CN106521230B - A kind of graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission and preparation method thereof - Google Patents
A kind of graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission and preparation method thereof.The graphite flakes reinforcement that the composite of the present invention is arranged by high orientation mixes with matrix copper.The preparation method of the present invention is included in the steps such as the layers of copper plating on graphite flakes surface, copper powder ball milling flaking, the formation of preform and pressure sintering setting.The product of the present invention has relatively low and adjustable thermal coefficient of expansion on scale sheet direction, and thermal coefficient of expansion is 4 10 × 10‑6K‑1, can effectively avoid impacting coplanar other devices；It is good to orient thermal conductivity：High parallel to scale sheet direction thermal conductivity, perpendicular to scale sheet direction, thermal conductivity is less than 50Wm‑1·K‑1.In addition, the product of the present invention is easy to machining, complicated shape is can be made into meet the design of the lost circuit of hot-fluid, and the cost of material used is relatively low, is adapted to 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, which has been increasingly becoming, restricts the key that 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 that 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.But with
That electronic equipment further minimizes, Highgrade integration proposes higher requirement to heat sink material.In the heat of multi-chip module
In management design, using isotropic material partial heat can be caused to be dissipated in package interior, heat transfer efficiency is not high.Therefore,
Exploitation oriented heat dissipating material is so that heat sheds and is just particularly important along designed lines orientation.
Graphite flakes have anisotropy, and the theoretical thermal conductivity in graphite plane is up to 2000Wm-1·K-1, vertically
Thermal conductivity is only 1/200 to the 1/20 of in-plane on graphite flakes direction.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 vertical with pressure direction, gained composite is in anisotropy.At present made by graphite flakes and metal composite
Composite be mainly used in two dimensional surface radiating, i.e., composite shown on the X-Y plane direction of vertical pressing pressure compared with
High heat conductance, while show thermal coefficient of expansion that is relatively low and matching with chip again in X-Y plane.When in use will be multiple
Condensation material X-Y plane fits with chip, on the one hand due to the two matched coefficients of thermal expansion in this plane, reduces to greatest extent
Thermal stress caused by heating, improve the stability of electronic device；On the other hand, the high heat conduction of plane is advantageous to heat edge
In-plane sheds.The patents of invention such as Chinese patent CN103924119B, CN101821415B and CN103014400A disclose
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 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.In this way,
Conplane electronic device can be horizontal positioned, and 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
The features such as sub- encapsulating material possesses radiating efficiency height, and directionality is 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 can only to be dissipated for existing graphite flakes enhancing metal-base composites in two dimensional surface direction
Heat, can not be vertical direction does oriented heat dissipating the problem of, there is provided a kind of highly thermally conductive direction is mutually perpendicular to low-thermal-expansion direction, energy
Enough so that graphite flakes/carbon/carbon-copper composite material and preparation method thereof derived from heat along plane vertical direction orientation where chip.
The technical scheme is that：
A kind of vertical orientation heat transmission graphite flakes/carbon/carbon-copper composite material, mixed by graphite flakes reinforcement with Copper substrate and
Into high orientation arranges graphite in the base, normal vector and the pressing pressure direction of its sheet-like plane of more than 90% graphite
Angle is less than 15；Wherein the volume content of graphite flakes is 20~80%；Graphite flakes degree of graphitization is average more than 95%
A diameter of 50~1000 μm, draw ratio 10-100；Gained composite is in anisotropy, scale sheet-like plane and pressing direction
The direction of vertically (substantially vertical), its high heat conduction direction and low thermal coefficient of expansion is mutually perpendicular to, 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 both of Cr, Ni, Zr, B of copper mass 0.2~5% above composition.
To strengthen the combination between graphite flakes and matrix copper, composite consistency is improved, the present invention is to graphite flakes
Carry out copper coating processing；To make graphite flakes, height is preferentially arranged in the base, is carried out flaking ball milling to spherical copper powder, is obtained
To with graphite flakes shape similar in flake copper, to eliminate the size incompatibility of scale and copper powder；Then by graphite flakes,
Flake copper mixes compacting with binder.Scale under containing binder environment because pressure acts on and orientation of verting, from
And obtain scale preferred orientation preform；Finally slough binder and obtained using pressure sintering or discharge plasma sintering process
Final graphite flakes/carbon/carbon-copper composite material.
The preparation method of graphite flakes/carbon/carbon-copper composite material of above-mentioned vertical orientation heat transmission, comprises the following 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) using planetary ball mill to copper powder carry out ball milling flaking, selected copper powder size between 20~150 μm,
It is adjusted according to using graphite flakes size, drum's speed of rotation is 100~400 revs/min, Ball-milling Time 1~9 hour, most
Obtain eventually with graphite flakes shape similar in flake copper；
(3) preparation of preform；Select graphite flakes and with its shape similar in flake copper, then exist with binder
It is sufficiently mixed at 60~80 DEG C uniformly, obtains mixing feeding；Mixing feeding is put into unidirectional mould and suppressed, pressing pressure
For 2~15MPa, mould is heated in pressing process, and suppressed repeatedly, further to improve scale orientation level, then,
Thermal debinding is carried out to compacting base and sloughs most of binding agent, obtain a small amount of adhesive residue, there is some strength and hand-holdable
Mobile preform；Degreasing process is：400~500 DEG C are risen to 5~10 DEG C/min heating rate 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；To protect
The directional effect of scale is demonstrate,proved, the addition of mixing feeding must be controlled according to die size size, makes finally to shape base and highly controls
At 0.5~3 millimeter；
(4) finally preform is stacked gradually, be placed in graphite jig, using vacuum hot-pressing or discharge plasma
Method carries out unidirectional pressurization and densified sintering product to preform, obtains graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission.
Further, the composition of described copper plating bath is：8~18g/L of cupric sulfate pentahydrate, 4~8g/L of formaldehyde, potassium tartrate
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, formalin 5g/L, the sodium potassium tartrate tetrahydrate of cupric sulfate pentahydrate 15g/L, mass fraction 36%
15g/L, EDTA 20g/L, sodium hydroxide 14.5g/L, second bipyridine 0.02g/L, potassium ferrocyanide 0.01g/L；The concentration of formaldehyde
Controlled by adding the formalin that mass fraction is 36%.
From the point of view of the mechanical property for improving composite, the mechanical milling process of copper powder can also add other alloy members
Element, such as Cr, Ni, Zr, B, the copper alloy powder that sheet is obtained by the method for mechanical alloying are used as matrices of composite material；As
Preferably, in the optional pure copper powder of copper powder ball milling flaking process, or copper powder and Cr, Ni, Zr, B of copper powder quality 0.2~5%
(in order to represent convenient, during containing other elements, also all Unified Expression is copper powder or sheet to the mixture of one or more kinds of compositions
Copper powder).
Further, binder is molten by paraffin, polyethylene (high density polyethylene (HDPE)), stearic acid, polyethylene glycol and normal heptane
Liquid forms；Paraffin, high density polyethylene (HDPE), stearic acid, polyethylene glycol mass ratio are 12~18:2~5:1~2:1~2, be preferably
15:3:1:1。
Further, in step (3), the volume ratio of graphite flakes, flake copper and binder is 50~80：0~50：
50；Preferably 50~80：20~50：50.
Above-mentioned oil removing, roughening, sensitization, activation can use conventional method.
In present embodiment, the thermal conductivity of the parallel scale sheet-like plane of composite and the heat of vertical scale sheet-like plane
The coefficient of expansion can be adjusted by adding the percent by volume of graphite flakes.When graphite percent by volume is higher, step (3)
In it is contemplated that be added without flake copper, using the layers of copper of graphite surface plating as matrix, direct sintering shaping.
The technology of the present invention purpose is that prepare high heat conduction direction radiates with the orthogonal vertical orientation in low-thermal-expansion direction
Material, this purpose are by graphite flakes plating layers of copper and preparing the preform that scale high orientation arranges and realizing
, the low-thermal-expansion of the vertical graphite sheet-like plane of composite, which is derived from, to be had negative Gruneisen parameters, high anisotropy and puts down
Residual stress synergy in the graphite and composite of row arrangement.
Compared with prior art, 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 sheet direction
Number is in 4-10 × 10-6K-1, i.e., the capacity of heat transmission is poor in the horizontal direction, so as to effectively avoid to coplanar other devices
Part impacts.
(2) orientating products thermal conductivity of the invention is good：(it is more than fine copper thermal conductivity parallel to scale sheet direction thermal conductivity is high
400W·m-1·K-1), perpendicular to scale sheet direction, thermal conductivity is less than 50Wm-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.
Brief description of the drawings
Fig. 1 is the process flow diagram of the present invention.
Fig. 2 is to sinter obtained a diameter of 10mm blocks, the step of following process using sps methods.
Fig. 3 is using Fracture scan electron microscopic picture.
Embodiment
The present invention is described in further details with reference to specific embodiment, but the present invention is not limited thereto.
Embodiment 1
The thickness of graphite flakes is 10 μm in the present embodiment, and average diameter is 200 μm.Surface is carried out to graphite flakes first
Electroless copper processing：Graphite flakes are put into rinsing stirring 15 minutes in the NaOH solution that mass fraction is 20%, stands and falls
Rinsed after removing solution with ionized water to neutrality.Washed graphite flakes are put into 20ml/L HCl+20g/L SnCl2Enter in solution
Row sensitized reaction：Strong stirring 15 minutes is in cinerous with up to solution, stands and simultaneously 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
Explanation reaction is complete during color.The graphite flakes after activating will be sensitized to pour into plating copper electrolyte, graphite treatment amount is 1g/L.Plating solution is matched somebody with somebody
Side is cupric sulfate 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 and carry out copper coating processing, plating pH is 12.5, temperature 45 C,
Plating time is 20 minutes.Distilled water 1000ml is added after plating to dilute plating solution.Filtered off using the method for vacuum filtration
After plating solution, add a large amount of distilled water and copper facing scale is washed to neutrality, be put into drying box drying.Obtaining coating surface has 1 μm of copper
Graphite flakes.
Zirconium oxide balls in mass ratio 40 by granularity for 20 μm of spherical copper powder 20g and a diameter of 10mm:1 ratio adds
Enter ball grinder, then add absolute ethyl alcohol 150ml, start ball milling after stearic acid 3g.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 binder example 50 by volume:50:50 stirred at 80 DEG C it is mixed
Close, paraffin wherein in binder, high density polyethylene (HDPE), the mass ratio of stearic acid and polyethylene glycol are 15:3:1:1.It will mix equal
Even feeding is put into graphite jig, and the vertical pressure for applying 10MPa is oriented compacting, obtains the thin slice that thickness is 1.5mm
Shape base substrate.Then base substrate is put into the tube furnace for be connected with argon atmosphere and carries out thermal debinding and obtain preform base substrate.It is de-
Fat technique is：Rise to 450 DEG C with 5 DEG C/min heating rate, wherein 220 DEG C, 320 DEG C, 450 DEG C respectively be incubated 20min,
30min、10min。
Preform base substrate multiple-layer stacked is put into graphite jig, then uses spark plasma sintering method thermal sintering,
Sintering temperature is 890 DEG C, sintering pressure 30MPa, is incubated 3 minutes, produces graphite flakes/carbon/carbon-copper composite material.Composite squama
Piece sheet-like plane thermal conductivity is 443Wm-1·K-1, vertical scale sheet-like plane direction thermal coefficient of expansion 6 × 10-6K-1。
Embodiment 2
The thickness of graphite flakes is 10 μm in the present embodiment, and average diameter is 150 μm.Surface is carried out to graphite flakes first
Electroless copper processing：Graphite flakes are put into mass fraction as rinsing stirring 15 minutes in 20%NaOH solution, stands and goes
Rinsed after solution with ionized water to neutrality.Washed graphite flakes are put into 20ml/L HCl+20g/L SnCl2Carried out in solution
Sensitized reaction：Strong stirring 15 minutes is in cinerous with up to solution, stands and simultaneously 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.The graphite flakes after activating will be sensitized to pour into plating copper electrolyte, graphite treatment amount is 1g/L.Electroplate liquid formulation
For cupric sulfate 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 and carry out copper coating processing, plating pH is 12.5, temperature 45 C, during plating
Between be 20 minutes.Distilled water 1000ml is added after plating to dilute plating solution.After plating solution being filtered off using the method for vacuum filtration,
Add and copper facing scale is washed to neutrality with a large amount of distilled water, be put into drying box drying.Obtaining coating surface has the graphite of 1 μm of copper
Scale.
The zirconium oxide balls for spherical copper powder 20g, Cr powder 0.5g, Zr powder 0.2g and a diameter of 10mm that granularity is 20 μm are pressed
Mass ratio 40:1 ratio adds ball grinder, then adds absolute ethyl 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 binder example 60 by volume:40:50 stirred at 80 DEG C it is mixed
Close, paraffin wherein in binder, high density polyethylene (HDPE), the mass ratio of stearic acid and polyethylene glycol are 15:3:1:1.It will mix equal
Even feeding is put into graphite jig, and after mould is heated to 80 DEG C, the vertical pressure for applying 2MPa to tailing is oriented compacting, presses
Number 5 times, each pressurize 5s processed, obtain the laminar base substrate that thickness is 1mm.Then 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 5 DEG C/min heating rate,
Wherein 20min, 30min, 10min are incubated respectively in 220 DEG C, 320 DEG C, 450 DEG C.
Preform base substrate multiple-layer stacked is put into graphite jig, then shaped using vacuum heating-press sintering, sintering temperature
For 980 DEG C, sintering pressure 40MPa, 120 minutes are incubated, produces black scale/carbon/carbon-copper composite material.Composite scale sheet is put down
Face thermal conductivity is 512Wm-1·K-1, vertical scale sheet-like plane direction thermal coefficient of expansion 4.5 × 10-6K-1。
Embodiment 3
Selection thickness is 5 μm in the present embodiment, average diameter is about 70 μm and thickness is 10 μm, average diameter is about 150 μ
Two kinds of various sizes of graphite flakes of m by volume 1:1 mixing is as enhancing phase.Graphite flakes are carried out at Electroless copper
Reason：Graphite flakes are put into rinsing stirring 15 minutes in the NaOH solution that mass fraction is 20%, stands and is used after removing solution
Ionized water is rinsed to neutrality.Washed graphite flakes are put into 20ml/L HCl+20g/L SnCl2Carry out being sensitized instead in solution
Should：Strong stirring 15 minutes is in cinerous with up to solution, stands and simultaneously goes redundant solution.Activation stage：After sensitization
Graphite flakes add 20ml/L HCl+0.5g/L PdCl2Solution strong stirring more than 15 minutes, solution illustrate when being in light brown
Reaction is complete.The graphite flakes after activating will be sensitized to pour into plating copper electrolyte, graphite treatment amount is 1g/L.Electroplate liquid formulation is five water
Copper sulphate 15g/L, sodium potassium tartrate tetrahydrate 15g/L, EDTA20g/L, second bipyridine 0.02g/L, potassium ferrocyanide 0.01g/L.And add
Enter formaldehyde [w (HCHO)=36%] 5g/L and carry out copper coating processing, plating pH is 12.5, temperature 45 C, plating time 30
Minute.Distilled water 1000ml is added after plating to dilute plating solution.After filtering off 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 box drying.Obtaining coating surface has the graphite flakes of 2 μm of copper.
Graphite flakes after plating are directly mixed with binder, the volume ratio of scale and binder is 80:20 80
DEG C, 80 DEG C of mixing temperature, paraffin in binder, high density polyethylene (HDPE), the mass ratio of stearic acid and polyethylene glycol are 15:3:1:1.
Well mixed feeding is put into graphite jig, and the vertical pressure for applying 10MPa is oriented compacting, obtaining thickness is
1.5mm laminar base substrate.Then base substrate is put into the tube furnace for be connected with argon atmosphere and carries out thermal debinding and obtain pre-
Shape base substrate.Degreasing process is：450 DEG C are risen to 5 DEG C/min heating rate, wherein in 220 DEG C, 320 DEG C, 450 DEG C of difference
It is incubated 20min, 30min, 10min.
Finally preform base substrate multiple-layer stacked is put into graphite jig, shaped using vacuum heating-press sintering, sintering temperature
For 980 DEG C, sintering pressure 40MPa, 30 minutes are incubated, produces black scale/carbon/carbon-copper composite material.Composite scale sheet-like plane
Thermal conductivity is 487Wm-1·K-1, vertical scale sheet-like plane direction 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, and high orientation arranges graphite in the base, and normal vector and the compacting of its sheet-like plane of more than 90% graphite are pressed
The angle of force direction is less than 15 °；Composite is in anisotropy；Its preparation method, comprise the following steps：
(1) using chemical-copper-plating process in graphite flakes surface metallization layers of copper, including oil removing, roughening, sensitization, activation,
Chemical plating, described chemical plating, using copper plating bath, copper-plating technique condition：Plating solution pH is 12.0 ~ 13, plating temperature 40 ~ 50
DEG C, plating time 5 ~ 30 minutes；
(2) using planetary ball mill to copper powder carry out ball milling flaking, 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, is finally given
With graphite flakes shape similar in flake copper；
(3) preparation of preform；Select graphite flakes and with its shape similar in flake copper, then with binder 60
It is sufficiently mixed at ~ 80 DEG C uniformly, obtains mixing feeding；Mixing feeding is put into unidirectional mould and suppressed, pressing pressure 2
~ 15MPa, mould is heated in pressing process, and suppressed repeatedly, further to improve scale orientation level, then, to pressure
Base carries out thermal debinding, obtains preform；Degreasing process is：Risen under argon gas atmosphere with 5 ~ 10 DEG C/min heating rate
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, be placed in graphite jig, using vacuum hot-pressing or discharge plasma method
Unidirectional pressurization and densified sintering product are carried out to preform, obtains graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission.
2. graphite flakes/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 for graphite flakes degree of graphitization more than 95%, average diameter is 50 ~ 1000 μm, draw ratio
For 10 ~ 100.
3. graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission according to claim 1, it is characterised in that matrix
Copper is the mixture of one or both of Cr, Ni, Zr, B of fine copper or copper and copper mass 0.2 ~ 5% above composition.
4. the preparation method of 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, comprise the following steps：
(1) using chemical-copper-plating process in graphite flakes surface metallization layers of copper, including oil removing, roughening, sensitization, activation, change
Learn plating, 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) using planetary ball mill to copper powder carry out ball milling flaking, 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, is finally given
With graphite flakes shape similar in flake copper；
(3) preparation of preform；Select graphite flakes and with its shape similar in flake copper, then with binder 60
It is sufficiently mixed at ~ 80 DEG C uniformly, obtains mixing feeding；Mixing feeding is put into unidirectional mould and suppressed, pressing pressure 2
~ 15MPa, mould is heated in pressing process, and suppressed repeatedly, further to improve scale orientation level, then, to pressure
Base carries out thermal debinding, obtains preform；Degreasing process is：Risen under argon gas atmosphere with 5 ~ 10 DEG C/min heating rate
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, be placed in graphite jig, using vacuum hot-pressing or discharge plasma method
Unidirectional pressurization and densified sintering product are carried out to preform, obtains graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission.
5. the preparation method of graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission according to claim 4, its feature
It is, the composition of described copper plating bath is：8 ~ 18g/L of cupric sulfate pentahydrate, the g/L of formaldehyde 4 ~ 8, the g/L of sodium potassium tartrate tetrahydrate 8 ~ 18,
The g/L of EDTA 15 ~ 25, the g/L of sodium hydroxide 12 ~ 16,0.01 ~ 0.04g/L of second bipyridine, potassium ferrocyanide 0.01 ~
0.02g/L。
6. the preparation method of graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission according to claim 4, its feature
It is, copper powder ball milling flaking process uses pure copper powder, or copper powder and one kind in Cr, Ni, Zr, B of copper powder quality 0.2 ~ 5%
Or the mixture of two or more compositions.
7. the preparation method of graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission according to claim 4, its feature
It is, binder 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 graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission according to claim 4, its feature
It is, step（3）In, the volume ratio of graphite flakes, flake copper and binder is 50 ~ 80：20~50：50.
9. the preparation method of graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission according to claim 4, its feature
It is, preform is highly controlled at 0.5 ~ 3 millimeter, and the addition that feeding is mixed by controlling is realized.
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| 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 |
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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 |