CN102745674B - Manufacturing mold and manufacturing method of flake graphite film - Google Patents
Manufacturing mold and manufacturing method of flake graphite film Download PDFInfo
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Abstract
The invention relates to a manufacturing mold and a manufacturing method of a flake graphite film, and the method comprises the following steps: selecting a biaxially-oriented polyimide film as a raw material film, setting a manufacturing mold, placing the cut raw material film into the mold in a spaced and laminated manner, pressing the raw material film, performing a carbonization procedure in a carbide furnace, cooling, adjusting the pressure applied to the raw material film, performing a graphitization procedure, naturally cooling to obtain the finished product graphite film. The invention provides a complete and particular manufacturing process suitable for batch production of flake graphite films with high thermal conductivity, can realize batch production of artificial graphite films with high quality; the graphite film has good heat diffusivity and strong bending resistance, and is suitable for the solution of the heating problem for miniature electronic product components.
Description
Technical field
The present invention relates to a kind of mfg. moulding die and manufacture method of the graphite film as heat sink material, relate to especially a kind of mfg. moulding die and manufacture method of graphite film of sheet.
Background technology
Along with the continuous renewal of electronic product is regenerated, day by day to thinner, lighter future development, the heating problem of its electronic devices and components is also more and more outstanding.Traditional utilize metal fin, tinsel are carried out the method for heat conduction and heat radiation, and utilize the method for fan forced heat radiation more and more cannot meet electronic product change request with rapid changepl. never-ending changes and improvements.
Utilize metal fin to electronic product radiating, exist shortcomings such as taking electronic product internal space is large, increase Quality of electronic products.Use separately tinsel (as Copper Foil, aluminium foil or other metallic substance etc.) heat radiation, the work-ing life of electronic devices and components or speed of response can reduce, because the thermal conductivity of metallic substance itself is not high (for the copper of electronic component heat radiation, that in metal, radiating effect is best, its thermal conductivity is in 400W/mK left and right, thermal conductivity refers under steady heat transfer condition, the temperature difference of the both side surface of 1 meter of thick material is 1 degree, the heat transmitting by 1 square metre of area in 1 second), the heat that can leave is less, it is inadequate that the relative high electronic devices and components of thermal value simply utilize tinsel heat radiation, its thermal equilibrium temperature finally reaching can exceed the normal use temperature of electronic devices and components, cause electronic devices and components shorter work-ing life.Be directed to the electronic devices and components that thermal value is large, such as the cpu of computer etc., its radiating mode often adopts metal fin collocation fan to dispel the heat.But there is following shortcoming in fan cooling: the one, and the easy dust suction of fan, along with the increase of working hour of fan, can residual a certain amount of dust on fan and electronic devices and components, overstocked dust can affect greatly the radiating rate of electronic devices and components; The 2nd, noise is larger, even if so-called quiet fan also cannot avoid a certain amount of noise to exist completely now; The 3rd, take up room larger, along with the market requirement of the light-dutyer more thinning of electronic product, the use volume of fan is to there is certain obstruction.
Carbon is a kind of very magical element.The material that occurring in nature thermal conductivity is the highest is exactly carbon simple substance---diamond, and its thermal conductivity is 2300W/mK.The allotropic substance of carbon---graphite, has the high conductivity properties comparing favourably with diamond.The graphite-structure material that is typically used as heat conduction, heat radiation has graphite block, graphite flake (common graphite block, graphite flake thickness are between 0.3mm to 3mm), expandable graphite sheet (claiming again natural stone ink film) and rostone ink film.
Graphite block and graphite flake are mainly used to make all kinds of high-temperature resistant containers, or as heating pipeline, and the pad of hot-fluid pipeline etc., also apply as heat sink material gradually in recent years.Such as, high-power LED lamp is with regard to the method for useful graphite flake heat conduction, and the heat conductive silica gel, the high hot silicone grease that replace in the past serve as heat-conducting pad use.In addition, the matrix material such as ceramic graphite, plastics graphite of graphite-containing composition, alternative metals section bar uses as radiating equipment, but many-sided defect such as its snappiness is poor, is existing to bend, frangible.
Natural stone ink film (expandable graphite sheet) is to utilize natural graphite powder or graphite scale through acidic solution processing, adds the compression mouldings under certain temperature condition such as tackiness agent.The thermal conductivity of natural stone ink film is the highest at present can only reach 500W/mK, generally only has 300 to 400 W/mK.The thermal conductivity of natural stone ink film is suitable with the copper of present stage, and the less demanding electronic product that generally can only be confined to dispel the heat uses.
Rostone ink film refers to the graphite film that utilizes the polymeric membrane of carbon containing to make through carbonization, graphitization technique.The basic characteristics of rostone ink film are: thin, the thinlyyest can accomplish 10 microns, generally all below 100 microns; Thermal conductivity high (thermodiffusion performance in other words good, thermal diffusivity high), good heat conductivity, the thermal conductivity of its in-plane is generally more than 800 W/mK, manufacture craft is good, the plane thermal conductivity of the more than 90% rostone ink film of degree of graphitization can reach 1500 to 1800 W/mK, and perfectly the thermal conductivity of the in-plane of rostone ink film can reach 2400W/mK in theory; Snappiness is good, and resistance to bending performance is splendid; Conductivity is strong.The purposes of rostone ink film is very extensive, can be applied to the multiple fields such as electronics, space flight, military project.Be specially adapted to solve the heating problem of small-sized electronic product heating element, such as cpu, battery etc. for electronic products such as smart mobile phone, notebook computer, panel computer, navigating instruments, can reach desirable radiating effect, and be suitable for very convenient.Through deposited processing, can directly be attached on the heating element of electronic product, solve its heating problem.Rostone ink film will be made very important contribution towards thinner, lighter, integrated future development for above-mentioned electronic product.
The current research at rostone ink film of Japan, production field are in leading status.More domestic important research mechanisms, the rostone ink film that begins one's study from the early 1980s such as institutes, has also obtained pleasurable achievement so far.But, numerous synthetic graphite film production patents and document be unexposed complete synthetic graphite film production method all, as the publication number patent of invention that is CN101687647A, the invention of a kind of " graphite film and graphite composite film " is disclosed, its content is mainly set forth the making of selection, polyimide of preparation bending resistance folding endurance synthetic graphite film and greying exert pressure scope and the contents such as way of heating, and does not tell about its concrete manufacture craft.For another example the patent of invention that publication number is CN1826288A discloses a kind of " filmy graphite and manufacture method thereof ", what its content was mainly set forth is the manufacture as synthetic graphite pleurodiaphragmatic in terspace material film polyimide for people's likewise known, does not openly make the concrete technology of graphite film.For another example the domestic literature of Zhang Peng, Chi Weidong, Shen Zengmin " impact of high temperature cabonization on polyimide (PI) membrane structure and performance ", do not set forth the manufacture craft of graphite film yet, just told about the change procedure of raw material in carbonization, greying engineering with and the variation of physicochemical property.Chinese patent literature CN102149633A(application number is 2009801359470) graphite film that discloses a kind of manufacture method of carbonaceous film and made by it, it discloses a kind of long size, the manufacture method of the graphite film of web form, this manufacture method is the integrity that keeps film in the carbonization process of making processes by the frictional force producing between raw material film, thereby make the not fold of graphite film of manufacturing, do not produce ripple, but the graphite film that this method is made due in the process of manufacturing, do not give certain pressure easily guarantee its decomposition course in the planarization of surface restructuring, therefore the heat conductivility of the actual graphite film of making is insuperior, its the crystal structure of graphite is flourishing not, even if the later stage can not change by rolling processing the defect that this making method is brought.
Not only all unexposed complete synthetic graphite film production methods of numerous synthetic graphite film production patents and document, and the concrete making method of rostone ink film itself have diversified feature, are not limited to a kind of mode.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of mfg. moulding die and concrete manufacture method of high thermal conductivity graphite film complete, that be applicable to batch production sheet.
The technical scheme that realizes first object of the present invention is to provide a kind of mfg. moulding die of flake graphite film, comprises base, column, upper cover, barrier sheet and heatproof weight.Column has 4.
Base is a graphite block that is round pie, and its thickness is 1 to 3 centimetre, and diameter is 20 to 50cm.The front, rear, left and right portion of base is respectively provided with the through hole of 1 upward and downward, and the adjacent through-holes of 4 through holes arranges with respect to the central axis equal angles of base, and the axis of 4 through holes is positioned on a cylindrical side concentric with base, and 4 through holes are equipped with internal thread.
4 root posts are made by graphite, and it is cylindric that column is, and its diameter is corresponding with the diameter of the through hole on base, and the bottom of every root post is provided with the outside screw matching with the internal thread of the through hole of base.4 root posts are screwed in corresponding 1 through hole of base from top to bottom by its threaded portion, lower end respectively, thereby 4 root posts are fixed on base, thereby obtain lower membrane module.
Barrier sheet has a rectangular shape, the foursquare length of side of imagination that its side ratio 4 root posts surround little by 0% to 0.2%.Barrier sheet is made up of high temperature material.Barrier sheet is horizontally set on while use in the space that base and 4 root posts surround.
Heatproof weight is made up of high temperature material.The shape of heatproof weight is consistent or slightly little with the shape of barrier sheet, and lower surface is smooth.Heatproof weight is horizontally set on while use in the space that base and 4 root posts surround.
The shape of upper cover and size are identical with base, and upper cover is a graphite block that is round pie, and its thickness is 1 to 3 centimetre, the equal diameters of diameter and base.The front, rear, left and right portion of upper cover is respectively provided with the through hole of 1 upward and downward, and the adjacent through-holes of 4 through holes arranges with respect to the central axis equal angles of base, and the axis of 4 through holes is positioned on a cylindrical side concentric with upper cover, and 4 through holes of upper cover are unthreaded hole.When upper cover uses, pass from top to bottom respectively a corresponding root post by its 4 through holes, and be fixed on the top of 4 root posts.
The preferred graphite flake of manufactured materials, rostone ink film or the natural stone ink film of barrier sheet, more preferably natural stone ink film.
The preferred carbon element class of the manufactured materials material of heatproof weight, more preferably graphite block.Heatproof weight is bottom shape and barrier sheet rectangular-shaped weight of a size.
The technical scheme that realizes second object of the present invention is to provide a kind of manufacture method of flake graphite film, comprises the steps:
1. choose starting material, choose that diaxial orientation, double refractive inde are greater than 0.1, Young's modulus is greater than 400kgf/mm
2, the polyimide film of tensile strength more than 50Mpa be as raw material film.
2. mfg. moulding die is set, and above-mentioned mfg. moulding die adopts the mfg. moulding die of above-mentioned flake graphite film.
3. the raw material film 1. step being obtained is cut into the shape that is suitable for being placed in the mfg. moulding die that 2. step obtain.The foursquare shape size surrounding according to 4 root posts of mfg. moulding die, the polyimide film that 1. step is obtained is cut into corresponding square shape and obtains raw material film, and the length of side of the foursquare barrier sheet of side ratio of the raw material film of the complete every square shape of cutting is little by 0.5% to 1%.
4. the raw material film 3. step being obtained and the spacing piece 4 of respective numbers are placed in the lower membrane module that 2. step obtain in the mode of interval lamination, be specially first raw material film of the smooth placement of upper surface of the base of the lower membrane module 2. obtaining in step, then overlapping placement first barrier sheet on first raw material film, second raw material film of overlapping placement again, then second barrier sheet of overlapping placement on second raw material film, so superimposed until all raw material films and barrier sheet are all placed in mfg. moulding die in the overlapping mode in space, thereby obtain the subassembly of interval lamination and counterdie.The process of the above-mentioned overlapping placement in space is referred to as interval lamination process, and the overlapping placement in space is referred to as interval lamination.
5. the raw material film in the interval lamination 4. step being obtained and the subassembly of counterdie is exerted pressure, heatproof weight is placed on the upper surface of the barrier sheet that is positioned at the top of interval lamination that 4. step obtain and die assembly, thereby obtains the interval lamination of weight application and the parts of mould.The pressure range of exerting pressure is 3 to 10g/cm
2.The interval lamination of the weight application 6. 5. step being obtained and the parts of mould are put into the inner chamber of carbide furnace.
The inner chamber of the carbide furnace of the interval lamination of having put into weight application 7. 6. obtaining in step and the parts of mould, first vacuumizes the inner chamber of carbide furnace, then is filled with nitrogen or rare gas element and forms inert environments.
8. under the inert environments 7. obtaining in step, carbide furnace is heated to the interval lamination of weight application and the parts of mould raw material film carbonization temperature and start carbonization, and under the highest carbonization temperature, be incubated 30 to 120 minutes and complete carbonization, then naturally cooling.The highest carbonization temperature arranging in insulation is at 1000 ℃ to 1400 ℃.
The adjustment of exerting pressure of raw material film after the carbonization of the interval lamination of the weight application 9. 8. step being obtained and the parts of mould, open the bell of carbide furnace, above the parts of the interval of weight application lamination and mould, replace heatproof weight, the pressure range of exerting pressure is 5.0 to 100g/cm
2.
10. the carbide furnace that 9. step is obtained being provided with the parts of the interval lamination adjusted after exerting pressure and mould forms inert environments again.First will in stove, vacuumize, then applying argon gas or helium are to normal pressure, pressure-fired or micro-negative pressure.
Step specified operational procedure is 7.: first carbide furnace is vacuumized, then fill the rare gas element such as nitrogen or argon gas to normal pressure or pressure-fired, micro-negative pressure.And then vacuumize again, then fill the rare gas element such as nitrogen or argon gas to normal pressure or pressure-fired, micro-negative pressure.
Rare gas element preferred nitrogen, the preferred micro-negative pressure of pressure condition.
Step 1. in, polyimide raw material film preferably all benzene type acid dianhydride and p-phenyl's diamines as the prepared polyimide film of polymer raw of polyimide.
Step 8. in, temperature-rise period when above-mentioned carbonization starts, is included in 500 ℃ to 700 ℃ especially 550 ℃ to 650 ℃ time, keeps slowly heating up with 5 ℃/speed below min.
In step carbonization process 8., in the time of 500 ℃ to 700 ℃, take the operation of further decompression, the warm area air pressure that makes carbide furnace is micro-negative pressure-0.1KPa to-0.01KPa, after 700 ℃, keeps atmospheric pressure state.
Step
in, in above-mentioned graphitization process, heating schedule is warming up to top temperature in graphitization process with the speed of 10 ℃ of-50 ℃/min.
After 4. step completes, before 5. step carry out, upper cover is arranged on the subassembly that 4. step obtain interval lamination and counterdie, upper cover is enclosed within respectively on the upper-end part of driving of corresponding 1 root post from top to bottom by its 4 through holes, until the lower surface of upper cover contacts with the upper surface in uppermost barrier sheet, thereby step heatproof weight 5. and is 9. placed on the upper surface of upper cover.
The present invention has positive effect: the mfg. moulding die of (1) flake graphite film of the present invention and manufacture method provide a kind of concrete manufacturing process complete, that be applicable to the high thermal conductivity graphite film of batch production sheet, can produce high-quality rostone ink film in batches, this graphite film thermal diffusivity is good, bending resistance folding endurance is strong, is suitable for solving small-sized electronic product components and parts heating problem.
(2) mfg. moulding die of flake graphite film of the present invention and manufacture method have adopted the method that raw material film is suitably exerted pressure in carbonization, graphited process, fully guaranteed the planarization of produced graphite film and the prosperity of graphite crystallization structure, therefore its thermal diffusivity is more superior.
(3) mfg. moulding die of flake graphite film of the present invention and the manufacture method temperature of carbide furnace in graphitizing process is controlled at more than 2800 ℃, has guaranteed graphited adequacy.
(4) mfg. moulding die of flake graphite film of the present invention and manufacture method are taked slowly to heat up and are made raw material film guarantee not occur flaw in violent process of decomposing restructuring as far as possible in the temperature-rise period of 500 to 700 ℃ of carbonization process, and reaction all should.
(5) mfg. moulding die of flake graphite film of the present invention and manufacture method can be taked constant temperature measures in carbonization process, with guarantee raw material film certain specific warm spot reaction all should, fully, thereby make the graphite film of desired characteristic.
Accompanying drawing explanation
Fig. 1 is the structural representation of the mould in embodiments of the invention 1;
Fig. 2 is the upward view of Fig. 1.
Mark in above-mentioned accompanying drawing is as follows: base 1, column 2, upper cover 3, barrier sheet 4, heatproof weight 5, raw material film 6.
Embodiment
(mfg. moulding die of embodiment 1, flake graphite film)
See Fig. 1, the mfg. moulding die of the present embodiment comprises base 1, column 2, upper cover 3, barrier sheet 4 and heatproof weight 5.Column 2 has 4.
See Fig. 1 and Fig. 2, base 1 is a graphite block that is round pie, and its thickness is 1 to 3 centimetre (the present embodiment is 2 centimetres), and diameter is 30cm.The front, rear, left and right portion of base 1 is respectively provided with the through hole of 1 upward and downward, the adjacent through-holes of 4 through holes arranges with respect to the central axis equal angles of base 1, and the axis of 4 through holes is positioned on a cylindrical side concentric with base 1, and 4 through holes are equipped with internal thread.
4 root posts 2 are made by graphite, and column 2 is cylindric, and its diameter is corresponding with the diameter of the through hole on base 1, and the bottom of every root post 2 is provided with the outside screw matching with the internal thread of the through hole of base 1.4 root posts 2 are screwed in corresponding 1 through hole of base 1 from top to bottom by its threaded portion, lower end respectively, thereby 4 root posts 2 are fixed on base 1, thereby obtain lower membrane module.
The shape of upper cover 3 and size are identical with base 1, and upper cover 3 is graphite blocks that are round pie, and its thickness is 1 to 3 centimetre (the present embodiment is 2 centimetres), and diameter is 30cm.The front, rear, left and right portion of upper cover 3 is respectively provided with the through hole of 1 upward and downward, the adjacent through-holes of 4 through holes arranges with respect to the central axis equal angles of base 1, and the axis of 4 through holes is positioned on a cylindrical side concentric with upper cover 3, and 4 through holes of upper cover 3 are unthreaded hole.
Barrier sheet 4 has a rectangular shape, the foursquare length of side of imagination that its side ratio 4 root posts 2 surround little by 0% to 0.2%.Barrier sheet 4 adopts the various types of materials more than top temperature that fusing point sets in carbonation process to make, preferably graphite flake, rostone ink film or natural stone ink film, more preferably natural stone ink film.Because the thickness of graphite flake is more than 0.3mm, and more crisp, after exerting pressure, adding that high-temperature expansion is easily cracked, the space that thickening takies can be large, affect volume production; Rostone ink film is more expensive, and matter is soft, easily breakage; So barrier sheet 4 selects natural stone ink film to make the best, the thickness of natural stone ink film is at 0.1mm to 0.5mm, and the natural stone ink film of this thickness has had certain hardness, easily lamination.The size of the barrier sheet of the present embodiment is 21cm*21cm, and thickness is 0.2mm, adopts natural graphite coiled material to cut and makes.
(manufacture method of embodiment 2, flake graphite film)
The manufacture method of the flake graphite film of the present embodiment comprises following several step:
1. choose starting material.
Can be generally the one in the high-temperature resistant aromatic polymeric membranes such as polyimide (PI), polyoxadiazole (POD), polyamide (PA), polybenzoxazole (PBO), polyphenyl two oxazole (PBBO), polybenzothiozole (PBT), polyphenyl double thiazole (PBBT), polybenzimidazole (PBI), polyphenyl two imidazoles (PBBI) as the polymeric membrane raw material of preparing graphite film.Wherein (PI), with polyoxadiazole (POD) is preferred raw material, is more preferably polyimide to polyimide.Because acid dianhydride and diamines as the raw material of synthesis of polyimides have diversity.The polymeric membrane raw material of the manufacture flake graphite film that the present invention adopts is exactly polyimide.
The polyimide material that the present invention adopts requires the molecular orientation of its in-plane good, the easier carbonization of such polyimide material, greying, the orientation of graphite crystallization also can improve, and the graphite film bending resistance folding endurance that makes is good, thermal conductivity is high (thermal diffusivity is high), the isotropy degree on surface is high.
In-plane molecular orientation refers to that the molecule segment of polymeric membrane is abreast to same direction arrangement.The in-plane of the polymeric membrane molecule segment of not oriented is arranged and vertical direction (thickness direction) is arranged all free arrangement in polymerization process, is determined by intermolecular interaction force.Do not having under External Force Acting impact, intermolecular interaction force is identical, so physics, the chemical property of all directions of the polymeric membrane molecule segment of not oriented (comprising in-plane and vertical direction) are same sex character.But the isotropy of this polymeric membrane molecule segment is not the isotropy that is applicable to making graphite film, just molecule segment is arranged the same sex producing under equimolecular power interacts.Making good graphite film must make polymeric membrane make under external force its molecule segment have orientation at in-plane.
Applying the aligned of external force has two kinds, and one is uniaxial orientation, and another kind is diaxial orientation.Uniaxial orientation refers in a direction of polymeric membrane and applies pulling force, thereby makes polymeric membrane to extended by force direction.As in length direction unilateral stretching, the length of film can increase, and thickness and width dwindle, and the molecule segment of length direction has had orientation.Diaxial orientation refers to that external force is at two orthogonal direction stretching polymeric membranes, be length direction and width two-way stretch, the length of the polymeric membrane of diaxial orientation and width all can increase, its thickness reduces, the molecule segment of polymeric membrane is arranged with respect to stretching plane parallel, and the molecule segment of stretching plane inner side (can be considered thickness direction) is random alignment.The polymeric membrane of visible diaxial orientation has horizontal direction isotropic nature in stretching plane, and out-of-plane other directions that stretch are different in nature character with respect to stretching plane.Therefore, utilize in-plane and the vertical direction of the rostone ink film that polymeric membrane makes also to exist anisotropy.
The polyimide film of diaxial orientation is exactly the raw material polymeric membrane that the present embodiment is selected.There is orientation just to have orientation degree, orientation degree is higher, orientation the is better easier carbonization of polyimide raw material film, greying, the quality (thermal diffusivity, electroconductibility etc.) of the graphite film that can make is higher: raw material film is after diaxial orientation, the molecule segment of Extrude Face is arranged in parallel and is more conducive to the transmission of intermolecular heat, heat loses less in intermolecular transmittance process, and efficiency is better; Simultaneously molecular chain is subject to make after force-extension intermolecular reactive force itself to reduce, and its molecular breakdown is reset needed energy and just relatively reduced like this, so easily carbonization, greying.
The orientation degree of determining Kapton has a lot of methods, as: wide-angle x-ray diffraction, By Birefringence Method, sound wave propagate method, infrared dichroism method etc.These methods be all based on orientation after its stretching in-plane of Kapton and the physical properties of thickness direction be anisotropy.Determine that take By Birefringence Method raw material film orientation degree is as example: double refractive inde is the refractive index (establishing Nx represents) that represents raw material membrane plane direction and longitudinal poor perpendicular to the refractive index (establishing Nz represents) of the thickness direction of membrane plane, i.e. Δ n=Nx-Nz.The larger expression raw material of Δ n value film orientation degree is better, and the material Δ n selected as the present embodiment answers ﹥ 0.10.Nx should many values,, in the multiple angles of raw material membrane plane (as 0 ° of direction, 30 ° of directions, 45 ° of directions etc.) value, use obtained multiple Nx to subtract Nz, get its mean value and are considered as Δ n more accurately.Nz also can many values, but the difference of Nz is very little, are sometimes to cause minute differences due to operation or instrument, so can suitably lack value.Another object of the many values of Nx can judge whether raw material film belongs to diaxial orientation.For example, represent the refractive index of 0 ° of direction (can freely determine) in membrane plane with Nx1, represent in membrane plane the refractive index value of the 90 ° directions vertical with 0 ° of direction with Nx2, as the value of Nx1-Nx2 close to zero or the illustrative material that equals zero be diaxial orientation, otherwise illustrate that raw material film is uniaxial orientation, the preferred material of the present embodiment is the polyimide of diaxial orientation.
Tensile strength also can be considered as an index of raw material film orientation degree judgement, and tensile strength is higher, and raw material film orientation degree is better; The judge index of more direct raw material film orientation degree is exactly tensile strength, and tensile strength is larger, and orientation degree will be higher.But the prerequisite of these two indexs is raw material films is diaxial orientations.
The Young's modulus of raw material film is higher in addition, and the graphite film quality making is also better, and its Young's modulus of polyimide raw material film that the present embodiment adopts should be greater than 400kgf/mm
2(every square millimeter of kilogram force refers to apply on the area of every square millimeter the pressure of 1 kilogram force).Can detect the Young's modulus of raw material film by LaWave Young's modulus detector.As the polymer raw of polyimide, preferably all benzene type acid dianhydride and p-phenyl's diamines more easily make the polyimide raw material film of desired properties.
The model that the present embodiment adopts Liyang Huajing Electronic Material Co., Ltd. to produce be H type, length is that 10 meters, width are 500 millimeters, the coiled material type polyimide film of 25 microns of thickness, tensile strength 50MPa, the diaxial orientation starting material as raw material film.
2. mfg. moulding die is set.Adopt the mfg. moulding die of the flake graphite film being obtained by embodiment 1.
3. the polyimide film 1. step being obtained is cut into the shape that is suitable for being placed in mould.
The foursquare shape size surrounding according to 4 root posts 2 of mfg. moulding die, the polyimide film that 1. step is obtained is cut into corresponding square shape and obtains raw material film 6, and the length of side of the foursquare barrier sheet 4 of side ratio of the raw material film 6 of the complete every square shape of cutting is little by 0.5% to 1%.It is that raw material film can produce and expand in the carbonization course of processing that the size of every tablet raw material film is set as being slightly less than the maximum sized reason that can place in mfg. moulding die, if the size of raw material film is the same with the overall dimension that mfg. moulding die can be placed, raw material film can be because wiping in expansion and the edge of mfg. moulding die mutually in the course of processing so, thereby cause raw material membrane portions edge curvature, fold or breakage that carbonization is good, in the greying course of processing, must not repair equally, affect the overall quality of graphite film.The square shape that the size of every tablet raw material film of the present embodiment is 20.8cm*20.8cm, totally 200.
4. the raw material film 6 3. step being obtained is placed in the lower membrane module that 2. step obtain in the mode of interval lamination, obtains the subassembly of interval lamination and counterdie.
See Fig. 1, first raw material film 6 of the smooth placement of upper surface of the base 1 of the lower membrane module 2. obtaining in step, then overlapping placement first barrier sheet 4 on first raw material film 6, second raw material film 6 of overlapping placement again, then second barrier sheet 4 of overlapping placement on second raw material film 6, so superimposed until all 200 raw material films 6 are all placed in mfg. moulding die in the overlapping mode in space with barrier sheet 4, thus the subassembly of interval lamination and counterdie obtained.
The process of the above-mentioned overlapping placement in space is referred to as interval lamination process, and the overlapping placement in space is referred to as interval lamination.In the lamination process of interval, should keep the smooth of raw material film 6 as far as possible, and aiming between raw material film 6 and barrier sheet 4.
To prevent that raw material film 6 is welded together in following process process by barrier sheet 4 for the reason of interval lamination.
5. upper cover 3 is arranged on the subassembly that 4. step obtain interval lamination and counterdie, upper cover 3 is enclosed within respectively on the upper-end part of driving of corresponding 1 root post 2 from top to bottom by its 4 through holes, until the lower surface of upper cover 3 with contact in the upper surface of uppermost barrier sheet 4, thereby obtain the parts of interval lamination and mould.
6. the raw material film 6 in interval lamination and the die assembly 5. step being obtained is exerted pressure.Heatproof weight 5 is placed on the upper surface of upper cover 3 of interval lamination that 5. step obtain and die assembly, thereby obtains the interval lamination of weight application and the parts of mould.
The gravity of heatproof weight 5 applies certain pressure to carry out carbonization process by upper cover 3 to the raw material film 6 after lamination.
Exert pressure is the planarization in order to guarantee carbonization process Raw film 6 and the graphite film that makes required quality.In carbonization process, raw material film 6 molecules can decompose and carry out molecular recombination, exert pressure if inappropriate, and the raw material film 6 of carbonization can produce the flaws such as ripple.In carbonization process, when raw material film 6 decomposes, produce by a relatively large margin and shrink at its in-plane, if pressure is excessive, hinders it and shrink, raw material film 6 will crack, hole or fracture.In carbonization process, molecular breakdown can produce tar in addition, if the excessive discharge that is unfavorable for tar of pressure is residual even if decompression also has minute quantity tar, thereby affects the quality of graphite film.The pressure range that carbonization process is exerted pressure is 3 to 10g/cm
2(gram every square centimeter).In addition, exerting pressure is also evenly to have created condition for the good raw material film 6 of carbonization in the graphite-like structure growth of its in-plane, is conducive to greying.In this step, the quality settings of heatproof weight 5 is 2000g.
The interval lamination of the weight application 7. 6. step being obtained and the parts of mould are put into the inner chamber of carbide furnace.The high temperature cabonization equipment that the present embodiment adopts Changsha Nuo Tian Electronic Science and Technology Co., Ltd. to produce.
The inner chamber of the carbide furnace of the interval lamination of having put into weight application 8. 7. obtaining in step and the parts of mould, forms inert environments.First the inner chamber of carbide furnace is vacuumized, then be filled with nitrogen or rare gas element and form inert environments.Form the object of inert environments and be center warm area in order to protect carbide furnace not contaminated, extension device work-ing life, be also to prevent that airborne gas from high temperature reacting with raw material film 6 simultaneously.Raw material film 6 can not carry out carbonization under natural air atmosphere.Specified operational procedure is: first carbide furnace is vacuumized, then fill the rare gas element such as nitrogen or argon gas to normal pressure or pressure-fired, micro-negative pressure, described pressure-fired refers to the gaseous tension state of surveyed environmental stress higher than normal pressure (i.e. a normal atmosphere) 1 to 400Pa; Described micro-negative pressure refers to the gaseous tension state of surveyed environmental stress lower than normal pressure (i.e. a normal atmosphere) 1 to 400Pa, for example, be 1Mpa at the normal atmosphere of external environment, and the absolute pressure value of micro-negative pressure-0.1KPa is 99.9KPa; Now can vacuumize again, the air of not discharging when previous vacuumizing so further obtains dilution and is pumped, and then fills the rare gas element such as nitrogen or argon gas to normal pressure or pressure-fired, micro-negative pressure.Rare gas element is preferably both economical, and inertia degree is inferior to the nitrogen of argon gas and helium.Generally before heating schedule starts, vacuumize, the operation of inflated with nitrogen or rare gas element, although there is not the selection of atmosphere before raw material decomposition temperature, once but heating schedule starts, follow-up be difficult to control vacuumize and the operation of inflated with nitrogen or rare gas element, and airborne impurity also contaminated feedstock likely before raw material film 6 decomposition temperatures, so be chosen in before heating schedule starts vacuumize, the operation of inflated with nitrogen or rare gas element.
The inert environments forming in the present embodiment is for being full of nitrogen.Carbide furnace keeps the condition atmospheric condition of normal pressure, pressure-fired or micro-negative pressure until carbonization finishes, and is cooled to normal temperature, or 300 ℃ of following blow-on temperature blow-ons are all fine; Micro-negative pressure is the pressure condition of comparative optimization, produces because have tar in raw material film 6 carbonization processs, and micro-negative pressure is relatively applicable to tar exhausting, protection body of heater and the stove heart.
9. under the inert environments 8. obtaining in step, carbide furnace is heated to the interval lamination of weight application and the parts of mould raw material film 6 carbonization temperature and start carbonization, under carbonization temperature, be incubated about 30 minutes and complete carbonization.The highest carbonization temperature arranging in insulation is at 1000 ℃ to 1400 ℃, and general 1000 ℃, preferably 1200 ℃, more preferably 1400 ℃.More than 1000 ℃, the carbonization of raw material film 6 refers to after the molecular breakdown of raw material film 6 goes out carbon and recombinates, basically forms the hexagonal carbon stratum reticulare face of graphite-like structure, and is that the graphited operation of carrying out next step has been created condition.The reason that the high temperature of 1000 ℃ of above for example 1200 ℃ or 1400 ℃ is set is to make 6 carbonizations of raw material film more abundant, and in the graphite film of carbon after molecular recombination, content is higher, and graphite-like structure generates Du Genggao, and degree of graphitization is also just higher.
Temperature-rise period when described carbonization starts, is included in 500 ℃ to 700 ℃ especially 550 ℃ to 650 ℃ time, keeps slowly heating up with 5 ℃/speed below min, and all the other temperature sections can be according to the requirement design of technique separately.In carbonization, also can design the time period of constant temperature.The object that constant temperature time section is set is that material breakdown restructuring is more even like this in order to guarantee raw material film 6 at one time, decompose the reaction that reassembles into charcoal solid under same temperature as far as possible; If keep persistently overheating, because the temperature of each point of device interior warm area is at one time actual and inhomogeneous, cause that raw material film 6 is actual at one time can not decompose accordingly recombining reaction at identical temperature, the level of response of natural raw material film 6 each points is also just different, just has the possibility that has flaw.In addition, the object of constant temperature is also in order to allow raw material film 6 in the time that the acquisition of thermostat temperature point is fully reacted and unified degree is reacted, to reach the object of good uniformity.The reason slowly heating up is also the same, because slowly intensification make to a certain extent raw material film 6 at one time in suffered temperature be identical substantially, level of response is also just substantially the same like this, and the flaw occurring after the molecular breakdown restructuring of raw material film 6 is just few.Select slow temperature rise rate at 500 ℃ to 700 ℃ temperature sections, because the decomposition of the molecule of raw material film 6 restructuring is very violent 500 ℃ to 700 ℃ time, wherein 550 ℃ to 650 ℃ is the most violent temperature section, must be at this section by raw material film 6 homogeneous reactions, the flaw after molecular breakdown restructuring is just few like this.
The present embodiment is warming up to 1200 ℃ with the speed of 3 ℃/min, constant temperature 30 minutes, then naturally cooling.
The adjustment of exerting pressure of raw material film 6 after the carbonization of the interval lamination of the weight application 10. 9. step being obtained and the parts of mould.Open the bell of carbide furnace, above the upper cover 3 of the parts of the interval of weight application lamination and mould, replace heatproof weight 5, and the raw material film 6 after carbonization is applied to certain pressure to carry out graphitizing process.
When greying, do not exert pressure, the crystal structure of graphite poor continuity of graphite film, physicals is also just poor.But the pressure of exerting pressure in carbonization process must be less than the pressure of exerting pressure in graphitizing process, because the reaction major part of raw material film 6 molecular breakdown, restructuring is at carbonization process, graphitizing process molecular reaction is more light and slow.And in graphitizing process pressure little rise steep oneself-meeting many, crystal structure of graphite flourishing not (being crystalline structure poor continuity), the physicalies such as heat conduction are also just poor, so the pressure of exerting pressure of graphitizing process wants large.The pressure range that graphitizing process is exerted pressure is 5.0 to 100g/cm
2, the pressure of exerting pressure in graphitizing process can not be excessive, if pressure is higher than 100g/ cm
2, too encourage the prosperity of the crystal structure of graphite of surface direction, obtain bubble degree very little, the very large hard graphite film of bubble area.So exert pressure, pressure is excessive, and graphite film finished product can be more crisp, and snappiness is poor, fragile.
In this step, the quality adjustment of heatproof weight 5 is set to 6000g.
the carbide furnace that 10. step is obtained being provided with to the parts of the interval lamination adjusted after exerting pressure and mould forms inert environments again.First will in stove, vacuumize, then applying argon gas or helium are to normal pressure, pressure-fired or micro-negative pressure.Air pressure range is little on the impact of graphite film quality, can be according to the feature design of technique separately.The graphitization process of the present embodiment is chosen under the atmosphere of inert gases condition of pressure-fired and carries out, and atmospheric condition is preferably argon gas and helium.Although nitrogen is also inactive gas, the γ-ray emission that nitrogen exists and the 6 continuation decomposition of raw material film discharge under graphitizable high temperature condition reacts and the risk of contaminated feedstock film 6 and device core warm area.
(embodiment 3)
The process of the present embodiment is substantially substantially the same manner as Example 2, and its difference is: do not carry out step 6. in step before 7., exert pressure in carbonization process, to raw material film 6.The graphite film making has ripple, and carbonizing apparatus core warm area has light contamination.
(embodiment 4)
The process of the present embodiment is basic identical with embodiment 2, and its difference is: after 9. step completes, progressive suddenly 10., in graphitizing process to raw material film 6 adjustment of exerting pressure.The graphite film quality that makes is partially soft, thermal diffusivity is slightly poor, and carbonizing apparatus core warm area has light contamination.
(embodiment 5)
The process of the present embodiment is substantially substantially the same manner as Example 2, its difference is: in step carbonization process 9., when temperature is heated to 500 ℃ to 700 ℃, taked the operation of decompression, making carbide furnace equipment warm area internal gas pressure is micro-negative pressure-0.01KPa, after 700 ℃, keeps atmospheric pressure state.The graphite film making does not have welding phenomenon, and carbonizing apparatus core warm area does not pollute.
(embodiment 6)
The process of the present embodiment is substantially substantially the same manner as Example 2, and its difference is: step 6. in, the raw material film 6 in mfg. moulding die is exerted pressure, the quality of the weight 5 of exerting pressure changes 3000g into;
Step
in, the quality of the weight 5 of exerting pressure is adjusted into 10000g.The graphite film making does not have welding phenomenon, and carbonizing apparatus core warm area has light contamination.
(embodiment 7)
The process of the present embodiment is substantially substantially the same manner as Example 2, and its difference is: step 1. in, adopt the polyimide film of 50 microns of thickness, tensile strength 50MPa that Liyang Huajing Electronic Material Co., Ltd. produces, diaxial orientation as raw material film 6;
In step carbonization process 9., when being heated to 500 ℃ to 700 ℃, temperature takes the operation of decompression, and making carbide furnace equipment warm area internal gas pressure is micro-negative pressure-0.01KPa, after 700 ℃, keeps atmospheric pressure state.The graphite film making does not have welding phenomenon, and carbonizing apparatus core warm area has light contamination.
(embodiment 8)
The process of the present embodiment is substantially substantially the same manner as Example 7, and its difference is: step 6. in, the raw material film 6 in mfg. moulding die is exerted pressure, the quality of the weight 5 of exerting pressure changes 3000g into;
Step
in, the quality of the weight 5 of exerting pressure is adjusted into 10000g.The graphite film making does not have welding phenomenon, and carbonizing apparatus core warm area does not produce pollution.
(comparative example)
Adopt the resistance to LFA447 of the speeding thermal conductivity test instrument of Germany that the graphite film making is carried out to thermal diffusivity mensuration.To in the atmospheric condition in the experimentation of embodiment 1 to 7, whether welding, thermal diffusivity, carbide furnace, there be the data such as pollution-free to count table one.
Table one
Quality, quality and the technique of rostone ink film have much relations, as exert pressure, quality that intensification etc. all affects finished product graphite, how design technology makes the graphite film of wanting will be designed according to demand separately.Technique of the present invention can be produced high-quality rostone ink film in batches, and this graphite film thermal diffusivity is good, bending resistance folding endurance is strong, is suitable for solving small-sized electronic product components and parts heating problem.
Claims (7)
1. a mfg. moulding die for flake graphite film, is characterized in that: comprise base (1), column (2), upper cover (3), barrier sheet (4) and heatproof weight (5); Column (2) has 4;
Base (1) is a graphite block that is round pie, and its thickness is 1 to 3 centimetre, and diameter is 20 to 50cm; The front, rear, left and right portion of base (1) is respectively provided with the through hole of 1 upward and downward, the adjacent through-holes of 4 through holes arranges with respect to the central axis equal angles of base (1), and the axis of 4 through holes is positioned on a cylindrical side concentric with base (1), and 4 through holes are equipped with internal thread;
4 root posts (2) are made by graphite, and column (2) is cylindric, and its diameter is corresponding with the diameter of the through hole on base (1), and the bottom of every root post (2) is provided with the outside screw matching with the internal thread of the through hole of base (1); 4 root posts (2) are screwed in corresponding 1 through hole of base (1) from top to bottom by its threaded portion, lower end respectively, thereby it is upper to make 4 root posts (2) be fixed on base (1), thereby obtain lower membrane module;
Barrier sheet (4) has a rectangular shape, and the foursquare length of side of imagination that its side ratio 4 root posts (2) surround is little by 0% to 0.2%; Barrier sheet (4) is made up of high temperature material; Barrier sheet (4) is horizontally set on while use in the space that base (1) and 4 root posts (2) surround;
Heatproof weight (5) is made up of high temperature material; The shape of heatproof weight (5) is consistent or slightly little with the shape of barrier sheet (4), and lower surface is smooth; Heatproof weight (5) is horizontally set on while use in the space that base (1) and 4 root posts (2) surround;
The shape of upper cover (3) and size are identical with base (1), and upper cover (3) is a graphite block that is round pie, and its thickness is 1 to 3 centimetre, the equal diameters of diameter and base (1); The front, rear, left and right portion of upper cover (3) is respectively provided with the through hole of 1 upward and downward, the adjacent through-holes of 4 through holes arranges with respect to the central axis equal angles of base (1), and the axis of 4 through holes is positioned on a cylindrical side concentric with upper cover (3), and 4 through holes of upper cover (3) are unthreaded hole; When upper cover (3) uses, pass from top to bottom respectively a corresponding root post (2) by its 4 through holes, and be fixed on the top of 4 root posts (2).
2. a manufacture method for flake graphite film, comprises the steps:
1) choose starting material, choose that diaxial orientation, double refractive inde are greater than 0.1, Young's modulus is greater than 400kgf/mm
2, the polyimide film of tensile strength more than 50MPa be as raw material film;
2) mfg. moulding die is set, described mfg. moulding die adopts the mfg. moulding die of flake graphite film as claimed in claim 1;
3) raw material film step 1) being obtained is cut into and is suitable for being placed on step 2) shape in the mfg. moulding die that obtains; The foursquare shape size surrounding according to 4 root posts (2) of mfg. moulding die, the polyimide film that step 1) is obtained is cut into corresponding square shape and obtains raw material film (6), and the length of side of the foursquare barrier sheet of side ratio (4) of the raw material film (6) of the complete every square shape of cutting is little by 0.5% to 1%;
4) the raw material film (6) step 3) being obtained and the spacing piece 4 of respective numbers are placed on step 2 in the mode of interval lamination) in the lower membrane module that obtains, be specially in step 2) upper surface first raw material film of smooth placement (6) of the base (1) of the lower membrane module that obtains, then at the upper overlapping placement first barrier sheet (4) of first raw material film (6), second raw material film of overlapping placement (6) again, then at upper second barrier sheet of overlapping placement (4) of second raw material film (6), it is so superimposed until all raw material films (6) and barrier sheet (4) are all placed in mfg. moulding die in the overlapping mode in space, thereby obtain the subassembly of interval lamination and counterdie, the process of the above-mentioned overlapping placement in space is referred to as interval lamination process, and the overlapping placement in space is referred to as interval lamination,
5) the raw material film (6) in interval lamination step 4) being obtained and the subassembly of counterdie is exerted pressure, heatproof weight (5) is placed on the upper surface of the barrier sheet that is positioned at the top (4) of interval lamination that step 4) obtains and die assembly, thereby obtains the interval lamination of weight application and the parts of mould; The pressure range of exerting pressure is 3 to 10g/cm
2;
6) the interval lamination of weight application step 5) being obtained and the parts of mould are put into the inner chamber of carbide furnace;
7) inner chamber of the carbide furnace of the interval lamination of having put into weight application obtaining in step 6) and the parts of mould, first vacuumizes the inner chamber of carbide furnace, then is filled with nitrogen or rare gas element and forms inert environments;
8) under the inert environments obtaining in step 7), carbide furnace is heated to the interval lamination of weight application and the parts of mould raw material film (6) carbonization temperature and start carbonization, and under the highest carbonization temperature, be incubated 30 to 120 minutes and complete carbonization, then naturally cooling; The highest carbonization temperature arranging in insulation is at 1000 ℃ to 1400 ℃;
9) adjustment of exerting pressure of the raw material film (6) after the carbonization of the interval lamination of weight application step 8) being obtained and the parts of mould, open the bell of carbide furnace, above the parts of the interval of weight application lamination and mould, replace heatproof weight (5), the pressure range of exerting pressure is 5.0 to 100g/cm
2;
10) carbide furnace that step 9) is obtained being provided with the parts of the interval lamination adjusted after exerting pressure and mould forms inert environments again; First will in stove, vacuumize, then applying argon gas or helium are to normal pressure, pressure-fired or micro-negative pressure;
11), under the inert environments obtaining in step 10), carbide furnace is heated to graphitization temperature and carries out graphitization process; In graphitization process top temperature be arranged on 2800 ℃ to 3200 ℃, and remain in said temperature region a certain target value 30 to 120 minutes;
12) wait for after carbide furnace naturally cooling, take out mfg. moulding die and obtain finished product graphite film.
3. the manufacture method of flake graphite film according to claim 2, is characterized in that: in step 1), the preferably equal benzene type acid dianhydride of polyimide raw material film and p-phenyl's diamines are as the prepared polyimide film of polymer raw of polyimide.
4. the manufacture method of flake graphite film according to claim 2, is characterized in that: in step 8), temperature-rise period when described carbonization starts, while being included in 500 ℃ to 700 ℃, keeps slowly heating up with 5 ℃/speed below min.
5. the manufacture method of flake graphite film according to claim 4, it is characterized in that: in the carbonization process of step 8), in the time of 500 ℃ to 700 ℃, take the operation of further decompression, the warm area air pressure that makes carbide furnace is micro-negative pressure-0.1KPa to-0.01KPa, after 700 ℃, keeps atmospheric pressure state.
6. the manufacture method of flake graphite film according to claim 2, is characterized in that: in step 11), in described graphitization process, heating schedule is warming up to top temperature in graphitization process with the speed of 10 ℃ of-50 ℃/min.
7. according to the manufacture method of the flake graphite film one of claim 2 to 6 Suo Shu, it is characterized in that: after step 4) completes, before step 5) carries out, upper cover (3) is arranged on the subassembly that step 4) obtains interval lamination and counterdie, upper cover (3) is enclosed within respectively on the upper-end part of driving of corresponding 1 root post (2) from top to bottom by its 4 through holes, until the lower surface of upper cover (3) with contact in the upper surface of uppermost barrier sheet (4), thereby the step 5) of making and 9) heatproof weight (5) be placed on the upper surface of upper cover (3).
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| CN104291311B (en) * | 2012-12-28 | 2016-06-15 | 苏州斯迪克新材料科技股份有限公司 | The preparation technology of electronic equipment graphite heat-conducting fin |
| JPWO2015080264A1 (en) * | 2013-11-28 | 2017-03-16 | 株式会社カネカ | Method for producing graphite film |
| WO2015110034A1 (en) * | 2014-01-27 | 2015-07-30 | 嘉兴中易碳素科技有限公司 | Method for preparing graphite film |
| CN103864068B (en) * | 2014-03-26 | 2016-02-17 | 苏州格优碳素新材料有限公司 | A kind of preparation method of high conduction graphite film |
| CN103864067B (en) * | 2014-03-26 | 2017-01-11 | 苏州格优碳素新材料有限公司 | Preparation method of high thermal conductivity graphite membrane-copper composite material |
| CN103889196B (en) * | 2014-04-11 | 2016-06-22 | 江苏悦达新材料科技有限公司 | A kind of preparation method of high heat conduction electrographite film |
| CN103906416A (en) * | 2014-04-11 | 2014-07-02 | 江苏悦达新材料科技有限公司 | Method for manufacturing artificial graphite radiating film with catalytic graphitization technology |
| CN104401972B (en) * | 2014-10-23 | 2016-06-08 | 江西德思恩科技有限公司 | A kind of manufacture method of the graphite film longer or wider than 550 millimeters |
| CN104495795B (en) * | 2014-11-24 | 2017-03-08 | 云南云天化股份有限公司 | A kind of graphite flake and preparation method thereof |
| TWI548590B (en) * | 2015-02-13 | 2016-09-11 | Pin-Yu Ke | Artificial graphite sheet manufacturing method and its products |
| CN105000885A (en) * | 2015-06-30 | 2015-10-28 | 东莞市思泉实业有限公司 | Method for producing graphite film |
| JPWO2017183705A1 (en) * | 2016-04-22 | 2019-01-31 | 株式会社カネカ | Highly oriented graphite and method for producing highly oriented graphite |
| CN109911893B (en) * | 2018-12-04 | 2022-02-01 | 重庆云天化瀚恩新材料开发有限公司 | Preparation method of heat-conducting artificial graphite gasket |
| CN113292971A (en) * | 2021-06-01 | 2021-08-24 | 江西德思恩新材料有限公司 | Artificial graphite film with enhanced tensile strength for heat dissipation function and preparation method thereof |
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| WO2009060818A1 (en) * | 2007-11-06 | 2009-05-14 | Kaneka Corporation | Process for production of graphite films |
| US8858847B2 (en) * | 2008-09-11 | 2014-10-14 | Kaneka Corporation | Method for producing carbonaceous film, and graphite film obtained by the same |
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