CN108588461A - A kind of polyimide-based graphite-metal composite material and preparation method - Google Patents
A kind of polyimide-based graphite-metal composite material and preparation method Download PDFInfo
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- CN108588461A CN108588461A CN201810388089.1A CN201810388089A CN108588461A CN 108588461 A CN108588461 A CN 108588461A CN 201810388089 A CN201810388089 A CN 201810388089A CN 108588461 A CN108588461 A CN 108588461A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/38—Coating with copper
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/52—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
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Abstract
The invention discloses a kind of polyimide-based graphite metal composite material, which contains the polyimide-based powdered graphite of 20~95% volumes and the metal powder matrix of 80~5% volumes, and the relative density of the composite material is 95% or more.The polyimide-based graphite metal composite material of the present invention can be prepared into the sheet material, plank and block of larger thickness, have higher intensity and adjustable coefficient of thermal expansion, and have higher thermal conductivity in a thickness direction.It solves common graphite metal composite material thermal conductivity and is less than 600W/mK, and the thickness of the polyimide-based graphite film of high heat conduction cannot do big and too low thickness direction thermal conductivity technological deficiency.
Description
Technical field
The invention belongs to heat-conductive composite material field more particularly to a kind of polyimide-based graphite-metal composite material and
Preparation method.
Background technology
With the rapid development of microelectronics industry, electronic device and equipment are constantly to high-power, High Density Integration and miniature
The direction of change is developed, and the heating problem thus caused proposes sternness to the performance, reliability and service life of electronic product
Challenge.Material for electronic product thermal management not only requires the thermal conductivity of superelevation, it is also necessary to have certain thermal capacity.
Thermal capacity is directly proportional to the quality of material, when area is certain, increases thermal capacity meaning of the thickness to raising Heat Conduction Material
It is great.
In recent years, the polyimide-based graphite of high heat conduction (PIG) film for using polyimides (PI) film to be prepared for raw material,
Be widely used in the electronic equipments such as smart mobile phone, laptop, plane thermal conductivity reach 1500W/mk with
On.However by PI film preparation thickness limited and PI films it is thicker be more difficult to it is graphited influence, polyimide-based high heat conduction stone
The thickness of ink film cannot meet increasingly lightening electronic product to high heat capacity at 100 μm hereinafter, be commonly 25 μm or so
The active demand of amount, high-heat conductivity graphite material.
Graphite-metal composite material, in particular by powder metallurgical technique prepare graphite-metal composite material, due to
With thermal conductivity height, coefficient of thermal expansion is small, intensity is high, can be prepared into the characteristics such as arbitrary shape and size, is answered in thermal management material
It is had been a concern in.Flaky graphite powder is often used in the graphite material as graphite-metal composite material, heat conduction
Rate is usually in 400W/mK or so.High thermal conductivity, large-sized high-quality flaky graphite powder are difficult acquisition, and graphite-metal
The performance of composite material is heavily dependent on the characteristic of graphite composite powder, the thermal conductivity of flaky graphite-metallic composite
600W/mK can be generally less than, heat conductivility needs to be further increased.
Invention content
It is an object of the present invention to overcome the shortcomings of to mention in background above technology and defect, provide a kind of can expire simultaneously
The polyimide-based graphite-metal composite material and preparation method of sufficient high thermal conductivity and high heat capacity.Solve common graphite-
Metallic composite thermal conductivity is less than 600W/mK, and polyimide-based high heat conduction graphite film leads to thermal capacity because thickness limits
Smaller problem.
Big L/D ratio and large-sized flake graphite powder can be formed after polyimide-based high heat conduction graphite film is broken,
Plane thermal conductivity can reach 1500W/mk or more, the polyimide-based graphite-metal composite wood prepared using powder metallurgical technique
Material is not limited by thickness, can be inherited the high thermal conductivity of polyimide-based graphite film and be increased thickness to improve heat
Capacity.
In order to solve the above technical problems, technical solution proposed by the present invention is：
A kind of polyimide-based graphite-metal composite material, the polyamides that the composite material contains 20~95% volumes are sub-
The relative density of the metal powder matrix of amido powdered graphite and 80~5% volumes, the composite material is 95% or more.
Relative density in the present invention indicates actual density relative to the volume by polyimide-based powdered graphite and matrix
The ratio of percentage and the calculated ideal density of real density, is calculated by following formula.
(relative density)=(actual density)/(ideal density)
(ideal density)=(real density of polyimide-based powdered graphite) × (body of polyimide-based powdered graphite
Product %)/100+ (real density of matrix) × (the volume % of matrix)/100
When relative density is 95% or more, it is ensured that it there's almost no the gap for harming heat transfer in the composite,
And the characteristics such as mechanical strength is made to improve.
Above-mentioned composite material, it is preferred that the average aspect ratio of the polyimide-based powdered graphite is 5~100, and/
Or 20~2000 μm of average grain diameter.Wherein average aspect ratio refers to the representative length of the graphite flake bedding angle of particle relative to thickness
The average value of degree, average grain diameter refer to the representative average length of the graphite flake bedding angle of powder.Average aspect ratio is too small (to be less than
5) or average grain diameter is too small (being less than 20), is unfavorable for the ordered arrangement of powder, and the thermal contact resistance between powder increases, to composite wood
The heat conductivility of material is unfavorable；Average aspect ratio is excessive (being more than 100), and the difficulty of processing of powder is big；Average grain diameter is excessive (to be more than
2000 microns), the compacting sintering of composite material is difficult.
Above-mentioned composite material, it is preferred that the metal powder matrix is one kind in copper, aluminium or its alloy.Copper is led
Hot coefficient is only second to silver in a metal, and gold, the thermal coefficient of aluminium are slightly worse, consider from price, and preferably copper and aluminium are matrix.
Above-mentioned composite material, it is preferred that the average grain diameter of the metal powder matrix is 2~120 μm, and average thickness is
100~500nm.From the point of view of improving thermal conductivity and alleviating metal metaphosphate analysis, the smaller metal powder of preferable particle size.Average thickness
Degree is less than 100 nanometers, and metal powder prepares difficult；Average thickness is more than 500 nanometers, is unfavorable for metal powder in graphite composite powder
Dispersion.
The inventive concept total as one, the present invention also provides a kind of systems of polyimide-based graphite-metal composite material
Preparation Method comprises the steps of：
(1) Kapton is fired into polyimide-based graphite film, then polyimide-based graphite film is broken into poly-
Acid imide
Base powdered graphite；
(2) polyimide-based powdered graphite and metal powder are mixed to get mixture of powders；
(3) sintering precursor is made in above-mentioned mixture of powders；
(4) to above-mentioned sintering precursor pressure sintering.
It is by being carbonized and being graphitized two that Kapton, which is fired into polyimide-based graphite film, in the step (1)
A process.Wherein, the detailed process of carbonization is that Kapton and graphite paper are put into carbide furnace, is vacuumized, first with 5-
The heating rate of 15 DEG C/min rises to 500 DEG C from room temperature, then rises to 600-650 DEG C with the heating rate of 1-5 DEG C/min, heat preservation
30-120min, then the heating rate of 1-5 DEG C/min rise to 700-800 DEG C, 30-120min are kept the temperature, finally with 5-15 DEG C/min's
Heating rate rises to 900-1500 DEG C, keeps the temperature 0.5-4h.It needs to slow down heating rate in 500-800 degree (quick decoking stage)
(being less than or equal to 5 degree), heating rate is excessively slow, and the process time is long, and production efficiency is low；Heating rate is too fast, and PI films carbonized
The exhaust gas such as a large amount of tar generated in journey are difficult quickly to deviate from from PI films, cause that film decoking is not clean or tar occurs in surface
The product defects such as point.In 900-1500 degree, PI films are basically completed decoking charing.
Graphited detailed process is that the carbonized film after PI films are carbonized is placed in graphitizing furnace, and being passed through argon gas makes
Furnace pressure maintains micro-positive pressure, and (micro-positive pressure refers to the atmospheric pressure that furnace inner gas pressure is slightly above furnace body external environment, that is, is protected
Demonstrate,proving extraneous air cannot enter in furnace body), it then is warming up to 2500-3000 DEG C with the heating rate of 5-30 DEG C/min, heat preservation
0.5-4h completes graphitizing process.2500-3000 degree can guarantee that graphite film reaches required graphitization temperature, and higher temperature is then
To equipment requirement height, high energy consumption.
The thickness of the Kapton is 5~150 μm；The thermal conductivity of the polyimide-based graphite film reaches
1500W/mk or more.PI film preparation of the thickness less than 5 microns is difficult, and PI film of the thickness more than 150 microns also prepares difficulty, and PI
Film is blocked up, and decoking is difficult in carbonization process, and the graphite film degree of graphitization of preparation is relatively low, and thermal conductivity reduces.
Above-mentioned method, it is preferred that the raw material that polyimide-based powdered graphite is used to prepare in the step (1) is polyamides
Imines film scrap or polyimide-based graphite film leftover pieces.Advantage using these leftover pieces is can to reduce polyimides
The cost of base powdered graphite.
Above-mentioned method, it is preferred that polyimide-based graphite film is broken by polyimides foundation stone using the method for ball milling
Ink powder end.The method of ball mill crushing is efficient.Wherein, the detailed process of ball milling is by stainless steel abrading-ball, the anhydrous second of ball-milling medium
Alcohol and polyimide-based graphite film (3~20) in mass ratio/(0.1~10)/1 are added into ball grinder, on ball-grinding machine with
The rotating speed ball milling 0.5 of 200~600r/min~for 24 hours, then remove abrading-ball and absolute ethyl alcohol, drying, sieving.Polyamides is sub- after broken
The average aspect ratio of amido powdered graphite is 5~100, and average grain diameter is 20~2000 μm.
The method for mixing polyimide-based powdered graphite and metal powder in the step (2), can use the technology
Any means known to field carry out, and inert fluid Jie can be added in polyimide-based powdered graphite and metal powder
Matter is mixed using planetary ball mill, and then inert liquid medium is dried using drier, obtains mixed-powder.Polyamides
The mixed proportion of imido grpup powdered graphite and metal powder should make final polyimide-based powdered graphite account for the 20 of composite material
~95 volume %.
Above-mentioned method, it is preferred that using the pressure of 5~150MPa to the powder that is filled into mold in the step (3)
Last mixture carries out uniaxial compression, to make polyimide-based powdered graphite as possible with the face direction of graphite flake layer perpendicular to pressurization side
To mode be orientated, take multi-pass filling, compacting mode come complete sintering precursor preparation.Obtained sintering precursor compact
Density height, good moldability.
Above-mentioned method, it is preferred that obtained sintering precursor is sintered while uniaxial compression in the step (4),
Form composite material.Obtained Composite Sintering density is high, favorable orientation, and thermal coefficient is high.Detailed process is that will first be sintered
Precursor is placed in tungsten carbide die and is put into hot-pressed sintering furnace, and then vacuumizing makes to keep 10 in stove-3The vacuum degree of Pa, also can be
Nitrogen or argon gas are passed through in stove as inert protective gas, then in the hot pressing pressure of 60~200MPa, 800~1000 DEG C of burning
Under junction temperature, 0.5~2h, last furnace cooling are kept the temperature, you can obtain the polyimide-based graphite-that relative density is 95% or more
Metallic composite.
Above-mentioned method, it is preferred that before polyimide-based powdered graphite and metal powder mixing, to polyimides foundation stone
Ink powder end carries out copper coating or processing of aluminizing.It, can in polyimide-based powdered graphite copper coating or by way of aluminizing
So that the proportion of copper facing or polyimide-based powdered graphite of aluminizing improves, alleviate powdered graphite and metallic copper/aluminum matrix difference in specific gravity
It is not excessive and caused by be segregated, the compatibility of polyimide-based powdered graphite and metallic copper/aluminum matrix can also be made to improve, and can
So that the performances such as mechanical strength of gained composite material improve.
Above-mentioned method, it is preferred that copper coating processing include mainly coarsening process, activation process, activation process,
Dispergation process and plating process.Detailed process is：
(a) by the polyimide-based powdered graphite obtained by step (1) temperature be 60-80 DEG C, mass fraction 60%-
1-3h is impregnated in 65% concentrated nitric acid, take out and is cleaned up, roughening treatment is completed；Roughening is i.e. using concentrated nitric acid to powdered graphite
Surface is aoxidized, and the surface-active of powdered graphite is improved.
(b) the polyimide-based powdered graphite after roughening is impregnated into 5-10min in the stannous chloride solution of pH=1.5,
Make one layer of SnOHCl colloidal film with viscosity and reproducibility of polyimide-based powdered graphite adsorption, is spent after then taking out
Ionized water cleans, and completes activation process；The effect of activation process is that one layer of polyimide-based powdered graphite adsorption is made to have
The SnOHCl colloidal films of viscosity and reproducibility.
(c) the polyimide-based powdered graphite after sensitization is immersed in the palladium chloride solution or 0.5-3g/L nitre of 0.5-3g/L
5-10min in sour silver solution, makes generation simple substance palladium or elemental silver be adsorbed on polyimide-based powdered graphite surface, then takes out simultaneously
It is cleaned with deionized water, completes activation process；Activation process i.e. oxidant palladium ion or silver ion are generated with activation process
Reducing agent SnOHCl reaction generate simple substance palladium or elemental silver, be adsorbed on the surface of polyimide-based powdered graphite；
(d) the polyimide-based powdered graphite after activation is placed in the fluoborate aqueous solution of 1-2g/L, impregnates 3-5min,
It is cleaned with deionized water after taking-up, completes dispergation process；The concentration of fluoboric acid is too low, and solution composition variation is fast, technology stability
Difference, it is excessive that fluoboric acid excessive concentration is likely to cause dispergation.The purpose of dispergation is to effectively remove colloid palladium or the outer bread of Argent grain
The stannous ion enclosed makes palladium or galactic nucleus in colloidal solid be exposed, with directly effectively catalysis starts electroless copper reaction；
(e) copper plating solution is configured, contains 10~15g/L of cupric sulfate pentahydrate, 10~15ml/L of formaldehyde, winestone in copper plating solution
40~60g/L of sour potassium sodium, 10~15g/L of sodium hydroxide, cupric sulfate pentahydrate provide copper particle, and formaldehyde makees reducing agent, potassium tartrate
Sodium, which is complexing agent, can prevent copper ion from forming hydroxide Precipitation, and sodium hydroxide is pH adjusting agent.Plating solution pH value be 9.0~
13.0, PH is too low, copper facing reaction without or carry out speed it is excessively slow.By dispergation, treated that polyimide-based powdered graphite immerses
In plating solution, it is heated to plating temperature, and keeps certain plating time, that is, completes plating process.Wherein plating temperature 60-90
DEG C, plating time 2-60min；The polyimide-based powdered graphite of copper facing is cleaned with deionized water after the completion of plating, then
Drying for standby.Plating temperature is less than 60 degree, and copper facing rate is too low；Temperature is higher than 90 degree, and copper facing rate is too fast, causes uneven coating
Uniform coating peeling；Plating time is short, and uneven coating is even；Overlong time, coating is too thick to be also easy to cause coating and graphite
Powder combines insecure.
Its weight increases by 2~40% after polyimide-based Copper-Plating Process of Graphite Powder.Copper facing is very little less than 2% coating,
It is uneven；Copper facing higher than 40% coating it is too thick, be easy to cause coating combined with graphite composite powder it is insecure, and waste plating solution.
Compared with prior art, there are following advantages by the present invention：
(1) polyimide-based graphite-metal composite material of the invention can be prepared into the sheet material of larger thickness, plank and
Block has higher intensity and adjustable coefficient of thermal expansion, and has higher thermal conductivity in a thickness direction.
(2) present invention can also be prepared using Kapton leftover pieces or polyimide-based graphite film tailing
Polyimide-based powdered graphite realizes waste reclamation.
Specific implementation mode
To facilitate the understanding of the present invention, it more comprehensively, is meticulously retouched below in conjunction with preferred embodiment to inventing to do herein
It states, but protection scope of the present invention is not limited to following specific examples.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art
Together.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention's
Protection domain.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1
PI films and graphite paper that thickness is 25 μm are intersected and stacked, is positioned in carbide furnace；To first be carbonized stove evacuation
To 20Pa, then starts heating power supply and carbide furnace is risen to 500 DEG C from room temperature with the heating rate of 10 DEG C/min；Then with
The heating rate of 2 DEG C/min rises to 600 DEG C, keeps the temperature 30min；750 DEG C are risen to the heating rate of 2 DEG C/min again, heat preservation
30min；1200 DEG C finally are risen to the heating rate of 10 DEG C/min, 1h is kept the temperature, completes the carbonization of Kapton.
Carbonized film after PI films are carbonized is placed in graphitizing furnace, and being passed through argon gas makes furnace pressure maintain micro-positive pressure,
Then start heating power supply and be warming up to 2850 DEG C with the heating rate of 15 DEG C/min, keep the temperature 0.5h, that is, complete polyimides foundation stone
The preparation of ink film.
Stainless steel abrading-ball, absolute ethyl alcohol and polyimide-based graphite film in mass ratio 9/5/1 are added into ball grinder, added
Material volume accounts for the 2/3 of ball milling tank volume, with the rotating speed ball milling 4h of 350r/min on planetary ball mill, then filters out abrading-ball and nothing
Water-ethanol and to obtain average thickness dry 3 hours in 70 DEG C of hot air drier, after sieving be 6 μm, average grain diameter is 150 μ
The polyimide-based powdered graphite of m.
Polyimide-based powdered graphite is impregnated into 2h in the concentrated nitric acid that temperature is 80 DEG C, mass fraction is 65%, is taken out
And clean up, complete roughening treatment；Then stannous chloride of the polyimide-based powdered graphite in pH=1.5 after roughening is molten
8min is impregnated in liquid, makes one layer of SnOHCl colloidal film with viscosity and reproducibility of polyimide-based powdered graphite adsorption,
It is cleaned with deionized water after taking-up, completes activation process；The polyimide-based powdered graphite after sensitization is immersed in 1g/L's again
5min in palladium chloride solution makes generation simple substance palladium be adsorbed on polyimide-based powdered graphite surface, clear with deionized water after taking-up
It washes, completes activation process；Polyimide-based powdered graphite after activation is placed in the fluoborate aqueous solution of 1g/L, is impregnated
5min is cleaned after taking-up with deionized water, completes dispergation process；Configure cupric sulfate pentahydrate be 10g/L, formaldehyde 10ml/L, wine
Stone acid potassium sodium is 40g/L, sodium hydroxide 10g/L, the plating solution that pH value is 12.0, by dispergation treated polyimide-based graphite
Powder immerses in plating solution, and 70 DEG C of plating temperature, plating time 20min is cleaned and dried with deionized water after taking-up, gathers after plating
Imide powdered graphite weightening 10%；
The polyimide-based powdered graphite of copper facing, copper powder, ethyl alcohol and stainless steel ball are added with mass ratio for 5/3/3/24
It is added in the ball grinder of planetary ball mill, wherein the average grain diameter of copper powder is 20 μm, and average thickness 200nm makes planet
Ball mill mixes 30min under the rotating speed of 150r/min, the mixture of powders of gained is taken out from planetary ball mill, then 70
DEG C hot air drier in dry 3 hours；
By in the tiling to mold of the powder of gained, the thickness of powder tiling is 1-3mm or so, using 30MPa pressure into
The uniaxial compacting of row, then continues to powder filler and suppresses, until obtaining the powder compact of required thickness；
The green body suppressed is placed in tungsten carbide die and is put into hot-pressed sintering furnace, vacuumizing makes vacuum degree in stove arrive
10-3Pa, being then passed through argon gas makes furnace pressure rise to atmospheric pressure, continues to keep the argon flow amount of 5L/min and opens sintering
Then the air outlet valve of stove is warming up to 900 DEG C under the pressure of 200MPa, keep the temperature 1h, and last furnace cooling is more than to get to thickness
500 μm of polyimide-based graphite-copper composite materials.The density of the composite material is 3.16g/cm3, relative density 97%, 25
DEG C test in-plane thermal conductivity be 830W/mk, thickness direction thermal conductivity be 25.2W/mK, bending strength 33.5MPa.
Embodiment 2
In addition to when making mixture of powders by the polyimide-based powdered graphite of copper facing, copper powder, ethyl alcohol and stainless steel
Other than ball is added to for 2/3/3/24 in the ball grinder of planetary ball mill with mass ratio, repeatedly the step of embodiment 1 is multiple to manufacture
Condensation material.The density of gained composite material is 4.118g/cm3, relative density 97.5%, the in-plane heat conduction of 25 DEG C of tests
Rate is 720W/mk, and thickness direction thermal conductivity is 35.2W/mK, bending strength 40.5MPa.
Embodiment 3
Other than following aspect, the step of repeating embodiment 1, manufactures composite material.
Thickness is used to replace 25 μm of PI films by 50 μm of PI films；Polyimide-based graphite film ball milling prepares polyamides Asia
It is 10 μm that average thickness is obtained with the rotating speed ball milling 8h of 350r/min on planetary ball mill when amido powdered graphite, after sieving,
The polyimide-based powdered graphite that average grain diameter is 50 μm；The plating time of polyimide-based powdered graphite is changed to 40min, is applied
Polyimide-based powdered graphite weightening 30% after plating；When making mixture of powders by the polyimide-based powdered graphite of copper facing, gold
Belong to copper powder, ethyl alcohol and stainless steel ball with mass ratio to be added in the ball grinder of planetary ball mill for 1/3/3/18.
The density of gained composite material is 5.85g/cm3, relative density 96%, the in-plane thermal conductivity of 25 DEG C of tests
For 630W/mk, thickness direction thermal conductivity is 45.2W/mK, bending strength 52.5MPa.
Comparative example 1
Other than using crystalline flake graphite powder to replace polyimide-based powdered graphite, the step of repeating embodiment 1, makes
Composite material is made, the plane thermal conductivity that gained composite material is tested at 25 DEG C is 450W/mK, and thickness direction thermal conductivity is 37W/
mK。
Above example illustrates that technology provided by the invention can prepare thickness and be more than 500 μm, plane aspect thermal coefficient
More than 600W/mK, thickness direction thermal coefficient is more than the high-heat-conductive composite material of 25W/mK.The composite material and use scale stone
Ink is that the graphite-metal composite material of raw material is compared, and has higher plane thermal conductivity.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, any made by repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of polyimide-based graphite-metal composite material, which is characterized in that the composite material contains 20~95% volumes
Polyimide-based powdered graphite and 80~5% volumes metal powder matrix, the relative density of the composite material is 95%
More than；
(relative density)=(actual density)/(ideal density)；
(ideal density)=(real density of polyimide-based powdered graphite) × (the volume % of polyimide-based powdered graphite)/
100+ (real density of matrix) × (the volume % of matrix)/100.
2. polyimide-based graphite-metal composite material according to claim 1, which is characterized in that the polyimides
The average aspect ratio of base powdered graphite is 5~100 and/or average grain diameter is 20~2000 μm.
3. polyimide-based graphite-metal composite material according to claim 1, which is characterized in that the metal powder
Matrix is one kind in copper, aluminium or its alloy.
4. according to the polyimide-based graphite-metal composite material of claim 1-3 any one of them, which is characterized in that described
The average grain diameter of metal powder matrix is 2~120 μm, and average thickness is 100~500nm.
5. a kind of preparation method of graphite-metal composite material polyimide-based as described in claim any one of 1-4, feature
It is, comprises the steps of：
(1) Kapton is fired into polyimide-based graphite film, then polyimide-based graphite film is broken into polyamides Asia
Amido powdered graphite；
(2) above-mentioned polyimide-based powdered graphite and metal powder are mixed to get mixture of powders；
(3) sintering precursor is made in above-mentioned mixture of powders；
(4) to above-mentioned sintering precursor pressure sintering.
6. the preparation method of polyimide-based graphite-metal composite material according to claim 5, which is characterized in that institute
It states in step (1), the raw material for being used to prepare polyimide-based powdered graphite is Kapton leftover pieces or polyimide-based
Graphite film leftover pieces.
7. the preparation method of polyimide-based graphite-metal composite material according to claim 5, which is characterized in that institute
It states in step (3), uniaxial compression is carried out to the mixture of powders being filled into mold using the pressure of 5~150MPa；It takes more
Passage filling, compacting mode come complete sintering precursor preparation.
8. the preparation method of polyimide-based graphite-metal composite material according to claim 5, which is characterized in that institute
It states in step (4), obtained sintering precursor is sintered while uniaxial compression；10 are kept in sintering process-3The vacuum degree of Pa,
The hot pressing pressure of 60~200MPa, 800~1000 DEG C of sintering temperature.
9. the preparation method of polyimide-based graphite-metal composite material according to claim 5, which is characterized in that
Before polyimide-based powdered graphite and metal powder mixing, copper coating or place of aluminizing are carried out to polyimide-based powdered graphite
Reason.
10. the preparation method of polyimide-based graphite-metal composite material according to claim 9, which is characterized in that institute
It includes coarsening process, activation process, activation process, dispergation process and plating process to state copper coating processing mainly；
The coarsening process is by polyimide-based powdered graphite temperature is 60-80 DEG C, mass fraction is the dense of 60%-65%
1-3h is impregnated in nitric acid；
The activation process is that the polyimide-based powdered graphite after roughening is impregnated 5- in the stannous chloride solution of pH=1.5
10min；
The activation process be by sensitization after polyimide-based powdered graphite be immersed in 0.5-3g/L palladium chloride solution or
5-10min in 0.5-3g/L silver nitrate solutions；
The dispergation process is that the polyimide-based powdered graphite after activation is placed in the fluoborate aqueous solution of 1-2g/L, is impregnated
3-5min；
The plating process is to immerse the polyimide-based powdered graphite after dispergation in plating solution, 60-90 DEG C of plating temperature, plating
Time 2-60min；The plating solution include 10~15g/L of cupric sulfate pentahydrate, 10~15ml/L of formaldehyde, sodium potassium tartrate tetrahydrate 40~
60g/L, 10~15g/L of sodium hydroxide, plating solution pH value are 9.0~13.0.
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| CN103924119A (en) * | 2014-04-23 | 2014-07-16 | 北京科技大学 | Ultrahigh heat conduction graphite flake/copper composite material and preparation method thereof |
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| CN103924119A (en) * | 2014-04-23 | 2014-07-16 | 北京科技大学 | Ultrahigh heat conduction graphite flake/copper composite material and preparation method thereof |
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