CN1754079A - Flexible graphite thermal management devices - Google Patents

Flexible graphite thermal management devices Download PDF

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Publication number
CN1754079A
CN1754079A CNA200380109925XA CN200380109925A CN1754079A CN 1754079 A CN1754079 A CN 1754079A CN A200380109925X A CNA200380109925X A CN A200380109925XA CN 200380109925 A CN200380109925 A CN 200380109925A CN 1754079 A CN1754079 A CN 1754079A
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Prior art keywords
graphite
management device
case
heat management
core
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CNA200380109925XA
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CN100575853C (en
Inventor
D·W·克拉索夫斯基
G·G·陈
T·W·伯克特
B·H·福德
J·-W·曾
J·诺尔利
M·D·斯马尔克
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Graftech Inc
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Graftech Inc
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D15/00—Heat-exchange apparatus with the intermediate heat-transfer medium in closed tubes passing into or through the conduit walls ; Heat-exchange apparatus employing intermediate heat-transfer medium or bodies
    • F28D15/02—Heat-exchange apparatus with the intermediate heat-transfer medium in closed tubes passing into or through the conduit walls ; Heat-exchange apparatus employing intermediate heat-transfer medium or bodies in which the medium condenses and evaporates, e.g. heat pipes
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/48—Macromolecular compounds
    • C04B41/4857—Other macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D15/00—Heat-exchange apparatus with the intermediate heat-transfer medium in closed tubes passing into or through the conduit walls ; Heat-exchange apparatus employing intermediate heat-transfer medium or bodies
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D15/00—Heat-exchange apparatus with the intermediate heat-transfer medium in closed tubes passing into or through the conduit walls ; Heat-exchange apparatus employing intermediate heat-transfer medium or bodies
    • F28D15/02—Heat-exchange apparatus with the intermediate heat-transfer medium in closed tubes passing into or through the conduit walls ; Heat-exchange apparatus employing intermediate heat-transfer medium or bodies in which the medium condenses and evaporates, e.g. heat pipes
    • F28D15/04—Heat-exchange apparatus with the intermediate heat-transfer medium in closed tubes passing into or through the conduit walls ; Heat-exchange apparatus employing intermediate heat-transfer medium or bodies in which the medium condenses and evaporates, e.g. heat pipes with tubes having a capillary structure
    • F28D15/046—Heat-exchange apparatus with the intermediate heat-transfer medium in closed tubes passing into or through the conduit walls ; Heat-exchange apparatus employing intermediate heat-transfer medium or bodies in which the medium condenses and evaporates, e.g. heat pipes with tubes having a capillary structure characterised by the material or the construction of the capillary structure
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F23/00—Features relating to the use of intermediate heat-exchange materials, e.g. selection of compositions
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/50—Flexible or elastic materials

Abstract

The invention provides to thermal management devices constructed from flexible graphite. In one embodiment, the thermal management device includes a wick structure (16) inside a shell (14). In certain preferred embodiments, the wick structure is composed of a mass of expanded graphite. In another embodiment, the shell of the device includes flexible graphite and an optional wick structure. In certain preferred embodiments, the flexible graphite shell is fluid impermeable. The invention further includes methods of making the aforementioned thermal management devices.

Description

The soft graphite heat management device
Technical field
The present invention relates to heat management device, and relate to this device that contains soft graphite and the preparation method of this device in more detail.
Background technology
Heat management device is heat pipe for example, is the device of knowing in art of heat transfer.Heat pipe is a heat transfer closed system basically, and wherein the small amount of liquid in the chamber that seals and find time circulates by evaporation and condensation cycle.A certain position enters heat in the chamber at described position evaporating liquid on shell, produces steam, and steam moves to position colder on the shell and in this place's condensation.Moving by the small steam pressure difference between evaporimeter and condenser locations of steam promotes.Basically move to condenser locations with steam in the heat of evaporation that produces steam and also discharge as condensation heat herein, heat transfer is achieved.
Be able to continuously for making to conduct heat, the liquid of condensation must be got back to evaporimeter by condenser, and it will be evaporated once more herein.Although this recurrence can be finished by simple condition as gravity, adopt the capillary core body to make heat pipe can not rely on the effect of gravity relatively usually.This capillary core body extends to the position of its evaporimeter that need be evaporated near the position the condenser that produces liquid.
About structural material, shell is made by copper or other metals usually, and be prepared into the wall of adequate thickness, structurally can bear the steam pressure in the heat pipe, and guarantee that it is impermeable for concentrating the outer incondensible gas of steam or heat pipe shell to guarantee it.
In research is that the heat conducting material that can be used as the core body capillary pipe structure again drop into considerable effort.The modal of these materials is to adopt metal screen cover and the metal dust that is sintered in the structure that is connected shell in multilayer.It is very important that the heat-conductive characteristic of these core bodys is considered to, thus enter that the heat of heat pipe will be imported into and by core body at evaporimeter, and the liquid in the evaporation core body.Equally usually preferably in heat pipe construction core body be connected on the shell wall at evaporimeter, make the heat of input can directly enter the liquid in the core body.
Yet traditional heat conduction structure can not be satisfactory in some purposes.Metal shell and metallic core have increased weight, rigidity and the electric conductivity of heat pipe, but this makes them inapplicable under certain conditions.Portable computer, so-called " notebook computer " is that the traditional hot conduit is difficult to be used for one of purposes wherein.In these purposes, weight and space are special The key factor.In addition, the expense of the core body of metal shell and sintering is disadvantageous in the market of the high competition of portable computer.In addition, not corrosion-resistant from the core component of traditional material.Therefore there are the needs of finding the new material of structure heat pipe.
The disclosure of the Invention content
An embodiment of the invention provide the case that comprises fluid impermeable basically and the heat management device of the core in the case.In some preferred implementation, this core body comprises mass of expanded graphite.
Another embodiment of the invention provides preparation and have the method for the heat management device of the core that forms by mass of expanded graphite.
Another embodiment of the invention provides heat management device with the case that constitutes by soft graphite.
Additional embodiment of the present invention comprises that preparation has the method for the heat management device of the case that is made of soft graphite, and this embodiment is conspicuous for those skilled in the art after having read this specification.
Heat management device of the present invention has many advantages with respect to their traditional corresponding intrument, and the some of them advantage comprises excellent weight, acceptable rigidity and gratifying thermal conductivity.In addition, the core of apparatus of the present invention has also improved corrosion resistance with respect to traditional core material.
Other features and advantages of the present invention will be enumerated in following detailed description, and partly will be conspicuous for those skilled in the art or be familiar with by implementing the present invention described here from specification, comprise the following detailed description, claim and appended accompanying drawing.
It will be appreciated that the generality of carrying out is previously described and following detailed has been set forth embodiments of the present invention, and purpose is to be provided for understanding the general picture and the framework of nature of invention required for protection and characteristic.Appended accompanying drawing in being included in provides further understanding of the present invention, and is dissolved into this specification and constitutes the part of this specification.Accompanying drawing has been set forth different embodiment of the present invention, and is used from explanation principle of the present invention and operation with description one.
Fig. 1 is the plane of the internal state of cylindrical heat pipe.
Fig. 2 is the exploded view of the assembly of vertical heat pipe.
Fig. 3 is the plane of a specific implementations of the creationary heat pipe in the heat propagation device.
Fig. 4 is the cross-sectional view of a specific implementations with heat management device of fin keel.
Best implementation method of the present invention
The feature of graphite can be the stepped construction of carbon, and just, structure is combined by weak Fan Dehuali by the overlapping layer of carbon atom or lamination and constitutes.Consider the structure of graphite, indicate with two axles or direction usually, that is, and " c " axle or direction and " a " axle or direction.For simplicity, " c " axle or direction can be understood as the direction vertical, " a " axle or direction with carbon-coating can be understood as the direction parallel with carbon-coating or with the vertical direction of " c " direction.The graphite that is applicable to the production flexible graphite sheet is the graphite with very high degree of orientation.
As mentioned above, the adhesion that the parallel layers of carbon atom is combined only is weak Fan Dehuali.Native graphite can be processed, make can be suitable in overlapping carbon-coating or the space between lamination open, to be provided on the direction perpendicular to layer, promptly, in " c " direction, the significant expansion, and therefore form the graphite-structure that expands or enlarge, wherein the stack characteristic of carbon-coating is kept substantially.
The graphite flake that greatly expands and more particularly expand into " c " direction size that has final thickness or can form about 80 times or higher multiple of size on " c " direction originally, and need not to use adhesive, for example (being commonly referred to as " soft graphite ") such as net, paper, bar, winding, thin slice, pads at the interior poly-sheet material or the integral sheet of expanded graphite.Be expanded to the constituent of graphite granule of " c " size that has final densities or be equivalent to about 80 times or the higher multiple of original " c " direction size, need not to use any binding material, obtain the overall flexibility sheet material by compression, be considered to possible, this is because of the mechanical interlocked or cohesive force that obtains between the graphite granule by volumetric expansion.
Above-mentioned sheet material, except flexibility, also have been found that the anisotropy that has for heat and electrical conduction and diffuse fluid height, than the native graphite initiation material, owing to stand high compression (for example rolling), the opposite face of the sheet material that the orientation of expanded graphite particles and graphite sheet are arranged essentially parallel to.Zhi Bei sheet material has the flexibility of excellence, good intensity and orientation very highly like this.
In brief, preparation is flexible, the technology of the anisotropic graphite sheet (for example net, paper, bar, winding, thin slice, pad etc.) of adhesive-free, be included under the predetermined load and do not exist the condition lower compression or the compacting of adhesive, has the expanded graphite particles that has about 80 times or the higher multiple of original particle in " c " direction size, to form smooth, flexible basically whole graphite sheet.Expanded graphite particles is normally as worm or vermiform outward appearance, in case through overcompression, will keep compression mould to set and the alignment of sheet material corresponding main surfaces.The density of sheet material and thickness can change by the degree of control compression.The density of sheet material can be in the scope of the about 2.0g/cc of about 0.04g/cc-.The flexible graphite sheet material list reveals the anisotropy of significance degree, this be because the arrangement of graphite granule be parallel to sheet material mainly towards, parallel surfaces, the increase of anisotropic degree depends on the degree that causes the roller roll compacting that density increases.In the anisotropic sheet material material of roller roll compacting, its thickness, promptly perpendicular to comprising " c " direction towards, the direction that is parallel to sheet surface and in the direction in long and wide region, promptly, along or be parallel to towards, first type surface comprises that the calorifics of " a " direction and sheet material is very different with electrical properties, has the difference of the order of magnitude in " c " and " a " direction.
Propose by the method for graphite granule article of manufacture is existing.For example, the United States Patent (USP) 5882570 of authorizing Hayward discloses a kind of method, wherein grind flexible untreated graphite to nominal particle size, these particles of thermal shock make its expansion, these expanded graphites and thermoset phenolic resin are mixed, the injection moulding molten mixture is to form low-density bulk and other shapes, and these blocks of heat treatment are with the described material of heat cure then.The block of gained can be used for the insulating materials of stove etc.
All be to authorize the WO 00/54953 of Hayward and the technology that United States Patent (USP) 6217800 has further described United States Patent (USP) 5882570.Described Hayward technology only limit to their employed raw-material scope and they the type of fertile end product.Hayward only uses untreated graphite parent material and its end product, and only the mixed with resin by graphite granule and big ratio and injection moulding molten mixture are to form goods, and it is subsequently by heat cure.
Speak of graphite, known graphite is that the layered planes by carbon atom hexagonal array or network constitutes.The layered planes of the carbon atom of these hexagonal arraies be basically the plane with orientation or be arranged as and make and to be parallel to each other basically and equidistant.The basic plane of carbon atom, the sheet material of parallel equidistant or layer are commonly referred to graphite linings (graphene layer) or basic side (basal plane), connect or key connects together and their point set is arranged with crystal grain.Constitute the graphite of high-sequential by a certain size crystal grain.Described crystal grain is highly to arrange mutually or carbon-coating orientation and that have high-sequential.In other words, the graphite of high-sequential has the very preferred degree of grain alignment of high level.Therefore it should be noted that graphite has anisotropic structure and shows or have for example heat transfer of many short transverses and the character of electric conductivity and diffuse fluid.
The present invention can comprise provides for example parent material of the flexible sheet material of graphite material.Described parent material generally includes graphite, and the crystal habit of carbon atom is included on the layered planes of plane atom and connects with covalent bond and link to each other with more weak key between the plane.Be to obtain the parent material of for example above-mentioned graphite flexible sheet material, graphite granule, natural graphite flake is for example handled with the insertion agent of the solution of for example sulfuric acid and nitric acid usually, and the crystal structure of graphite reaction forms graphite and inserts the compound of agent.Treated graphite granule is called " graphite granule through inserting " hereinafter.By standing high temperature, the insertion agent in the graphite is decomposed and volatilization, cause graphite granule through inserting in the mode of similar gauffer on " c " direction, promptly, on direction perpendicular to the crystrallographic plane of graphite, expand into the size of about 80 times or the bigger multiple of its original volume size.The graphite granule outward appearance of peeling off is a vermiform, and therefore is commonly referred to worm.These worms are compressed in and form flexible sheet material together, and are different with original graphite flake, and it can form and be cut into difformity and be equipped with little transverse opening by the mechanical shock that causes being out of shape.
Being suitable for the graphite parent material that is used for flexible sheet material of the present invention comprises the carbonaceous material of the high graphitization that can insert organic or inorganic acid and halogen and stands to add thermal expansion then.The carbonaceous material of these high graphitizations most preferably has about 1.0 degree of graphitization.As the term " degree of graphitization " that uses in this disclosure with reference to value g according to following formula:
g = 3.45 - d ( 002 ) 0.095
Wherein d (002) is the distance of the graphite layers of the carbon measured with angstrom unit in crystal structure.Distance ' ' d ' ' in graphite layers is measured with the standard X-ray diffractive technology.Measured the position corresponding to the diffraction maximum of (002), (004) and (006) Miller indices, and adopted standard least-squares to derive distance, this overall error with all these peaks minimizes.The example of the carbonaceous material of high graphitization comprises the native graphite from various sources, and other carbonaceous materials are as the carbon by preparations such as chemical vapour despositions.In many examples, native graphite is preferred.
The graphite parent material that is used for flexible sheet material of Shi Yonging can contain non-carbon component in the present invention, as long as the crystal structure of parent material keeps required graphited degree and them to peel off.Usually, any carbonaceous material as long as its crystal structure has required degree of graphitization and it can peel off, is fit to application of the present invention.This graphite preferably has the ash that is lower than 20 weight percentages.In some cases, the graphite of employing will have the purity at least about 94%.Under other preferable case, the graphite of employing will have the purity at least about 99%.
A kind of commonsense method that is used for preparing graphite sheet is recorded in people such as Shane at U.S.Patent 3404061, and its disclosure is incorporated herein by reference.In the typical practice of people's such as Shane method, natural graphite flake comprises for example solution of the mixture of nitric acid and sulfuric acid by thin slice is dispersed in, and the level of the graphite flake (pph) of per 100 weight portions of insertion solution of about 300 weight portions of advantageously about 20-is inserted.Insert solution and contain oxidant and other insertion agent well known in the prior art.Example comprises that those contain oxidant and oxidisability mixture, the solution that for example contains nitric acid, potassium chlorate, chromic acid, potassium permanganate, potassium chromate, potassium bichromate, perchloric acid etc., or mixture such as red fuming nitric acid (RFNA) and chlorate, chromic acid and phosphoric acid, sulfuric acid and nitric acid, or strong organic acid (for example trifluoroacetic acid) and dissolve in the mixture of organic acid strong oxidizer.Perhaps, can apply electromotive force and make graphite generation oxidation.The chemical substance that can adopt the electrolyte oxidation to be incorporated in the graphite crystal comprises sulfuric acid and other acid.
In a preferred embodiment, inserting agent is sulfuric acid or sulfuric acid and phosphoric acid, and oxidant, the i.e. mixture solution of nitric acid, perchloric acid, chromic acid, potassium permanganate, hydrogen peroxide, acid iodide or periodic acid etc.Insert solution sometimes even can contain metal halide for example iron chloride and the iron chloride that mixes with sulfuric acid, or halogen is for example as the solution of bromine and sulfuric acid or the bromine of the solution form of bromine in organic solvent.
The amount of inserting solution can be in the scope of the about 150pph of about 20-, also usually in the about 120pph scope of about 50-.After thin slice is inserted into, usually any excessive being dissolved in from thin slice is blotted and thin slice is washed.Perhaps, the amount of inserting solution can be restricted to the about 50pph of about 10-, and this is exempted rinsing step, and instruction and description in United States Patent (USP) 4895713, and its disclosure is incorporated herein by reference.
Through the graphite coating granules that insertion solution-treated can, randomly, be touched, for example mix with the reducing agent that is selected from alcohol, sugar, aldehyde and ester, these reducing agents are in 25 ℃ of-125 ℃ of temperature ranges and the oxidation skin covering of the surface reaction of inserting solution.Suitable specific organic reagent comprises hexadecanol, octadecanol, 1-octanol, sec-n-octyl alcohol, decyl alcohol, 1,10 decanediols, capraldehyde, 1-propyl alcohol, 1,3 propane diols, ethylene glycol, polypropylene glycol, glucose, fructose, lactose, sucrose, farina, ethylene glycol monostearate, diethylene glycol dibenzoate, propylene glycol monostearate, glycerine monostearate, dimethyl oxalate, diethy-aceto oxalate, methyl formate, Ethyl formate, ascorbic acid and lignin derivative compound be Sodium Lignosulphonate for example.The consumption of organic reducing agent is generally about 0.1%-5 weight % of particles of graphite flake.
Before inserting, during or insert after use bulking promoter immediately and also can provide and improve effect.Improve at these and can reduce exfoliation temperature in effect and to increase expanding volume (being also referred to as " worm volume ").Bulking promoter can advantageously a kind ofly can fully be dissolved in and insert the organic material of solution to obtain to expand and improve in context.Narrow sense ground more can preferably exclusively adopt the organic material of the type that contains carbon, hydrogen and oxygen.Have been found that carboxylic acid is effective especially.The suitable carboxylic acid that is used for bulking promoter can be selected from monocarboxylic acid aromatics, aliphatic series and cyclic ester family, straight or branched, saturated and undersaturated, dicarboxylic acids and polycarboxylic acid, it has at least one carbon atom, and being no more than 15 carbon atoms usually, it dissolves in the detectable consumption that improves effect that one or more aspects of peeling off can be provided and inserts in the solution.Can adopt appropriate organic solvent to improve the dissolubility of organic expander auxiliary agent in inserting solution.
The representative example of aliphatic saturated monocarboxylic acid is for example to have formula H (CH 2) nThose acid of COOH, wherein " n " is the number of 0-about 5, comprises formic acid, acetate, propionic acid, butyric acid, valeric acid, caproic acid etc.Replace carboxylic acid also can adopt for example Arrcostab of aldehyde and reactive carboxylic acid derivatives.The representative example of Arrcostab is methyl formate and Ethyl formate.Sulfuric acid, nitric acid and other known water-baseds are inserted agent can decompose formic acid, finally is decomposed into water and carbon dioxide.Owing to this reason, formic acid advantageously inserts in the agent in water-based at thin slice with other responsive bulking promoters and contacts with graphite flake before the dipping.The representative example of dicarboxylic acids is the aliphatic dicarboxylic acid that contains 2-12 carbon atom, particularly oxalic acid, fumaric acid, malonic acid, maleic acid, butanedioic acid, glutaric acid, adipic acid, 1,5-pentane dicarboxylic acid, 1, the own dicarboxylic acids of 6-, 1,10-dicarboxylic acids in the last of the ten Heavenly stems, cyclohexane-1,4-dicarboxylic acids and aromatic dicarboxylic acid be phthalic acid and terephthalic acid (TPA) for example.The representative example of Arrcostab is dimethyl oxalate and diethy-aceto oxalate.The representative example of cycloaliphatic acids be cyclohexane-carboxylic acid and aromatic carboxylic acid's representative example be benzoic acid, naphthoic acid, ortho-aminobenzoic acid, p-aminobenzoic acid, salicylic acid, neighbour,, terephthalic acid (TPA), methoxy benzoic acid and ethoxybenzoic acid, acetoacetamidobenzoiacids acids and acetaminobenzoic acid, phenylacetic acid and naphthoic acid.The representative example of hydroxyaromatic acid is hydroxybenzoic acid, 3-hydroxyl-1-naphthoic acid, 3-hydroxyl-2-naphthoic acid, 4-hydroxyl-2-naphthoic acid, 5-hydroxyl-1-naphthoic acid, 5-hydroxyl-2-naphthoic acid, 6-hydroxyl-2-naphthoic acid and 7-hydroxyl-2-naphthoic acid.What give prominence in the polycarboxylic acid is citric acid.
Insert solution bulking promoter normally water-based and that can contain the consumption of the 1-10% that has an appointment, this consumption is done to peel off in order to reinforcement.Bulking promoter contacted with graphite flake before or after the graphite flake use is inserted solution impregnation in one embodiment, bulking promoter can for example mix with V-mixer with suitable manner with graphite, and generally the consumption with the about 10 weight % of about 0.1 weight %-of graphite thin layer mixes mutually.
After inserting graphite flake, and then will be to insert the graphite flake and organic reducing agent blending mutually that agent applies through inserting, blend stands the temperature of 25 ℃ of-125 ℃ of scopes to promote reducing agent and the reaction of inserting coating.The heating period is no more than about 20 hours, and the wherein short heating period (for example at least about 10 minutes) carries out in being higher than the temperature of above-mentioned scope.
The graphite granule of Chu Liing is sometimes referred to as " graphite granule through inserting " like this.Stand high temperature for example at least about 160 ℃ high temperature and a lot of situations under about 700 ℃-1200 ℃ and higher, graphite granule through inserting in Zhe shape mode on the c direction, that is, on the direction of the crystrallographic plane that constitutes perpendicular to graphite granule, expand into and be equivalent to their original volume 80-1000 doubly or higher multiple.Through expand, promptly, through what peel off, graphite granule is a vermiform in appearance, and therefore is commonly referred to worm.Described worm can be compressed into flexible sheet material together, is different from initial graphite flake, and it can form and be cut into difformity and be equipped with small transverse opening by the mechanical shock that causes being out of shape described below.
Flexible graphite sheet and paper tinsel are interior poly-, have good processing intensity, and can suitably compress (for example by roller roll compacting) become thickness for about 0.05mm-4.00mm and usually density restrain every cubic centimetre (g/cc) for about 0.1-1.5.As in United States Patent (USP) 5 902 762, describing (by reference it being introduced herein), can flood with the resin that is provided at the reinforcement in the final soft graphite product to the ceramic additive of the about 1.5-30 weight of the graphite flake blending % through inserting.Additive comprises the ceramic fiber particle with the about 0.1-1.5 millimeter of length.That the width of particle is suitable is about 0.05-0.001mm.Ceramic fiber particle is not with graphite reaction and be not attached to graphite, and is being stable up to about 1100 ℃, under preferred about 1400 ℃ or the higher temperature.Suitable ceramic fiber particle is quartz glass fibre, carbon fiber and graphite fibre, zirconia, boron nitride, carborundum and the magnesia fibers of dipping, for example machine-shapings such as calcium metasilicate fiber, aluminosilicate calcium fiber, alumina fibre of naturally occurring mineral fibres.
Flexible graphite sheet can also after curing, be strengthened the water proofing property and the processing intensity (that is, rigidity) of flexible graphite sheet advantageously with resin and absorption resin treatment in some cases, and the profile of " fixing " sheet material.Appropriate resin content is preferably at least about 5 weight %, more preferably from about 10-35 weight % and suitably up to about 60 weight %.Find that in practice of the present invention useful especially resin comprises acrylic resin, epoxy resin and phenolic group resin system, or their mixture.Suitable epoxy-resin systems comprises those and other the multifunctional resin system based on diglycidyl ether or bisphenol-A (DGEBA); The phenolic resins that can adopt comprises resol and novolac resin.In a certain preferred implementation, the glass transition temperature of resin can may be compared with the serviceability temperature of calorifics thermal management device.Even so, as above the graphite sheet of preparation can be cut and be modified into required goods.Soft graphite with resin treatment also is called as " soft graphite of resin dipping " or " soft graphite of dipping ".
The present invention is described heat pipe referring now to aforementioned figures, but the invention is not restricted to heat pipe, and can be used for the heat management device of other types, for example vapor chamber.As possible, adopt similar or identical mark to describe assembly similar or identical in the accompanying drawing.
Fig. 1 is the plane of the internal state of cylindrical heat pipe, briefly is marked as 10.The cylindrical heat pipe 12 of the horizontal direction of describing among Fig. 1 that is mounted in the common itinerary that flows with respect to working fluid.Heat pipe 12 comprises case 14 and core 16.Choose wantonly, heat pipe 12 comprises at least one fluid passage 18 outside core 16, also represents with arrow E.Heat pipe 12 can also be included at least one fluid passage 20 within the core 16, also represents with arrow I.Core 16 can also comprise a large amount of approximate radial fluid passages, and it allows working fluid to flow into passage 20 from passage 18 through core 16 at least.Randomly, heat pipe 12 also comprises evaporimeter 22 and condenser 26 at heat pipe 12 relative two ends.
Heat pipe 12 can comprise the kit 28 of thermal source 30.Randomly, kit 28 end identical that be positioned at heat pipe with evaporimeter 22.In a certain preferred embodiment, kit 28 has the surperficial contacted surface with thermal source 30, and the described surface of kit 28 randomly has and the minute surface pattern of thermal source 30 with kit 28 contacted surfaces.In other preferred implementation, kit 28 also contacts with the exterior section of heat pipe 12.The contacting of kit 28 and heat pipe 12 can promote from thermal source 30 to heat pipe heat transmission 12.The building material of suitable kit 28 comprises soft graphite, copper, aluminium and their combination at least.Comprise eGRAF for the example of the suitable material of kit 28 from Graftech company TMHS 400.An example of thermal source 30 is computer chips.
As illustrating in Fig. 1, heat pipe 12 can also comprise a large amount of fin keel 32 of at least a portion that is positioned at case 14.Randomly, fin keel 32 is arranged in an end at case 12 condensers 26 places at least.About an embodiment of the heat pipe 12 that comprises fin keel 32, preferred fin keel 32 usefulness soft graphites are constructed.The suitable material of other of fin keel 32 may comprise any combination of copper, aluminium and above-mentioned definition material.Fin keel 32 is not limited to be depicted in the embodiment of Fig. 1.The structure of any suitable fin keel 32 can use as part of the present invention.For example fin keel 32 can comprise base element and along the combination of the fin keel at a large amount of intervals that heat pipe 12 vertical direction extend out.An embodiment of the invention can comprise fan, make air fin keel 32 tops move distributing with the heat that keeps absorbing by fin keel 32.
As shown in Figure 1, heat produces in thermal source 30.The heat that produces in thermal source 30 is transmitted to heat pipe 12 and vaporized working fluid in evaporimeter 22 at least.The vapor phase of working fluid is flowed through passage 20 as shown by arrow I in condenser 26.Working fluid steam in condenser 26, be condensed into liquid form and the calorie spread that from working fluid, removes that causes by condensation to fin keel 32 and be dispersed in the surrounding environment.The liquid form of working fluid 18 flows back in the evaporimeter 22 along the direction shown in the arrow E along passage.Be used for liquid working fluid is comprised gravity, capillarity or their combination at least from the typical flow mechanism that condenser 26 is transferred to evaporimeter 22.
Randomly, heat pipe 12 can be operated under pressure below atmospheric pressure.By regulating the pressure in the heat pipe 12, the temperature of working fluid evaporation can be adjusted to the relevant specified temp excursion of heat that produces with thermal source 30 in the heat pipe 12.For example, operate under the pressure that reduces if working fluid is water and heat pipe 12, water will be lower than about 100 ℃ of evaporations down.
Second embodiment of heat pipe illustrates in Fig. 2, and is marked as 40 synoptically.Randomly, heat pipe 40 is installed in the vertical direction with respect to the glide path of working fluid.But heat pipe 40 can be installed with any structure.Heat pipe 40 contains case, and this case comprises 44u and two material sheets of 44l.Sheet material 44u and 44l are positioned at the relative two ends of heat pipe 40.Sheet material 44l can be called evaporimeter and sheet material 44u can be called condenser.
Heat pipe 40 also comprises core 46.As shown in the figure, core 46 comprises four (4) individual different slab construction 46a-46d.It should be noted that heat pipe 40 is not limited to any specific number of plates.When relating to the structure of slab construction 46a-46d, the glide path of preferred working fluid changes to adjacent panels from a flat board.About dull and stereotyped 46a and 46b, the glide path that has shown dull and stereotyped 46a is opposite with the flow direction of working fluid by dull and stereotyped 46b just roughly.The spoke-like glide path that for example dull and stereotyped 46a has central small hole and extends from the outside radioactivity of central small hole.On the contrary, dull and stereotyped 46b comprises a center hub and the spoke-like supporting component that extends from the outside radioactivity of center hub.In addition, preferably dull and stereotyped 46c provides the flow path with dull and stereotyped 46b complementation.Like this equally at dull and stereotyped 46c that is associated and 46d.The make of core 46 makes the working fluid in the heat pipe 40 transmit by capillarity at least.
About an embodiment of the invention, heat pipe 12 preferably includes the case 14 of fluid impermeable basically, and preferably case 14 is vacuum-packed cavitys, and core 16 is within case 14.Randomly, the case 14 of heat pipe 12 can be constructed with soft graphite.Randomly, have at least about 1.6g/cc, typically at least about 1.7g/cc, more typical by the case 14 of soft graphite structure at least about 1.9g/cc, the most typical pact density of 2.0g/cc at least.
Be used to form the soft graphite that the soft graphite of case 14 can yes or no be flooded by resin.In addition, case 14 can contain the soft graphite more than 1 layer.In other embodiments of case 14, the inner surface of case 14 can contain at least one pipeline, preferred a plurality of pipelines.As used herein vacuum seal be meant adopt vacuum discharge in the case 14 to small part, preferred whole basically inoperative fluid.The inoperative fluid is defined herein as at least what exist in case 14 be not the fluid of working fluid, for example air.
Under the situation of case 14, can adopt different technology to form the case of required form by the soft graphite structure.For example can adopt compression to make flexible graphite sheet form the required form of case 14.The general pressure that is used for compressed flexible graphite comprises about 4bar or lower pressure, is generally about 2bar or lower.In second kind of technology, can adopt adhesive to make soft graphite form the required form of case 14.Under some optimum condition, adhesive is insoluble to working fluid or vice versa.In the third technology, the longitudinal seam that soft graphite is compressed into drum and heat pipe 12 is by adopting compression or adhesive and form and adopting latch to form case 14 at the axially open of each cylinder.
In other technologies, one or more flexible graphite sheet can be compressed into tubulose and can insert latch at an end of pipe and form case 14.Randomly, described sheet material can be pressed lines and be formed pipeline with the inner surface at case 14.Flexible graphite sheet can be by wrinkling in another replacement scheme.In other technology, flexible graphite sheet can be surrounded axle to form case 14.When cladded sheet materials, sheet material can coat with any structure, such as but not limited to the screw type cladded sheet materials.In above-mentioned technology, flexible graphite sheet can be that resin floods or not be the resin dipping.When relating to the sheet material of resin dipping, resin can be cured before or after forming case 14.
In other embodiment, case 14 is made of the 3 d part of soft graphite.In sheet material, processed passage.Preferred passage does not expand to and passes through sheet material fully.The openend of passage can seal with above mentioned adhesive, compression or any of latch technology.
In some preferred implementation, core 16 contains a kind of porous material, more preferably is mass of expanded graphite, further preferably has the soft graphite that density is no more than about 1.5g/cc again.Soft graphite is described as forming the mass of expanded graphite of sheet material as used herein.More preferably, the soft graphite of core 16 has the density that is no more than about 1.1g/cc, more preferably no more than the density of about 1.0g/cc be most preferably not exceeding the density of about 0.5g/cc.Further preferred described soft graphite has the density at least about 0.25g/cc.An example of this soft graphite is from Lakewood, the obtainable GRAFOIL of Graftech company of OH
A method can measuring the density of soft graphite is to pass through immersion density test.In this test weighing the soft graphite sample weight and write down this weight.Sample is immersed in the water that pre-determines volume then.The volume of the water that the submergence of record by sample arranges.Density is determined divided by the volume of the water that is arranged by the weight of sample.How to measure density and be not limited to above-mentioned immersion density test.
The soft graphite of core 16 can be the soft graphite of resin dipping or non-impregnated soft graphite.In structure 16 is under the situation of resin dipping.In a certain preferred implementation, structure 16 is flooded to introduce porous mode to structure 16.Under this condition, more preferably resin floods the dispersion of strengthening Capillary Flow and/or working fluid.
Randomly, flexible graphite wick structure 16 can also comprise the metal wire of at least a portion that is incorporated into core 16.The example of the metal wire that is suitable for comprises copper, aluminium, stainless steel, titanium and their combination.Metal wire can be incorporated in the core 16 with distinct methods.
A kind of method is metal wire can be wrapped in around at least a portion of outside of core 16.Second method, metal wire adhesively are attached to inside or outside at least a portion of core 16.The third method has formed the lamination of soft graphite and metal wire.At least a portion of lamination contains metal wire.
Core 16 can also contain one or more flexible graphite sheet.In addition, each flexible graphite sheet can comprise two-layer or more soft graphite layers.
In a specific implementations, core 16 contains wrinkling flexible graphite sheet.Preferably, described gauffer comprises fine gauffer.More preferably, described fine gauffer has about 1mm or littler amplitude.Crimped device can be used to form these gauffers.The embodiment of core 16 can contain second sheet material of soft graphite.Under some environment, second sheet material of soft graphite does not have wrinkling.
In another embodiment, core 16 contains at least one passage.Described passage can comprise that size is fit to first and the big or small second portion that is fit to promote liquid flow that promotes that steam flows.Core 16 can press lines to form passage in structure 16.The size of passage can be identical or different.If the size of passage is different, some passage can be that size is fit to promote steam to flow and the other size is fit to promote liquid flow.For structure 16, in one embodiment, core 16 is connected on the evaporimeter 22 of heat pipe 12.
Perhaps, core can be by the structure of the material beyond the expanded graphite.Suitable alternate material comprises metal for example aluminium, copper, iron, nickel, titanium and their combination.Described alternate material can be used to replace expanded graphite or be used in combination with expanded graphite.
Heat pipe 12 can also comprise working fluid cycles in case 14.The preferred embodiment of working fluid comprises methyl alcohol, ethanol, other alcohols, water and fluorocarbon (Freon for example ) at least a.In one embodiment, the structure of heat pipe comprises the case-core device of the heat pipe of finding time and uses at least enough fluid backfill heat pipes in the space of filled core body structure 16 then.
In a certain preferred implementation, the enough saturated core 16 of the content of the working fluid in the heat pipe.More preferably, be charged to the more saturated core of the content of the working fluid in the case 14 16 required amount many about 10 percentage points (10%).
The amount that contains working fluid randomly up to than saturated core 16 required amount Duo about 20 percentage points (20%).In other embodiments, the amount of working fluid comprises the volume of condenser 26 in the heat pipe 12, preferred volume many about 10% than condenser 26.A technology that is used for evacuate shell 14 is to vacuumize in the inside of case 14.The function of evacuate shell 14 is residual air or other inoperative fluids that remove as far as possible in the case 14.
In a preferred embodiment, the environment in the heat pipe reaches liquid and balance of steam.When heat enters in the evaporimeter, described balance is transferred to steam one side and has been increased the air pressure of heat pipe inside.Under the condition that increases air pressure, steam can be diffused into condenser, and low slightly temperature causes the steam condensation and discharges its evaporation latent heat in condenser.The fluid of condensation is preferably got back to evaporimeter by the capillary force, diffusion or the gravity for transport that exist then in core 16.
The continuous circulation of working fluid has been transmitted a large amount of heats with low thermal gradient.Preferably, the operation of heat pipe is passive, only drives by the heat that is transmitted.The benefit of passive operation comprises excellent reliability and good service life.
As shown in Figure 3, described creationary heat pipe can be contained in the heat propagation assembly, is marked as 50 synoptically.Assembly 50 comprises heat pipe 52.In a certain preferred implementation, heat pipe 52 comprises case or the core that at least one is made of above-mentioned soft graphite.
As shown in Figure 3, assembly 50 can also randomly comprise base unit 54.Preferably base unit 54 is positioned at an end of assembly 50, comprising the condenser (not shown).The suitable material of the structure of base unit 54 comprises soft graphite, copper, aluminium and their combination.Base unit 54 contains surface 56, and surface 56 can be used for a plurality of fin keel (not shown) are connected to assembly 50.In addition, assembly 50 can comprise kit 58.Preferably, kit 58 is positioned at heat pipe 52 has an end of evaporimeter and contacts with thermal source.Kit 58 appropriate structures materials comprise above-mentioned kit 28 identical materials.
In an embodiment of assembly 50, three cases of all of heat pipe 52, pedestal 54 and kit 58 are constructed with soft graphite, that is, and and from the eGraf of Graftech company TMIn a certain preferred implementation, the soft graphite of at least one of heat pipe 52, pedestal 54 and element 58 comprises lamination.Described lamination can bond together structure by the flexible graphite sheet of high density (in one embodiment, preferably at least about 1.6g/cc, more preferably at least about 1.7g/cc with most preferably at least about 1.9g/cc).Perhaps, described flexible graphite laminate can be by the flexible graphite sheet structure of a plurality of resin dippings, and described flexible graphite sheet is through hot pressing and solidifies to form whole basically structure.
Shown in Fig. 4 is the cross-sectional view of an embodiment of heat management device 60 and thermal source 70.Device 60 comprise that the pedestal 62 by the bottom forms and with thermal source 70 contacted cases.Preferably, pedestal 62 is constructed by conductive of material, for example, and copper, aluminium or their alloy.Described case also further comprises the element 66 on top, and it contains soft graphite.The adhesive that upper element 66 and lower base 62 can for example adopt epoxy resin for example by any suitable technology 64 engages at the interface.In a certain preferred implementation, device 60 comprises a plurality of fin keels 32 that extend out from the upper end face of element 66.
Randomly, device 60 can also comprise one or more internal support components 68.Described internal support component is not limited to any specific shape or with any specific structural material.Support component 68 can be by the conductive of material structure of for example copper, aluminium, expanded graphite or their combination.In an alternative embodiment, support component 68 can comprise the one or more fin keels that extended by upper element 66.
The present invention also is applied to the heat management device such as the vapor chamber of other types.Vapor chamber is similar to heat pipe in many aspects.Similar heat pipe, the latent heat of the evaporation of vapor chamber use working fluid is with location transmission heat low than thermal source from the thermal source to the temperature.In operation, working fluid some position in evaporation cavity in the vapor chamber is evaporated and moves to position colder in the evaporation cavity and is condensed in this colder position.
In a certain preferred implementation, vapor chamber contains at least one case that is similar to the case of heat pipe.Under these conditions, the case of vapor chamber contains soft graphite.Typically, vapor chamber also can contain working fluid.The working fluid of vapor chamber can be identical with the working fluid of above-mentioned heat pipe.Randomly, vapor chamber can comprise one or more inner support.Preferably, for example soft graphite, copper, aluminium or their combination prepare described inner support by the heat conducting material of some types.Randomly, at least a portion of vapor chamber outer surface can comprise as about the described a large amount of fin keel of heat pipe.

Claims (20)

1, a kind of heat management device, it comprises:
A. the case of fluid impermeable basically;
B. the core in the described case, described core comprises mass of expanded graphite; With
C. the working fluid that in described case, circulates.
2, the heat management device of claim 1, wherein said core also comprise the metal wire that inserts described core at least a portion.
3, the heat management device of claim 1, wherein said graphite comprise the graphite of resin dipping.
4, the heat management device of claim 1, wherein said mass of expanded graphite comprise that the sheet material of one or more soft graphites and at least one described sheet material have the density that is no more than about 1.5g/cc.
5, the heat management device of claim 1, the structural material of wherein said case comprises soft graphite.
6, the heat management device of claim 5, wherein said case also comprises outer surface, at least a portion of described outer surface has a plurality of fin keels that extend out from described outer surface.
7, the heat management device of claim 1, wherein said working fluid comprises at least a of alcohol, water and fluorocarbons.
8, the heat management device of claim 1, wherein said core also comprises a plurality of passages.
9, the heat management device of claim 8, wherein said a plurality of passages comprise that size is fit to first and the big or small second portion that is fit to promote liquid flow that promotes that steam flows.
10, a kind of method for preparing heat management device comprises:
A. mass of expanded graphite is formed core; With
B. described core is inserted the inside of the case of described heat management device.
11, the method for claim 10 also comprises described mass of expanded graphite is formed one or more flexible graphite sheet.
12, a kind of heat management device comprises:
A. the case of fluid impermeable basically, the structural material of wherein said case comprises soft graphite; With
B. the working fluid that circulates in the described case.
13, the heat management device of claim 12 also comprises the core in the described case.
14, the heat management device of claim 12, wherein said case comprise vacuum-packed basically chamber.
15, the heat management device of claim 12, the density of the described soft graphite of wherein said case comprises at least about 1.6g/cc.
16, the heat management device of claim 12, wherein said case comprise a plurality of soft graphite layers.
17, the heat management device of claim 12, the described soft graphite of wherein said case also comprises resin.
18, the heat management device of claim 12, wherein said case also comprises outer surface, at least a portion of described outer surface has a plurality of fin keels that extend out from described outer surface.
19, the heat management device of claim 12, wherein said case contains the inner surface that comprises a plurality of passages.
20, the heat management device of claim 12 also is included in a plurality of inner track pattern elements in the described case.
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CN102967163A (en) * 2012-11-29 2013-03-13 南京卡立得热能科技有限公司 Thermal expansion board
CN104457362A (en) * 2013-09-13 2015-03-25 波音公司 Energy storage and thermal management using phase change materials in conjunction with heat pipes and foils, foams or other porous media
CN105674777A (en) * 2016-01-25 2016-06-15 云南科威液态金属谷研发有限公司 Intelligent device based on liquid metal
CN109574001A (en) * 2019-01-09 2019-04-05 哈尔滨工业大学 A kind of preparation method of the low temperature without sulphur, heavy metal free expansible graphite
CN109574001B (en) * 2019-01-09 2021-11-30 哈尔滨工业大学 Preparation method of low-temperature sulfur-free and heavy metal-free expandable graphite

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AU2003297158A1 (en) 2004-07-22
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JP4652818B2 (en) 2011-03-16
CA2511504A1 (en) 2004-07-15
US20090032227A1 (en) 2009-02-05
KR101012195B1 (en) 2011-02-08
EP1576656A2 (en) 2005-09-21
US20040118553A1 (en) 2004-06-24
KR20050085880A (en) 2005-08-29
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JP2006511782A (en) 2006-04-06
WO2004059696A3 (en) 2005-04-28

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