CN105637124A - Performance enhanced heat spreader - Google Patents
Performance enhanced heat spreader Download PDFInfo
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- CN105637124A CN105637124A CN201480053885.XA CN201480053885A CN105637124A CN 105637124 A CN105637124 A CN 105637124A CN 201480053885 A CN201480053885 A CN 201480053885A CN 105637124 A CN105637124 A CN 105637124A
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- thermal conductivity
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/02—Constructions of heat-exchange apparatus characterised by the selection of particular materials of carbon, e.g. graphite
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F21/00—Constructions of heat-exchange apparatus characterised by the selection of particular materials
- F28F21/08—Constructions of heat-exchange apparatus characterised by the selection of particular materials of metal
- F28F21/089—Coatings, claddings or bonding layers made from metals or metal alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
- H01L23/3733—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon having a heterogeneous or anisotropic structure, e.g. powder or fibres in a matrix, wire mesh, porous structures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
- H01L23/3736—Metallic materials
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/0001—Technical content checked by a classifier
- H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
Abstract
Embodiments of the present invention include methods of disposing a metallic coating layer comprising a metal in an amorphous and/or fine grain microstructure over at least a portion of a surface of a pyrolytic graphite substrate, the metal comprising Nickel, Iron, a Nickel-Iron Alloy, or any combination thereof, and the grains of the metal being of 1 nm to 10000 nm in size. Embodiments of the invention also encompass the coated pyrolytic graphite articles. The coated substrate exhibits a thermal conductivity not less than the uncoated substrate.
Description
Background technology
The method that the present invention relates to the base material that coating is put on pyrolytic graphite, and the pyrolytic graphite of this coating presents the heat conductivity of improvement. The pyrolytic graphite of coating can serve as radiator, for hot from equipment conduction. Electronic device becomes more little, and the requirement dispelled the heat also becomes more high. In order to distribute the heat produced by these electronic devices, between electronic device and heat extractor, use radiator. Radiator can be made up of solid conductive heat metal. Solid conductive metallic has the limited capability spreading heat, and has limited heat conductivity feature.
It is incorporated by reference into
By reference all publications mentioned in this manual, patents and patent applications are expressly incorporated herein specifically and to be individually appointed as such as each independent publication, patent or patent application and are incorporated by reference into, and such as the degree that each described independent publication, patent or patent application (including any figure in literary composition) are fully set forth.
Summary of the invention
The non-limiting embodiments of the present invention described in the paragraph of labelling below:
<0001>method that embodiment of the present invention include the metallicity coat comprising metal is arranged at least one of top on pyrolytic graphite substrate surface, this metal comprises nickel, ferrum, nickel-ferro alloy or their combination in any, and metallic is of a size of 1 nanometer (nm) to 10000 nanometers, this metal is unbodied, or both.
<0002>embodiment of the present invention include the goods of the metallicity coat comprising at least one of top being arranged on pyrolytic graphite substrate surface containing metal, this metal comprises nickel, ferrum, nickel-ferro alloy or their combination in any, and metallic is of a size of 1 nanometer (nm) to 10000 nanometers, this metal is unbodied, or both.
<0003>in embodiment of the present invention such as but not limited in the goods described in the method described in paragraph<0001>or paragraph<0002>, pyrolytic graphite substrate is height-oriented pyrolytic graphite, the pyrolytic graphite of chemical vapour deposition (CVD) or their combination.
<0004>in embodiment of the present invention such as but not limited in the goods described in the method described in paragraph<0001>or paragraph<0002>, pyrolytic graphite substrate isHT��SN��CN or their combination.
<0005>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0004>or in goods, it is arranged on the Nanovate above base materialTMN2040 coating includes metallicity coat.
<0006>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0005>or in goods, metallicity coat comprises the finely-divided metal of the metal particle diameter of 2 nanometers to 5000 nanometers.
<0007>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0006>or in goods, metallicity coat comprises the finely-divided metal of the metal particle diameter of 5 nanometers to 1000 nanometers.
<0008>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0007>or in goods, metallicity coat comprises the finely-divided metal of the metal particle diameter of 10 nanometers to 500 nanometers.
<0009>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0005>or in goods, metallicity coat comprises metal particle diameter and has selected from 2 nanometers, 5 nanometers, the minimum dimension of 10 nanometers also has selected from 100 nanometers, 500 nanometers, 1000 nanometers, the finely-divided metal in the maximum sized scope of 5000 nanometers and 10000 nanometers.
<0010>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0009>or in goods, coating comprises alloying additive.
<0011>in embodiment of the present invention such as but not limited in any one method described in paragraph<0010>or in goods, alloying additive is selected from B, C, H, O, P, S and their combination.
<0012>in embodiment of the present invention such as but not limited in any one method described in paragraph<0010>or in goods, alloying additive is selected from Ag, Au, B, Cr, Mo, P, Pb, Pd, Rh, Ru, Sn, Zn and their combination.
<0013>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0012>or in goods, coating comprises solid grain, wherein solid grain is metal; Metal-oxide; The carbide of B, Cr, Bi, Si, W, or their combination; Carbon; Glass; Polymeric material; MoS2; Or their combination in any.
<0014>in embodiment of the present invention such as but not limited in any one method described in paragraph<0013>or in goods, polymeric material is selected from politef, polrvinyl chloride, polyethylene, polypropylene, acrylonitrile-butadiene-styrene (ABS), epoxy resin and their combination.
<0015>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0014>or in goods, coating comprises up to the solid grain of 95 volume %.
<0016>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0014>or in goods, coating comprises by the solid grain of 1 volume % to 95 volume %.
<0017>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0016>or in goods, the thickness of metallicity coat be 10 ��m to 50mm.
<0018>in embodiment of the present invention such as but not limited in any one method described in paragraph<0017>or in goods, the thickness of metallicity coat be 25 ��m to 25mm.
<0019>in embodiment of the present invention such as but not limited in any one method described in paragraph<0018>or in goods, the thickness of metallicity coat be 30 ��m to 5mm.
<0020>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0019>or in goods, before applying metallicity coat, one or more mid-coat layer being put on base material.
<0021>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0020>or in goods, at least one mid-coat layer comprises metal, polymer or metal and polymer.
<0022>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0021>or in goods, the thickness of mid-coat layer is than the thickness little at least 20% of metallicity coat.
<0023>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0022>or in goods, metallicity coat and mid-coat layer, if it exists, cover whole outer surfaces of base material.
<0024>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0022>or in goods, metallicity coat and mid-coat layer, if it exists, only cover a part for base material.
<0025>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0024>or in goods, the thermal conductivity of the pyrolytic graphite of coating is not less than uncoated pyrolytic graphite substrate.
<0026>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0025>or in goods, be coated with the base material of metallicity coat demonstrate uncoated base material thermal conductivity about 105% thermal conductivity, or be not less than 105% and also thermal conductivity less than the 250% of uncoated base material of uncoated base material.
<0027>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0026>or in goods, be coated with the base material of metallicity coat demonstrate uncoated base material thermal conductivity about 110% thermal conductivity, or be not less than 110% and also thermal conductivity less than the 250% of uncoated base material of uncoated base material.
<0028>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0027>or in goods, be coated with the base material of metallicity coat demonstrate uncoated base material thermal conductivity about 115% thermal conductivity, or be not less than 115% and also thermal conductivity less than the 250% of uncoated base material of uncoated base material.
<0029>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0028>or in goods, it is coated with the base material of metallicity coat and demonstrates the bending strength that the bending strength of the base material more uncoated than this is big.
<0030>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0029>or in goods, be coated with the base material of metallicity coat demonstrate uncoated base material bending strength about 110% bending strength, or be not less than 110% and also bending strength less than the 2000% of uncoated base material of uncoated base material.
<0031>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0030>or in goods, metallicity coat has less than 25 �� 10 in all directions-6K-1Room temperature thermal linear expansion coefficient.
<0032>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0030>or in goods, metallicity coat has 5.0 �� 10 in all directions-6K-1To 25 �� 10-6K-1Room temperature thermal linear expansion coefficient.
<0033>in embodiment of the present invention such as but not limited in any one method described in paragraph<0001>-<0032>or in goods, this base material is radiator.
<0034>in embodiment of the present invention such as but not limited in any one method described in paragraph<0033>or in goods, radiator be those as described in U.S. Patent number 8085531,7859848,7808787 and 8059408 in any one.
The brief description of accompanying drawing
Fig. 1 illustrates an example of the structure of graphite flake.
Fig. 2 illustrates the manufacture method of height-oriented pyrolytic graphite.
Detailed description of the invention
In (including claims) herein, the use of odd number includes plural number, and vice versa, unless expressly stated otherwise. That is, " one (a) ", " one (an) " and " being somebody's turn to do " refer to the object that this word language one or more is modified. Such as, " goods " can refer to goods, two goods etc. For the same reason, for instance but the word being not limited to " goods " refers to goods and multiple goods, is not intended to so unless expressly stated or from context is clear.
As used herein, approximate word, for instance but it is not limited to " about ", " substantially ", " generally ", and " about " means that the word modified by this term or phrase need not to be write accurate like that, but is likely to change to a certain degree from this written description. The degree changed from the letter (i.e. absolute or perfect form) write will depend on establishing how big change, and the variant of amendment still has word or the character of phrase, feature and the ability of modification to make those of ordinary skill in the art recognize. But in the ordinary course of things, it is considered to discussion above, �� 15% can be changed from described value at this numerical value about modified by word, except as otherwise noted.
As used herein, it is proposed to any scope all include end points. Such as, " temperature of 10 DEG C-30 DEG C " or " temperature from 10 DEG C to 30 DEG C " include 10 DEG C and 30 DEG C, and any temperature therebetween.
As used herein, the material of the layer or film (such as coating) that are described as " being arranged on " described base material " top " such as refers to the coating of the material of at least some of top being deposited on substrate surface directly or indirectly. " layer " or " coating " of given material is the material area (such as length and width size can be at least the 5 of gauge in some embodiments, 10,20,50,100 times) that its thickness is less than its length and width. Direct precipitation means that this coating is directly applied to the surface of base material. Deposition means that this coating puts on the intermediary layer being deposited on directly or indirectly above base material indirectly. Coating is by the surface bearing of base material, no matter this coating directly or is indirectly deposited on the surface of base material. As used herein layer needs not to be plane, for instance be rendered as the profile of lower substrate. Layer can be discontinuous. Layer can have thickness heterogeneous. Term " coating ", " layer " and " coat " is used interchangeably, and means such as layer described in this paragraph, film or coating.
As used herein term " coating layer thickness " or " layer thickness " refer to the degree of depth in deposition direction.
The present invention is explained referring now to description below and non-limiting example. Without further describing, it is believed that those skilled in the art can use aforesaid explanation farthest to utilize the present invention. Therefore, embodiments below, it is interpreted only as only illustrative, and limits remainder of this disclosure never in any form.
Embodiment of the present invention include method, and the method includes applying one or more metallicity coats to the base material comprising pyrolytic graphite, and this metallicity coat includes metal, or includes metal matrix composite, or includes both. The microscopic structure of the metal of metallicity coat can be metal amorphous, particulate, or their combination. As it is used herein, " finely-divided metal " is to have 1 to 5, the metal of the mean diameter of 000nm. As it is used herein, pellet material term " metal matrix composite " (MMC) being defined as in that be embedded in particulate and/or unbodied metallic matrix (having 1 to 5, the metal of the mean diameter of 000nm). Metallicity coat has less than 25 �� 10 in all directions-6K-1Room temperature linear thermal expansion degree coefficient (CLTE), for instance 5.0 �� 10-6K-1To 25 �� 10-6K-1Scope in. Embodiment of the present invention also include the pyrolytic graphite goods of coating, and specifically include radiator.
Containing finely-divided metal, amorphous metal or both coatings and the method that applies them described in the U.S. Patent Application Publication No. 2010/0028714 announced on February 4th, 2010 and the U.S. Patent number 8394507 promulgated on March 12nd, 2013. This coating can with NanovateTMThe form of coating derives from IntegranTechnologies, the Inc. of Toronto. In a preferred embodiment, coating originates from the high intensity of IntegranTechnologies, the Inc. of Toronto, the nano-structured ferronickel coating of low thermal coefficient of expansion, NanovateTMN2040 coating.
From the high intensity of IntegranTechnologies, the Inc. of Toronto, the nano-structured ferronickel coating (Nanovate of low thermal coefficient of expansionTMN2040) coating to pyrolytic graphite base material (specificallyHT pyrolytic graphite) applying cause thermal conductivity increase about 10% in the sample. In all previous work, coating pyrolytic graphite causes the decline of thermal conductivity because of the thermostability of the increase of coating. Additionally, NanovateTMN2040 coating adds the mechanical performance of sample, for instance but it is not limited to bending strength.
MMC can be produced in the following way: such as when using electroplating technology by particle in suitable plating bath and pellet material is incorporated to electrodeposit by being mingled with, or such as when cold spraying by adding non deformable pellet to powder feed. Other method preparing metallicity coat includes direct current or pulse electrodeposition, electroless deposition, physical vapour deposition (PVD) (PVD), chemical vapour deposition (CVD) (CVD) and gas condensation etc. Some exemplary methods include describing in the following documents those: the U.S. Patent Application Publication No. 2005/0205425A1 of JIUYUE in 2005 announcement on the 22nd; The U.S. Patent number 7387578 that on June 17th, 2008 announces; And DE10288323.
The solid grain material that can use in forming MCC includes metal (Ag, Al, Cu, In, Mg, Si, Sn, Pt, Ti, V, W, Zn); Metal-oxide (Ag2O��Al2O3��SiO2��SnO2��TiO2, ZnO); The carbide of B, Cr, Bi, Si, W; Carbon (CNT, diamond, graphite, graphite fibre); Glass; Polymeric material (politef, polrvinyl chloride, polyethylene, polypropylene, acrylonitrile-butadiene-styrene (ABS) and epoxy resin); And self-lubricating material, for instance but it is not limited to MoS2. Solid grain can account for the at most 95 volume % of this coating, it is preferable that 1% to 95 volume %, more preferably 5% to 75 volume %, and even more preferably from from 10% to 50 volume %.
Alloy addition may be used in metallicity coat, and it is recorded in the U.S. Patent number 8394507 of U.S. Patent Application Publication No. 2010/0028714 and promulgation on March 12nd, 2013.
One or more mid-coat layer can be there is between substrate surface and metallicity coat. This mid-coat layer can include but not limited to metal, polymer, or metal and polymer. At the material used in the intermediate layer described in United States Patent (USP) 8394507 and U.S. Patent Application Publication 2010/0028714.
The surface of pretreating substrates can be come to form particular surface form, being called " anchoring structure " or " anchored site " as described in United States Patent (USP) 8394507 by suitable roughening or at least one surface to be coordinated of veining.
About the base material used, U.S. Patent number 8394507 discusses the polymer as base material or polymer composites, but does not disclose carbon substrate. U.S. Patent Application Publication 2010/0028714 discloses the base material of " carbon-based material selected from graphite, graphite fibre and CNT ".
Graphite is constituted by the plane layer of the network of carbon atom or six square arrays. Former these layer planes of the carbon of Hexagonal array be substantially flat and be orientation, thus substantially parallel and equally spaced from each other. The parallel layers of the substantially flat of carbon atom is referred to as basal plane, and connects in the race be arranged in crystallite or combine. Conventional or electrolysis graphite has the order random for crystallite. The graphite of high-sequential has the preferred crystallite orientation of height. As it is shown in figure 1, graphite flake 2 has six side's covalent bonds in stacking crystal structure, and the graphite linings of each graphite flake 2 is connected by Van der Waals force. The conductivity value that graphite flake 2 has at the X-Y plane of graphite flake 2 is bigger than the value on thickness direction and Z-direction. The another kind of method characterizing graphite is: have two main shafts, " c " axle or direction and " a " axle or direction, is somebody's turn to do " c " axle or direction is identified generally as the axle or direction that are perpendicular to carbon-coating, and be somebody's turn to do " a " axle or be oriented parallel to carbon-coating and transverse to c-axis. The nomenclature of this replacement is also depicted in Fig. 1. " c " axle is equal to Z-direction, and two " a " axles are equal to X-Y plane. Such as what use with reference to the axle of graphite flake, term " XY " can exchange with " a " and " a-a " and use, and term " Z " exchanges with " c " and uses.
Show height-oriented graphite material and include the graphite of native graphite and synthesis or pyrolysis. Native graphite is can with the form of thin slice (thin plate) or be purchased with powder. The graphite of pyrolysis is produced by the carbonaceous gas pyrolysis on suitable base material at elevated temperatures. Briefly, can in the stove of heating and carrying out pyrolysis deposition process under suitable pressure, wherein by appropriate hydrocarbon gas, such as methane, natural gas, acetylene etc. are incorporated in the stove of heating, and the surface thermal decomposition such as at the base material of suitable composition with the graphite of any desirable shape carries out. Can remove from pyrolytic graphite or separation substrate. Then further pyrolytic graphite can at high temperature be carried out thermal annealing to form the height-oriented pyrolytic graphite being commonly referred to HOPG.
In order to in radiator, it is preferred to use the thermal conductivity height-oriented pyrolytic graphite more than 1500 watts/ meter Du Kai, especially, the suitable example for this purposes is New York, the trade name that the MINTEQ international corporation of N.Y makesHT. Generally, thermal conductivity is caused by free electron and lattice vibration. The high thermal conductivity (1000-2000 watt/ meter Du Kai) of diamond is caused by lattice vibration, and extremely the thermal conductivity of anisotropic HT graphite equals to or less than diamond because of free electron and lattice vibration.
But,HT pyrolytic graphite has many useful characteristics, for instance following: density 2.22g/cc, hot strength 28900kPa (XY direction), elastic modelling quantity 50GPA (XY direction), bending modulus 33200MPa (XY direction), thermal coefficient of expansion 0.6 �� 10-6/ degree Celsius (XY direction), 25 �� 10-6/ (Z-direction), 1700 watts/ meter Du Kai of thermal conductivity (XY direction), 7 watts/inch degree centigrade open (Z-direction), 5.0 �� 10-4Than resistance �� cm (XY direction), 0.6 �� cm (Z-direction), oxidation threshold 650 degrees Celsius (XY direction) and permeability 10-6Mm mercury column.
Compared with the thermal conductivity of other material,HT pyrolytic graphite thermal conductivity on XY direction is high, for instance be about 4 times of value of the overall thermal diffusion of about 6 times of value of aluminium nitride (AlN) and beryllium oxide (BeO), particularly copper (Cu) material.
As in figure 2 it is shown, manufactured by CVDHT pyrolytic graphite. In room 20 under vacuum (by vacuum pump 21), the appropriate hydrocarbon gas as unstrpped gas that supplies from cylinder 22 is decomposed by being heated to the gas more than 2000 degrees Celsius by heater 23, and it is layered stacking for the small carbon core C of deposition and crystallization on base material 24 in formation with being deposited on simultaneously, createsHT pyrolytic graphite.HT pyrolytic graphite can obtain with the thickness of 0.25 to 20mm, and can produce the various sizes as the big structure to 300 square millimeters of square shapes by controlling stacking and sedimentation time.
New York, the MINTEQ international corporation of N.Y also manufactures also by CVD explained hereafterThe pyrolytic graphite of CN (continuous nucleation) rank andSN (base material nucleation). These have ratioThe thermal conductivity that HT pyrolytic graphite is low.
Embodiment of the present invention also include the pyrolytic graphite goods of coating. One particular use of the pyrolytic graphite of coating is radiator. In preferred embodiments, useHT pyrolytic graphite, although other rank can be usedGraphite, or the pyrolytic graphite of other ranks. In these embodiments, radiator is coated in all outer surfaces, or on essentially all outer surface, described outer surface has one or more metallicity coat, and optionally includes one or more intermediate layer. Coating embeds or encapsulates or substantially embed or encapsulating radiator. The example of the radiator that can be applied include described in U.S. Patent number 8085531,7859848,7808787 and 8059408 any those. In preferred embodiments, coating includes dilval (as finely-divided metal), amorphous metal or their combination, optionally includes solid grain, it will be preferred that the solid grain of polymeric material. In preferred embodiments, if finely-divided metal exists, there is the particle diameter of 2nm to 5000nm. In preferred embodiments, the coating thickness of metallic layers is 10 to 500 ��m.
In a preferred embodiment, base material isHT pyrolytic graphite, it is used as radiator, is coated on all surfaces or substantially all surface, and described surface has the Nanovate of 25 to 50 ��mTMN2040 coating, high intensity, (it is from the IntegranTechnologiesInc. of Toronto, and uses the Nanovate of 25-50 ��m on all surfaces or basic surface for the nano-structured ferronickel coating of low thermal coefficient of expansionTMN2040 coating is coated withThe method of HT pyrolytic graphite.
Embodiment
Only by illustrating that the mode of the present invention provides embodiment in this section, it is not intended to also be not interpreted as the scope being intended to limit the present invention in any manner.
Embodiment 1
The ASTME1461FlashMethod measured for thermal conductivity is used to test tenThe thermal conductivity of the sample of HT pyrolytic graphite. In Table 1, in first group of five sample, the thermal conductivity in XY orientation measurement, and for second group of five sample, measure thermal conductivity in Z-direction. As shown in table 1, it is 1567-1737 in XY direction thermal conductivity �� (counting with W/m-K).
Table 1
ASTME1461FlashMethod thermal conductivity result
Embodiment 2
The ASTME1461FlashMethod measured for thermal conductivity is used to test fiveThe thermal conductivity of the sample of HT pyrolytic graphite. It is labeled as the sample #1-#3 of UA1051, UA1052 and the UA1053 Nanovate being respectively coated with the coating layer thickness of 25 ��m, 50 ��m and 50 ��mTMDilval coating. Sample #4 and #5 is uncoated. Thermal conductivity in XY direction detection sample #1 and #2. For sample #3-#5, measure thermal conductivity in Z-direction. As shown in table 2, for the samples (sample #1 and #2) of two coatings each XY orientation measurement in the �� of W/m-K than any embodiment 1 in 5 non-coated samples recording high. It addition, the thermal conductivity in Z-direction relative to uncoated sample #4 and #5, coated sample #3 is higher.
Table 2
ASTME1461FlashMethod thermal conductivity result
Embodiment 3
Use ASTMD790 test program, at the temperature of 73 ��F and the relative humidity of 50%, measure 10 of thick 0.0625 inch, wide 0.5625 inch and long 0.90 inch uncoatedBending extension rate on the XY direction of the pyrolytic graphite sample of HT. The result of 10 samples is shown in Table 3:
Table 3
Embodiment 4
Use ASTMD790 test program, at the temperature of 73 ��F and the relative humidity of 50%, measure 4 of thick 0.0625 inch, wide 0.5625 inch and long 0.90 inch uncoatedBending extension rate in the Z-direction of the pyrolytic graphite sample of HT. The result of 10 samples is shown in Table 4:
Table 4
Embodiment 5
Use ASTMD790 test program, at the temperature of 73 ��F and the relative humidity of 50%, measure 4 coatings of thick 0.0625 inch, wide 0.5625 inch and long 0.90 inchBending extension rate in the Z-direction of the pyrolytic graphite sample of HT. With the Nanovate of thick 25 micronsTMNickel cobalt (alloy) coating coated sample #1. With the Nanovate of thick 25 micronsTMDilval coating coated sample #2. With the Nanovate of thick 50 micronsTMNickel cobalt (alloy) coating coated sample #3. With the Nanovate of thick 50 micronsTMDilval coating coated sample #4. Thered is provided by IntegranTechnologies company and apply NanovateTMCoating. The result of 4 samples is shown in Table 5:
Table 5
As shown in table 5, higher compared to the bending stress of each of four samples in the sample shown in table 4, table 5. For all samples in table 5, except sample #1, yield strain is higher.
It is therefore to be understood that the foregoing description of the present invention is prone to be carried out sizable amendment by those skilled in the art, change and adjust, and intending such amendment, change and adjust consideration within the scope of the invention, appended claim elaborates the scope of the present invention.
Claims (20)
1. a method:
The metallicity coat comprising metal is arranged at least one of top on pyrolytic graphite substrate surface, this metal includes nickel, ferrum, nickel-ferro alloy or their any combination, and the particle of this metal is of a size of 1nm to 10000nm, this metal is unbodied, or both.
2. method according to claim 1, wherein pyrolytic graphite is height-oriented pyrolytic graphite, the pyrolytic graphite of chemical vapour deposition (CVD) or their combination.
3. method according to claim 1, wherein this coating is NanovateTMN2040 coating.
4. the method according to any one in claim 1-3, wherein the particle diameter of this metal is 2 nanometers to 5000 nanometers.
5. the method according to any one in claim 1-3, wherein this coating includes alloying additive.
6. method according to claim 5, wherein alloying additive is selected from B, C, H, O, P, S and combination thereof.
7. the method according to any one in claim 1-3, wherein this coating includes the solid grain of metal; Metal-oxide; The carbide of B, Cr, Bi, Si, W, or their combination; Carbon; Glass; Polymeric material; MoS2; Or their combination in any.
8. method according to claim 7, wherein this coating includes the solid grain of at most 95 volume %.
9. the method according to any one in claim 1-3, wherein the thickness of metallicity coat be 10 ��m to 50mm.
10. the method according to any one in claim 1-3, wherein before the applying of metallicity coat, applies one or more mid-coat layer.
11. method according to claim 10, wherein said mid-coat layer includes metal, polymer or metal and polymer.
12. method according to claim 10, the thickness of wherein said mid-coat layer is less than the thickness of described metallicity coat.
13. according to the method described in any one in claim 1-3, wherein metallicity coat covers whole outer surfaces of base material.
14. according to the method described in any one in claim 1-3, wherein said metallicity coat covers the only a part of the outer surface of described base material.
15. according to the method described in any one in claim 1-3, the base material being wherein coated with metallicity coat demonstrates the thermal conductivity being not less than uncoated base material.
16. according to the method described in any one in claim 1-3, wherein be coated with the base material of metallicity coat demonstrate uncoated base material thermal conductivity about 105% thermal conductivity, or be not less than 105% and also thermal conductivity less than the 250% of uncoated base material of uncoated base material.
17. according to the method described in any one in claim 1-3, wherein be coated with the base material of metallicity coat demonstrate uncoated base material thermal conductivity about 110% thermal conductivity, or be not less than 110% and also thermal conductivity less than the 250% of uncoated base material of uncoated base material.
18. according to the method described in any one in claim 1-3, wherein be coated with the base material of metallicity coat demonstrate uncoated base material thermal conductivity about 115% thermal conductivity, or be not less than 115% and also thermal conductivity less than the 250% of uncoated base material of uncoated base material.
19. according to the method described in any one in claim 1-3, wherein metallicity coat has less than 25 �� 10 in all directions-6K-1Room temperature thermal linear expansion coefficient.
20. goods, comprise:
The base material of pyrolytic graphite;
It is deposited on the metallicity coat comprising metal of at least some of top on the surface of pyrolytic graphite substrate, this metal comprises nickel, ferrum, nickel-ferro alloy or their any combination, and the particle of this metal is of a size of 1nm to 10000nm, this metal is unbodied, or both.
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| US201361884818P | 2013-09-30 | 2013-09-30 | |
| US61/884,818 | 2013-09-30 | ||
| PCT/US2014/057816 WO2015048516A1 (en) | 2013-09-30 | 2014-09-26 | Performance enhanced heat spreader |
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| US (1) | US20150090434A1 (en) |
| EP (1) | EP3052676A1 (en) |
| JP (1) | JP2016535941A (en) |
| KR (1) | KR20160065141A (en) |
| CN (1) | CN105637124A (en) |
| CA (1) | CA2925816A1 (en) |
| SG (1) | SG11201601821VA (en) |
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| US10444515B2 (en) | 2015-01-20 | 2019-10-15 | Microsoft Technology Licensing, Llc | Convective optical mount structure |
| US10028418B2 (en) | 2015-01-20 | 2018-07-17 | Microsoft Technology Licensing, Llc | Metal encased graphite layer heat pipe |
| US9791704B2 (en) * | 2015-01-20 | 2017-10-17 | Microsoft Technology Licensing, Llc | Bonded multi-layer graphite heat pipe |
| US10108017B2 (en) | 2015-01-20 | 2018-10-23 | Microsoft Technology Licensing, Llc | Carbon nanoparticle infused optical mount |
| US9674986B2 (en) * | 2015-08-03 | 2017-06-06 | Apple Inc. | Parallel heat spreader |
| US10584927B2 (en) * | 2015-12-30 | 2020-03-10 | General Electric Company | Tube thermal coupling assembly |
| CN106328614A (en) * | 2016-09-28 | 2017-01-11 | 厦门恒坤新材料科技股份有限公司 | Graphite sheet and metal layer composed thermally conductive sheet and its composing method |
| GB201706783D0 (en) * | 2017-04-28 | 2017-06-14 | Cambridge Entpr Ltd | Composite layers, methods for their manufacture and uses thereof |
| WO2019060503A2 (en) * | 2017-09-20 | 2019-03-28 | eChemion, Inc. | Manufacturing enhanced graphite metallic bipolar plate materials |
| GB2569306A (en) * | 2017-12-12 | 2019-06-19 | Rolls Royce Plc | Thermal management device |
| JP7032348B2 (en) * | 2019-03-26 | 2022-03-08 | 矢崎総業株式会社 | Metal-plated carbon material and its manufacturing method |
| US20230073259A1 (en) * | 2020-02-18 | 2023-03-09 | Lam Research Corporation | High temperature substrate support with heat spreader |
| CN111690963B (en) * | 2020-06-24 | 2022-10-04 | 上海理工大学 | Method for preparing copper/graphite/copper laminated composite material with high thermal conductivity |
| US11882673B1 (en) * | 2020-11-25 | 2024-01-23 | Advanced Cooling Technologies, Inc. | Heat spreader having conduction enhancement with EMI shielding |
| TWI768966B (en) * | 2021-06-15 | 2022-06-21 | 許國誠 | Graphite based composite laminated heat dissipation structure and manufacturing method thereof |
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| KR20160065141A (en) | 2016-06-08 |
| JP2016535941A (en) | 2016-11-17 |
| SG11201601821VA (en) | 2016-04-28 |
| TW201524755A (en) | 2015-07-01 |
| WO2015048516A1 (en) | 2015-04-02 |
| EP3052676A1 (en) | 2016-08-10 |
| CA2925816A1 (en) | 2015-04-02 |
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