductive network better than using spherical particles alone.
- the additional graphene naneplatelets serve to better bridge the fillers with improved contact due to the 2 ⁇ e and flexible feature of graphene naneplatelets as illustrated in Figure 3. For example, the contact between two spheres is theoretically a single point contact.
- this invention comprises a TIM grease made with graphene -nanopiatei t coated alumina Sillers. mina fillers were coated with graphene-nanoplatelet by a process using a. mechanical billing machine, Th coating ocess was designee to effectively attach graphene naneplatelets onto alumina filler without
- the coated alumina filler is shown in Fig. 4.
- the IM Hiade with graphene coat3 ⁇ 4d alumina filler showed
- graphene coating of fillers is achieved by a wet met od, Graphene nanopiatelet;; and alumina are mi3 ⁇ 4ed together in a solution of appropriate organic solvent, where they are dispersed and agitated by ultrasonic mixing for 5 minates.
- T « sol en is t an evaporated, leaving behind a homogeneous powder. The powder is dispersed into silicone oil in. order to create a thermal grease, The resulting therc-ai grease shows enhanced thermal, conduc i city compared to a grease made with an equal loading of unmodified alumina, as shown in F gures ? and 8.
- g a h me nanopiatelets ar added to a TIM grease together with graphene-ooated alui3 ⁇ 4ina tillera.
- additional graphene nanopiateiet serve o better bridge the fillets one to the : 2TMS and flexible features of graphena nancpiatelets , h flex ble and lake-like oraphen hasoplafelefs can signxfioaru:Iy increase the contact area of conductive fillers as illustrated in Figure .
- the erm graphene as used in this invention shall include graphene nanopiatelets from fully exfoliated graphite to particles with thicknesses of less than lOOnm and/or number of layers less than .100, and preferably with thicknesses of less than 2Qnm and/or number of layers less than €0.
- Graphene nanoplatelets and alumina were added together into a canister with milling madia, and ball milled for id minutes.
- the resulting homogeneous powder was dispersed into silicone oil in order to create thermal grease..
- the resulting thermal grease showed
- Graphene nanopl Dustts and alumin were mixed together in a solution of appropriate organic solvent, whe e Lhoy w®r® dispersed and agitated by ultrasonic mixing for 5 minutes .
- the solvent was evaporated., leaving behind, a homogeneous powder-
- the resulting thermal grease showed enhanced thermal conductivity compared to a grease made with an equal loading of ij.nmadifi.ed alumin .
Abstract
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Priority Applications (2)
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CN201680070947.7A CN108368418B (en) | 2015-10-09 | 2016-10-07 | Two-dimensional heat conducting material and use thereof |
KR1020187012791A KR20180116229A (en) | 2015-10-09 | 2016-10-07 | Two-dimensional thermally conductive materials and their uses |
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US201562284797P | 2015-10-09 | 2015-10-09 | |
US62/284,797 | 2015-10-09 | ||
US15/285,967 US10568544B2 (en) | 2015-10-09 | 2016-10-05 | 2-dimensional thermal conductive materials and their use |
US15/285,967 | 2016-10-05 |
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WO2017062697A2 true WO2017062697A2 (en) | 2017-04-13 |
WO2017062697A3 WO2017062697A3 (en) | 2018-02-08 |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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TWI774360B (en) * | 2021-05-07 | 2022-08-11 | 大陸商河南烯力新材料科技有限公司 | Heat disspation structure and electronic device |
CN115475743A (en) * | 2022-10-28 | 2022-12-16 | 江苏萃隆精密铜管股份有限公司 | Manufacturing and processing technology for condenser pipe of condenser |
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US6620497B2 (en) * | 2000-01-11 | 2003-09-16 | Cool Options, Inc. | Polymer composition with boron nitride coated carbon flakes |
US8039961B2 (en) * | 2003-08-25 | 2011-10-18 | Samsung Electronics Co., Ltd. | Composite carbon nanotube-based structures and methods for removing heat from solid-state devices |
US8017228B2 (en) * | 2006-05-16 | 2011-09-13 | Board Of Trustees Of Michigan State University | Conductive composite compositions with fillers |
US20080291634A1 (en) * | 2007-05-22 | 2008-11-27 | Weiser Martin W | Thermal interconnect and interface materials, methods of production and uses thereof |
US9353304B2 (en) * | 2009-03-02 | 2016-05-31 | Honeywell International Inc. | Thermal interface material and method of making and using the same |
US20120080639A1 (en) * | 2010-10-04 | 2012-04-05 | Laird Technologies, Inc. | Potato shaped graphite filler, thermal interface materials and emi shielding |
KR101609199B1 (en) * | 2012-05-09 | 2016-04-08 | 라이르드 테크놀로지스, 아이엔씨 | Polymer matrices functionalized with carbon-containing species for enhanced thermal conductivity |
EP2856497B1 (en) * | 2012-06-05 | 2018-04-18 | Stratasys, Inc. | Composite made with graphene coated substrates and manufacturing process |
US20140085813A1 (en) * | 2012-09-27 | 2014-03-27 | Liquidcool Solutions | Film or composite that includes a nanomaterial |
US9716299B2 (en) * | 2012-10-25 | 2017-07-25 | The Regents Of The University Of California | Graphene based thermal interface materials and methods of manufacturing the same |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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TWI774360B (en) * | 2021-05-07 | 2022-08-11 | 大陸商河南烯力新材料科技有限公司 | Heat disspation structure and electronic device |
CN115475743A (en) * | 2022-10-28 | 2022-12-16 | 江苏萃隆精密铜管股份有限公司 | Manufacturing and processing technology for condenser pipe of condenser |
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