CN106521230A - Graphite flake/copper composite material used for vertical directional heat dissipation, and preparation method thereof - Google Patents
Graphite flake/copper composite material used for vertical directional heat dissipation, and preparation method thereof Download PDFInfo
- Publication number
- CN106521230A CN106521230A CN201611112137.1A CN201611112137A CN106521230A CN 106521230 A CN106521230 A CN 106521230A CN 201611112137 A CN201611112137 A CN 201611112137A CN 106521230 A CN106521230 A CN 106521230A
- Authority
- CN
- China
- Prior art keywords
- copper
- carbon
- graphite flakes
- composite material
- graphite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0084—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ carbon or graphite as the main non-metallic constituent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L23/00—Details of semiconductor or other solid state devices
- H01L23/34—Arrangements for cooling, heating, ventilating or temperature compensation ; Temperature sensing arrangements
- H01L23/36—Selection of materials, or shaping, to facilitate cooling or heating, e.g. heatsinks
- H01L23/373—Cooling facilitated by selection of materials for the device or materials for thermal expansion adaptation, e.g. carbon
Abstract
The invention discloses a graphite flake/copper composite material used for vertical directional heat dissipation, and a preparation method thereof. The composite material is formed by mixing highly-directionally arranged graphite flake reinforcement with base copper. The preparation method comprises the following steps: copper layer plating of the surface of graphite flakes, copper powder ball milling and tabletting, formation of a pre-formed green body, and pressure sintering shaping. The composite material has low and adjustable thermal expansion coefficient of (4-10)*10<-6>K<-1> in a direction perpendicular to the direction of flake sheets, effectively avoids influences on other devices in the same plane, has good directional thermal conductivity, and has high thermal conductivity in a direction paralleling to the direction of the flake sheets, and the thermal conductivity in a direction perpendicular to the direction of the flake sheets is lower than 50W.m<-1>.K<-1>. The composite material is easy to cut, and can be processed to form a complex shape in order to meet thermal flow dissipation line design, and the cost of raw materials adopted in the invention is low, so the composite material is suitable for large-scale industrial production.
Description
Technical field
The invention belongs to high-performance electronic encapsulation function Material Field, more particularly to a kind of highly thermally conductive direction and low-thermal-expansion
Graphite flakes/carbon/carbon-copper composite material of the orthogonal vertical orientation heat transmission in coefficient direction and preparation method thereof.
Background technology
With the fast development of large scale integrated circuit, the power density of electronic device is continuously increased, great-power electronic device
The heat dissipation problem of part has been increasingly becoming the key that restriction electronic device power is further lifted.Exploitation with high thermal conductivity, compared with
The Electronic Packaging heat sink material of low and adjustable thermal coefficient of expansion is to solve the problems, such as the maximally effective means of dissipation from electronic devices.For
This, researchers develop a series of isotropic heat sink material of function admirables, such as SiC/Al, diamond/copper etc..But with
The further miniaturization of electronic equipment, Highgrade integration to put forward higher requirement heat sink material.In the heat of multi-chip module
In management design, partial heat can be caused to be dissipated in package interior using isotropic material, heat transfer efficiency is not high.Therefore,
Exploitation oriented heat dissipating material is so that heat is shed along designed lines orientation.
Graphite flakes have anisotropy, and the theoretical thermal conductivity in graphite plane is up to 2000W m-1·K-1, vertically
On graphite flakes direction, thermal conductivity is only 1/200 to the 1/20 of in-plane.In compacting process, due to the work of external force
With normal vector (Z-direction) and the pressure direction of graphite flakes sheet-like plane keep basically identical, scale sheet-like plane (X-Y side
To) tend to it is vertical with pressure direction, gained composite be in anisotropy.Made by current graphite flakes and metal composite
Composite be mainly used in two dimensional surface radiating, i.e., composite show on the X-Y plane direction of vertical pressing pressure compared with
High heat conductance, while present thermal coefficient of expansion that is relatively low and matching with chip in X-Y plane again.When in use will be multiple
Condensation material X-Y plane is fitted with chip, on the one hand due to the two matched coefficients of thermal expansion in this plane, is reduced to greatest extent
The thermal stress produced when heating up, improves the stability of electronic device；On the other hand, the high heat conduction of plane is conducive to heat edge
In-plane sheds.The patents of invention such as Chinese patent CN103924119B, CN101821415B and CN103014400A are disclosed
This two dimensional surface heat sink material and preparation method thereof.But this two dimensional surface heat sink material also has limitation using upper：When same
Plane has multiple electronic devices and components, when particularly high-power heater members are in same plane with temperature sensor, uses two
Dimensional plane heat sink material will certainly cause to influence each other between device.For this problem, the present invention proposes a kind of with vertical fixed
Cu-base composites to heat sinking function and preparation method thereof.The characteristics of material is：Highly thermally conductive direction and low-thermal-expansion direction
It is mutually perpendicular to, material in the vertical direction has excellent heat conductivility, and the capacity of heat transmission is poor in the horizontal direction.Thus,
Conplane electronic device can horizontal positioned, the heat of its high-power heater members can be quickly vertically derived
Heat affecting will not be caused to temperature sensor adjacent in horizontal direction simultaneously.This electricity with vertical orientation heat sinking function
Sub- encapsulating material possesses the features such as radiating efficiency is high, and directionality are strong, can effectively enrich the design of heat sinking pathway, to breaking through electricity
The bottleneck of sub- equipment cooling problem, realize Electronic Packaging heat management high efficiency, can design have important practical significance.
The content of the invention
The purpose of the present invention is to strengthen metal-base composites for existing graphite flakes to dissipate in two dimensional surface direction
Heat, it is impossible to do the problem of oriented heat dissipating in vertical direction, there is provided a kind of highly thermally conductive direction and low-thermal-expansion direction are mutually perpendicular to, energy
Enough so that heat is along graphite flakes/carbon/carbon-copper composite material and preparation method thereof derived from the plane vertical direction orientation of chip place.
The technical scheme is that：
A kind of vertical orientation heat transmission graphite flakes/carbon/carbon-copper composite material, mixed with Copper substrate by graphite flakes reinforcement and
Into the high orientation arrangement in the base of, graphite, the normal vector of more than 90% graphite its sheet-like plane and pressing pressure direction
Angle is less than 15；Wherein the volume content of graphite flakes is 20～80%；Graphite flakes degree of graphitization more than 95%, averagely
A diameter of 50～1000 μm, draw ratio be 10-100；Gained composite is in anisotropy, scale sheet-like plane and pressing direction
Vertically (substantially vertical), its high heat conduction direction is mutually perpendicular to the direction of low thermal coefficient of expansion, highly thermally conductive to be oriented parallel to graphite
Scale sheet-like plane, low thermal coefficient of expansion direction is perpendicular to graphite flakes sheet-like plane；Described matrix copper be fine copper or copper with
The mixture of one or more compositions in Cr, Ni, Zr, B of copper mass 0.2～5%.
For strengthening the combination between graphite flakes and matrix copper, composite consistency is improved, the present invention is to graphite flakes
Carry out copper coating process；In order to make graphite flakes, height is preferentially arranged in the base, carries out flaking ball milling to spherical copper powder, obtains
To the flake copper close with graphite flakes shape, to eliminate the size incompatibility of scale and copper powder；Subsequently by graphite flakes,
Flake copper mixes compacting with plasticizer.Scale under containing plasticizer environment orientation of verting because pressure is acted on, from
And obtain scale preferred orientation preform；Finally slough plasticizer and obtained using pressure sintering or discharge plasma sintering process
Final graphite flakes/carbon/carbon-copper composite material.
The preparation method of the graphite flakes/carbon/carbon-copper composite material of above-mentioned vertical orientation heat transmission, comprises the steps：
(1) using chemical-copper-plating process in graphite flakes surface metallization layers of copper, including oil removing, roughening, sensitization, work
Change, chemical plating, described chemical plating, using copper plating bath, copper-plating technique condition：Plating solution pH be 12.0～13, plating temperature 40～
50 DEG C, plating time 5～30 minutes；
(2) carry out ball milling flaking to copper powder using planetary ball mill, selected copper powder size between 20～150 μm,
According to being adjusted using graphite flakes size, drum's speed of rotation is 100～400 revs/min, Ball-milling Time 1～9 hour, most
The flake copper close with graphite flakes shape is obtained eventually；
(3) preparation of preform；Graphite flakes and the flake copper close with its shape is selected, is then existed with plasticizer
It is sufficiently mixed at 60～80 DEG C uniformly, obtains mixing feeding；Mixing feeding is put in unidirectional mould and is suppressed, pressing pressure
For 2～15MPa, mould is heated in pressing process, and suppressed repeatedly, further to improve scale orientation level, subsequently,
Carry out thermal debinding and slough most of binding agent to suppressing base, obtain a small amount of adhesive residue, with some strength and hand-holdable
Mobile preform；Degreasing process is：400～500 DEG C are risen to the heating rate of 5～10 DEG C/min under argon gas atmosphere, its
In 200～250 DEG C, 300～350 DEG C, 450～500 DEG C respectively be incubated 15～25min, 25～35min, 5～15min；For protecting
The directional effect of card scale, must control the addition of mixing feeding according to die size size, make finally to shape base and highly control
At 0.5～3 millimeter；
(4) finally preform is stacked gradually, is placed in graphite jig, using vacuum hot-pressing or discharge plasma
Method carries out unidirectional pressurization densified sintering product to preform, obtains the graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission.
Further, described copper plating bath is consisted of：8～18g/L of copper sulphate pentahydrate, 4～8g/L of formaldehyde, Soluble tartar.
8～18g/L of sodium, 15～25g/L of EDTA, 12～16g/L of sodium hydroxide, 0.01～0.04g/L of second bipyridine, potassium ferrocyanide
0.01～0.02g/L；Preferably, copper sulphate pentahydrate 15g/L, formalin 5g/L of mass fraction 36%, sodium potassium tartrate tetrahydrate
15g/L, EDTA 20g/L, sodium hydroxide 14.5g/L, second bipyridine 0.02g/L, potassium ferrocyanide 0.01g/L；The concentration of formaldehyde
By adding the formalin control that mass fraction is 36%.
From from the point of view of the mechanical property for improving composite, the mechanical milling process of copper powder can also add other alloy units
Element, such as Cr, Ni, Zr, B etc., the copper alloy powder for obtaining lamellar by the method for mechanical alloying are used as matrices of composite material；As
Preferably, in Cr, Ni, Zr, B of the optional pure copper powder of copper powder ball milling flaking process, or copper powder and copper powder quality 0.2～5%
(convenient in order to represent, during containing other elements, also all Unified Expression is copper powder or lamellar to the mixture of one or more compositions
Copper powder).
Further, plasticizer is molten by paraffin, polyethylene (high density polyethylene (HDPE)), stearic acid, Polyethylene Glycol and normal heptane
Liquid is constituted；Paraffin, high density polyethylene (HDPE), stearic acid, Polyethylene Glycol mass ratio are 12～18:2～5:1～2:1～2, preferably
15:3:1:1。
Further, in step (3), the volume ratio of graphite flakes, flake copper and plasticizer is 50～80：0～50：
50；Preferably 50～80：20～50：50.
Above-mentioned oil removing, roughening, sensitization, activation can be using conventional methods.
In present embodiment, the heat of the thermal conductivity of the parallel scale sheet-like plane of composite and perpendicular squama piece sheet-like plane
The coefficient of expansion can be adjusted by the percent by volume of addition graphite flakes.When graphite percent by volume is higher, step (3)
In it is contemplated that be added without flake copper, based on the layers of copper of graphite surface plating, direct sintering shaping.
The technology of the present invention purpose is to prepare high heat conduction direction with the orthogonal vertical orientation radiating in low-thermal-expansion direction
Material, this purpose are by graphite flakes plating layers of copper and preparing the preform of scale high orientation arrangement realizing
, the low-thermal-expansion of the vertical graphite sheet-like plane of composite is derived from negative Gruneisen parameters, high anisotropy and puts down
The graphite of row arrangement and residual stress synergism in composite.
Compared to existing technology, the invention has the advantages that：
(1) product of the invention has relatively low and adjustable thermal coefficient of expansion, thermal expansion system on scale lamellar direction
Number is in 4-10 × 10-6K-1, i.e., the capacity of heat transmission is poor in the horizontal direction such that it is able to be prevented effectively to other coplanar device
Part is impacted.
(2) orientating products heat conductivity of the invention is good：Parallel to scale lamellar direction thermal conductivity height (more than fine copper thermal conductivity
400W·m-1·K-1), 50W m are less than perpendicular to scale lamellar direction thermal conductivity-1·K-1。
(3) product of the invention is easy to machining, can be made into complicated shape to meet the design of the lost circuit of hot-fluid.
(4) cost of material of the present invention is relatively low, is adapted to large-scale industrial production.
Description of the drawings
Fig. 1 is the process flow diagram of the present invention.
Fig. 2 is to sinter a diameter of 10mm blocks for obtaining, the step of following process using sps methods.
Fig. 3 is using Fracture scan electron microscopic picture.
Specific embodiment
The present invention is described in further details with reference to specific embodiment, but the present invention is not limited to this.
Embodiment 1
In the present embodiment, the thickness of graphite flakes is 10 μm, and average diameter is 200 μm.Surface is carried out to graphite flakes first
Electroless copper process：Graphite flakes are put into into rinsing stirring 15 minutes in the NaOH solution that mass fraction is 20%, are stood and is fallen
Rinsed to neutrality with ionized water after removing solution.Washed graphite flakes are put into into 20ml/L HCl+20g/L SnCl2Enter in solution
Row sensitized reaction：Strong stirring is in cinerouss with up to solution in 15 minutes, stands and goes redundant solution.Activation stage：Will
Graphite flakes after sensitization add 20ml/L HCl+0.5g/L PdCl2Solution strong stirring more than 15 minutes, solution is in shallow brown
During color, explanation reaction is complete.Graphite flakes after sensitization activation are poured in plating copper electrolyte, graphite treatment amount is 1g/L.Plating solution is matched somebody with somebody
Side is copper sulphate pentahydrate 15g/L, sodium potassium tartrate tetrahydrate 15g/L, EDTA20g/L, second bipyridine 0.02g/L, potassium ferrocyanide
0.01g/L.And add formaldehyde [w (HCHO)=36%] 5g/L to carry out copper coating process, plating pH is 12.5, temperature 45 C,
Plating time is 20 minutes.Plating adds distilled water 1000ml to dilute plating solution after finishing.Filtered off using the method for vacuum filtration
After plating solution, add a large amount of distilled water that copper facing scale is washed to neutrality, be put into drying baker drying.Obtain plated surface and be covered with 1 μm of copper
Graphite flakes.
By the zirconium oxide balls in mass ratio 40 of spherical copper powder 20g and a diameter of 10mm that granularity is 20 μm:1 ratio adds
Enter ball grinder, be subsequently added dehydrated alcohol 150ml, after stearic acid 3g, start ball milling.Rotating speed 400rpm, Ball-milling Time 5 hours.Ball
Slurries filtration, vacuum drying are obtained into flake copper after mill.
By the graphite flakes after plating, flake copper and plasticizer example 50 by volume:50:50 stir mixed at 80 DEG C
Close, wherein in plasticizer, the mass ratio of paraffin, high density polyethylene (HDPE), stearic acid and Polyethylene Glycol is 15:3:1:1.Will be mixing equal
Even feeding is put into graphite jig, and applies the vertical pressure of 10MPa and be oriented compacting, obtains the thin slice that thickness is 1.5mm
Shape base substrate.Subsequently base substrate is put in the tube furnace for be connected with argon atmosphere carries out thermal debinding and obtains preform base substrate.It is de-
Fat technique is：450 DEG C are risen to the heating rate of 5 DEG C/min, wherein 220 DEG C, 320 DEG C, 450 DEG C respectively be incubated 20min,
30min、10min。
Preform base substrate multiple-layer stacked is put in graphite jig, spark plasma sintering method thermal sintering is subsequently adopted,
Sintering temperature is 890 DEG C, and sintering pressure is 30MPa, is incubated 3 minutes, obtains final product graphite flakes/carbon/carbon-copper composite material.Composite squama
Piece sheet-like plane thermal conductivity is 443W m-1·K-1, perpendicular squama piece lamellar in-plane thermal coefficient of expansion 6 × 10-6K-1。
Embodiment 2
In the present embodiment, the thickness of graphite flakes is 10 μm, and average diameter is 150 μm.Surface is carried out to graphite flakes first
Electroless copper process：Graphite flakes are put into mass fraction to stir 15 minutes for rinsing in 20%NaOH solution, are stood and is gone
Rinsed to neutrality with ionized water after solution.Washed graphite flakes are put into into 20ml/L HCl+20g/L SnCl2Carry out in solution
Sensitized reaction：Strong stirring is in cinerouss with up to solution in 15 minutes, stands and goes redundant solution.Activation stage：Will be quick
Graphite flakes after change add 20ml/L HCl+0.5g/L PdCl2Solution strong stirring more than 15 minutes, solution is in light brown
When explanation reaction it is complete.Graphite flakes after sensitization activation are poured in plating copper electrolyte, graphite treatment amount is 1g/L.Electroplate liquid formulation
For copper sulphate pentahydrate 15g/L, sodium potassium tartrate tetrahydrate 15g/L, EDTA20g/L, second bipyridine 0.02g/L, potassium ferrocyanide 0.01g/
L.And adding formaldehyde [w (HCHO)=36%] 5g/L to carry out copper coating process, plating pH is 12.5, temperature 45 C, during plating
Between be 20 minutes.Plating adds distilled water 1000ml to dilute plating solution after finishing.Filtered off after plating solution using the method for vacuum filtration,
Copper facing scale is washed to neutrality with a large amount of distilled water by addition, is put into drying baker drying.Obtain the graphite that plated surface is covered with 1 μm of copper
Scale.
By the zirconium oxide balls of spherical copper powder 20g, Cr powder 0.5g, Zr powder 0.2g and a diameter of 10mm that granularity is 20 μm by
Mass ratio 40:1 ratio adds ball grinder, is subsequently added dehydrated alcohol 150ml, starts ball milling after stearic acid 3g.Rotating speed
400rpm, Ball-milling Time 5 hours.Slurries filtration, vacuum drying are obtained into sheet alloy copper powder after ball milling.
By the graphite flakes after plating, flake copper and plasticizer example 60 by volume:40:50 stir mixed at 80 DEG C
Close, wherein in plasticizer, the mass ratio of paraffin, high density polyethylene (HDPE), stearic acid and Polyethylene Glycol is 15:3:1:1.Will be mixing equal
Even feeding is put into graphite jig, after mould is heated to 80 DEG C, is oriented compacting to the vertical pressure that tailing applies 2MPa, presses
Number of times processed 5 times, each pressurize 5s obtain the laminar base substrate that thickness is 1mm.Subsequently base substrate is put into and is connected with argon atmosphere
Tube furnace in carry out thermal debinding and obtain preform base substrate.Degreasing process is：450 DEG C are risen to the heating rate of 5 DEG C/min,
Wherein 20min, 30min, 10min is incubated respectively in 220 DEG C, 320 DEG C, 450 DEG C.
Preform base substrate multiple-layer stacked is put in graphite jig, is subsequently shaped using vacuum heating-press sintering, sintering temperature
For 980 DEG C, sintering pressure is 40MPa, is incubated 120 minutes, obtains final product black scale/carbon/carbon-copper composite material.Composite scale lamellar is put down
Fever sensation of the face conductance is 512W m-1·K-1, perpendicular squama piece lamellar in-plane thermal coefficient of expansion 4.5 × 10-6K-1。
Embodiment 3
It is 10 μm, average diameter about 150 μ that thickness is chosen in the present embodiment for 5 μm, about 70 μm of average diameter and thickness
Two kinds of various sizes of graphite flakes of m by volume 1:1 mixing is used as enhancing phase.Graphite flakes are carried out at Electroless copper
Reason：Graphite flakes are put into into rinsing stirring 15 minutes in the NaOH solution that mass fraction is 20%, are used after standing and going solution
Ionized water is rinsed to neutrality.Washed graphite flakes are put into into 20ml/L HCl+20g/L SnCl2Carry out being sensitized instead in solution
Should：Strong stirring is in cinerouss with up to solution in 15 minutes, stands and goes redundant solution.Activation stage：After sensitization
Graphite flakes add 20ml/L HCl+0.5g/L PdCl2Solution strong stirring more than 15 minutes, explanation when solution is in light brown
Reaction is complete.Graphite flakes after sensitization activation are poured in plating copper electrolyte, graphite treatment amount is 1g/L.Electroplate liquid formulation is five water
Copper sulfate 15g/L, sodium potassium tartrate tetrahydrate 15g/L, EDTA20g/L, second bipyridine 0.02g/L, potassium ferrocyanide 0.01g/L.And plus
Entering formaldehyde [w (HCHO)=36%] 5g/L carries out copper coating process, and plating pH is 12.5, temperature 45 C, and plating time is 30
Minute.Plating adds distilled water 1000ml to dilute plating solution after finishing.Filtered off after plating solution using the method for vacuum filtration, add and use
Copper facing scale is washed to neutrality by a large amount of distilled water, is put into drying baker drying.Obtain the graphite flakes that plated surface is covered with 2 μm of copper.
Graphite flakes after plating are directly mixed with plasticizer, scale is 80 with the volume ratio of plasticizer:20 80
DEG C, 80 DEG C of mixing temperature, in plasticizer, the mass ratio of paraffin, high density polyethylene (HDPE), stearic acid and Polyethylene Glycol is 15:3:1:1.
The feeding of mix homogeneously is put into into graphite jig, and applies the vertical pressure of 10MPa and be oriented compacting, obtaining thickness is
The laminar base substrate of 1.5mm.Subsequently base substrate is put in the tube furnace for be connected with argon atmosphere carries out thermal debinding and obtains pre-
Shaping base substrate.Degreasing process is：450 DEG C are risen to the heating rate of 5 DEG C/min, wherein in 220 DEG C, 320 DEG C, 450 DEG C of difference
Insulation 20min, 30min, 10min.
Finally preform base substrate multiple-layer stacked is put in graphite jig, is shaped using vacuum heating-press sintering, sintering temperature
For 980 DEG C, sintering pressure is 40MPa, is incubated 30 minutes, obtains final product black scale/carbon/carbon-copper composite material.Composite scale sheet-like plane
Thermal conductivity is 487W m-1·K-1, perpendicular squama piece lamellar in-plane thermal coefficient of expansion 5 × 10-6K-1。
Claims (9)
1. a kind of graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission, it is characterised in that by graphite flakes reinforcement and base
Body copper is mixed, graphite high orientation arrangement in the base, the normal vector of more than 90% graphite its sheet-like plane and compacting
The angle of pressure direction is less than 15 °；Composite is in anisotropy.
2. graphite flakes/the carbon/carbon-copper composite material of vertical orientation heat transmission according to claim 1, it is characterised in that graphite
The volume fraction of scale is 20～80%, and more than 95%, average diameter is 50～1000 μm, length to graphite flakes degree of graphitization
Footpath ratio is 10～100.
3. graphite flakes/the carbon/carbon-copper composite material of vertical orientation heat transmission according to claim 1, it is characterised in that matrix
Mixture of the copper for one or more compositions in Cr, Ni, Zr, B of fine copper or copper and copper mass 0.2～5%.
4. the preparation method of the graphite flakes/carbon/carbon-copper composite material of the vertical orientation heat transmission described in any one of claims 1 to 3,
Characterized in that, comprising the steps of：
(1) using chemical-copper-plating process in graphite flakes surface metallization layers of copper, including oil removing, roughening, sensitization, activation, change
Plating is learned, described chemical plating, using copper plating bath, copper-plating technique condition：Plating solution pH be 12.0～13,40～50 DEG C of plating temperature,
Plating time 5～30 minutes；
(2) carry out ball milling flaking to copper powder using planetary ball mill, selected copper powder size between 20～150 μm, according to
It is adjusted using graphite flakes size, drum's speed of rotation is 100～400 revs/min, Ball-milling Time 1～9 hour, final
To the flake copper close with graphite flakes shape；
(3) preparation of preform；Select graphite flakes and the flake copper close with its shape, then with plasticizer 60～
It is sufficiently mixed at 80 DEG C uniformly, obtains mixing feeding；Mixing feeding is put in unidirectional mould and is suppressed, pressing pressure is 2
～15MPa, heats to mould in pressing process, and suppresses repeatedly, further to improve scale orientation level, subsequently, right
Compacting base carries out thermal debinding, obtains preform；Degreasing process is：With the heating rate liter of 5～10 DEG C/min under argon gas atmosphere
To 400～500 DEG C, wherein 200～250 DEG C, 300～350 DEG C, 450～500 DEG C respectively be incubated 15～25min, 25～
35min, 5～15min；
(4) finally preform is stacked gradually, is placed in graphite jig, using vacuum hot-pressing or discharge plasma method pair
Preform carries out unidirectional pressurization densified sintering product, obtains the graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission.
5. the preparation method of the graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission according to claim 4, its feature
It is that described copper plating bath is consisted of：8～18g/L of copper sulphate pentahydrate, 4～8g/L of formaldehyde, 8～18g/L of sodium potassium tartrate tetrahydrate,
EDTA15～25g/L, 12～16g/L of sodium hydroxide, 0.01～0.04g/L of second bipyridine, 0.01～0.02g/ of potassium ferrocyanide
L。
6. the preparation method of the graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission according to claim 4, its feature
It is that copper powder ball milling flaking process adopts pure copper powder, or in copper powder and Cr, Ni, Zr, B of copper powder quality 0.2～5%
The mixture of kind or two or more compositions.
7. the preparation method of the graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission according to claim 4, its feature
It is that plasticizer is made up of paraffin, polyethylene, stearic acid, Polyethylene Glycol and n-heptane solution；Paraffin, polyethylene, stearic acid,
Polyethylene Glycol mass ratio is 12～18:2～5:1～2:1～2.
8. the preparation method of the graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission according to claim 4, its feature
It is that, in step (3), the volume ratio of graphite flakes, flake copper and plasticizer is 50～80：0～50：50.
9. the preparation method of the graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission according to claim 4, its feature
It is that preform is highly controlled at 0.5～3 millimeter, is realized by the addition for controlling mixing feeding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611112137.1A CN106521230B (en) | 2016-12-06 | 2016-12-06 | A kind of graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611112137.1A CN106521230B (en) | 2016-12-06 | 2016-12-06 | A kind of graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106521230A true CN106521230A (en) | 2017-03-22 |
| CN106521230B CN106521230B (en) | 2018-03-09 |
Family
ID=58341727
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611112137.1A Active CN106521230B (en) | 2016-12-06 | 2016-12-06 | A kind of graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106521230B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108165809A (en) * | 2018-01-11 | 2018-06-15 | 湖南科技大学 | A kind of graphite-copper based composites with network blackboard and preparation method thereof |
| CN108588461A (en) * | 2018-04-26 | 2018-09-28 | 株洲时代新材料科技股份有限公司 | A kind of polyimide-based graphite-metal composite material and preparation method |
| CN109317665A (en) * | 2018-12-03 | 2019-02-12 | 中南大学 | A kind of high-performance copper/carbon composite and preparation method thereof |
| CN110343896A (en) * | 2019-08-02 | 2019-10-18 | 青岛滨海学院 | A kind of preparation method and application of crystalline flake graphite enhancing Cu-base composites |
| CN110453101A (en) * | 2019-08-08 | 2019-11-15 | 长春工业大学 | Press from both sides metallic copper crystalline flake graphite enhancing Cu-base composites and its preparation method and application |
| CN111069611A (en) * | 2019-12-23 | 2020-04-28 | 长飞光纤光缆股份有限公司 | Preparation method of graphite-graphene-metal composite material |
| CN111687417A (en) * | 2020-07-13 | 2020-09-22 | 广东省材料与加工研究所 | Copper-plated graphite-copper-based composite material, and preparation method and application thereof |
| CN115233043A (en) * | 2022-06-15 | 2022-10-25 | 有研工程技术研究院有限公司 | Directional high-thermal-conductivity aluminum-based composite material and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2718523C1 (en) * | 2019-11-15 | 2020-04-08 | федеральное государственное автономное образовательное учреждение высшего образования "Санкт-Петербургский политехнический университет Петра Великого" (ФГАОУ ВО "СПбПУ") | Method for production of powdered copper-based composite with improved strength characteristics |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586704A (en) * | 2012-03-23 | 2012-07-18 | 北京科技大学 | High thermal conductivity graphite whisker/copper composite and preparation method thereof |
| CN103911565A (en) * | 2014-04-23 | 2014-07-09 | 北京科技大学 | Preparation method of high-thermal-conductivity graphite whisker-oriented and reinforced metal-based composite material |
| 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 |
-
2016
- 2016-12-06 CN CN201611112137.1A patent/CN106521230B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102586704A (en) * | 2012-03-23 | 2012-07-18 | 北京科技大学 | High thermal conductivity graphite whisker/copper composite and preparation method thereof |
| CN103911565A (en) * | 2014-04-23 | 2014-07-09 | 北京科技大学 | Preparation method of high-thermal-conductivity graphite whisker-oriented and reinforced metal-based composite material |
| 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 |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108165809B (en) * | 2018-01-11 | 2019-11-08 | 湖南科技大学 | A kind of graphite-copper based composites and preparation method thereof with network blackboard |
| CN108165809A (en) * | 2018-01-11 | 2018-06-15 | 湖南科技大学 | A kind of graphite-copper based composites with network blackboard and preparation method thereof |
| CN108588461B (en) * | 2018-04-26 | 2020-07-24 | 株洲时代华鑫新材料技术有限公司 | Polyimide-based graphite-metal composite material and preparation method thereof |
| CN108588461A (en) * | 2018-04-26 | 2018-09-28 | 株洲时代新材料科技股份有限公司 | A kind of polyimide-based graphite-metal composite material and preparation method |
| CN109317665A (en) * | 2018-12-03 | 2019-02-12 | 中南大学 | A kind of high-performance copper/carbon composite and preparation method thereof |
| CN109317665B (en) * | 2018-12-03 | 2020-07-17 | 中南大学 | Copper/carbon composite material and preparation method thereof |
| CN110343896A (en) * | 2019-08-02 | 2019-10-18 | 青岛滨海学院 | A kind of preparation method and application of crystalline flake graphite enhancing Cu-base composites |
| CN110343896B (en) * | 2019-08-02 | 2020-11-03 | 青岛滨海学院 | Preparation method and application of flake graphite reinforced copper-based composite material |
| CN110453101B (en) * | 2019-08-08 | 2020-09-01 | 长春工业大学 | Metal-copper-flake-sandwiched graphite reinforced copper-based composite material and preparation method and application thereof |
| CN110453101A (en) * | 2019-08-08 | 2019-11-15 | 长春工业大学 | Press from both sides metallic copper crystalline flake graphite enhancing Cu-base composites and its preparation method and application |
| CN111069611A (en) * | 2019-12-23 | 2020-04-28 | 长飞光纤光缆股份有限公司 | Preparation method of graphite-graphene-metal composite material |
| CN111069611B (en) * | 2019-12-23 | 2021-07-30 | 长飞光纤光缆股份有限公司 | Preparation method of graphite-graphene-metal composite material |
| CN111687417A (en) * | 2020-07-13 | 2020-09-22 | 广东省材料与加工研究所 | Copper-plated graphite-copper-based composite material, and preparation method and application thereof |
| CN115233043A (en) * | 2022-06-15 | 2022-10-25 | 有研工程技术研究院有限公司 | Directional high-thermal-conductivity aluminum-based composite material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106521230B (en) | 2018-03-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106521230B (en) | A kind of graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission and preparation method thereof | |
| JP6351585B2 (en) | Resin-impregnated boron nitride sintered body and use thereof | |
| CN101973532B (en) | Method for preparing nano aluminum nitride powder | |
| CN103924119B (en) | A kind of super-high heat-conductive graphite flakes/carbon/carbon-copper composite material and preparation method thereof | |
| CN103589894B (en) | Method for preparing orientation-reinforced Cu composite material for two-dimensional heat dissipation | |
| CN105400977B (en) | The preparation method of aluminum-base silicon carbide | |
| CN111889676B (en) | Method for preparing diamond copper-based composite material by additive manufacturing process | |
| CN110079708B (en) | Powder metallurgy preparation method of nano graphite sheet/Al alloy based composite material | |
| CN109554588A (en) | A kind of aeroge reinforced aluminum matrix composites and preparation method thereof | |
| CN103302294A (en) | Method for preparing nano Cu coated SiC/Cu based composite by powder metallurgic method | |
| CN109811177A (en) | A kind of preparation method of highly conductive high-intensitive silver-graphene composite material | |
| CN107686109A (en) | A kind of preparation method of the double-deck carbon-based heat conduction film of high performance graphite graphene | |
| CN114309596A (en) | Preparation method of high-thermal-conductivity surface metallized diamond/copper composite substrate | |
| CN111393856B (en) | Graphene-based high-thermal-conductivity low-thermal-resistance thermal conductive paste and preparation method thereof | |
| CN112941431B (en) | Powder metallurgy preparation method of fine-particle diamond copper-based composite heat dissipation material | |
| CN102465213A (en) | High heat conduction diamond heat sink material and preparation method thereof | |
| CN107841669B (en) | High-thermal-conductivity active composite packaging material and preparation method thereof | |
| CN116550975B (en) | Preparation method of diamond/copper composite material | |
| CN111636006B (en) | Aluminum-silicon alloy graphite composite heat conduction material and preparation and application thereof | |
| CN114717441B (en) | Method for preparing diamond/copper composite material with low density and high thermal conductivity at low cost | |
| CN109351976A (en) | Semiconductor high-power device copper-molybdenum copper-carbon/carbon-copper composite material and preparation method thereof | |
| CN104868042B (en) | A kind of high thermal conductivity composite ceramic substrate | |
| CN114316868A (en) | Heat-conducting glue and preparation method and application thereof | |
| CN112853144A (en) | Preparation method of diamond/graphene/metal composite material | |
| CN112941430B (en) | Powder metallurgy preparation method of diamond composite heat dissipation material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20170322 Assignee: Jiangxi Desien New Material Co.,Ltd. Assignor: HUNAN University OF SCIENCE AND TECHNOLOGY Contract record no.: X2023430000001 Denomination of invention: A graphite flake/copper composite for vertically oriented heat dissipation and its preparation method Granted publication date: 20180309 License type: Exclusive License Record date: 20230110 |