CN105603248B - A kind of foamy graphite alkene skeleton enhancing Cu-base composites and preparation method - Google Patents
A kind of foamy graphite alkene skeleton enhancing Cu-base composites and preparation method Download PDFInfo
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Abstract
A kind of foamy graphite alkene skeleton enhancing Cu-base composites and preparation method, the composite are made up of foam substrate, graphene strengthening layer, matrix material, and foam substrate is foam metal or foamed ceramics or foamy carbon.Graphene strengthening layer be graphene film or graphene with diamond, CNT it is compound.Matrix material is copper and copper alloy.Composite produced by the present invention with aluminium in three dimensions keeps continuously distributed because of graphene, form network blackboard, so as to weaken compound interface significantly affecting on material calorifics and electric property, the good plasticity and toughness of metallic matrix in the composite can not be reduced, and can makes enhancing mutually turn into an entirety, heat conduction and the electrical efficiency of reinforcement are played to greatest extent, thermal conductivity, conductance and the mechanical strength conventional composite materials that compare of composite are greatly improved, are a kind of very promising novel and multifunctional composites.
Description
Technical field
The invention discloses a kind of foamy graphite alkene skeleton enhancing Cu-base composites and preparation method, belong to composite
Preparing technical field.
Background technology
Graphene (Graphene) is the only one layer of atomic thickness for being stripped out from graphite material, being made up of carbon atom
Two dimensional crystal.2004, Univ Manchester UK physicist An Deliegaimu and Constantine's Nuo Woxiao loves,
Graphene is isolated in success from graphite, it was demonstrated that therefore it can also obtain Nobel's thing in 2010 jointly with individualism, two people
Neo-Confucianism prize.Graphene is both most thin material, and most tough material, 200 times more taller than best steel of fracture strength.
It has good elasticity again simultaneously, and stretch range can reach the 20% of own dimensions.It is that current nature is most thin, intensity highest
Material, if making hammock with the graphene of one piece of 1 square metre of area, weight itself can be to bear one less than 1 milligram
One kilogram of cat.A kind of novel nano-material most strong as the most thin, maximum intensity, electrical and thermal conductivity performance that have now been found that, stone
Black alkene is referred to as " dark fund ", is " king of new material ", and scientist even foretells that graphene " will thoroughly change 21 century ".
On 05 08th, 2014, one group of youth scientific research personnel of industry Hang Cai institutes of Air China was first in international graphene research field
" alkene alloy " material is created, this has the great autonomous innovation of milestone significance, and not only having invented one kind has excellent properties
Novel high-end alloy material, China is also set to turn into the leader of this material science forward position basic and applied research of graphene.Alkene
Alloy is succeeded in developing, and the declaration new series material with special excellent properties of a generation is announced to the world splendidly, and has filled up world's material
The blank of scientific domain, and then this subject is pushed to brand-new field.
Graphene is current thermal conductivity (reaching as high as 5300W/mK) highest artificial material, and thermal coefficient of expansion and close
Spend it is extremely low, it is mutually compound with high-thermal conductive metal using graphene as enhancing, ensureing to possess preferable thermal coefficient of expansion and low-density
Meanwhile more excellent heat conductivility can be obtained.Because Cu has the thermal conductivity and conductance higher than Al, while thermal expansion system
Number is lower than Al, prepares Graphene powder enhancing metal-base composites using Cu as parent metal, the hot thing of composite can be achieved
The further lifting of rationality energy.Meanwhile Cu fusing point is high, Cu/ diamond composites is had wider array of use range.Cause
This, by graphene with copper is compound it is had the excellent combination property such as highly thermally conductive, highly conductive, low-thermal-expansion and high temperature resistant concurrently, it is existing
The study hotspot of electronic package material of new generation is turned into.
However, for traditional Graphene powder enhancing metal-base composites, the Graphene powder in such a composite construction
Last (thermal conductivity 5300W/mK) both adds two just as many heat conduction isolated islands connected by metallic aluminium (thermal conductivity 237W/mK)
Boundary quantity, the raw synergy of difficult labour, the heat conductivility for making graphene excellent are difficult to give full play to again.The innovation of the present invention is thought
Road is to build continuous graphene network skeleton in the composite, and change high heat conduction isolated island is high heat conduction passage.However, for passing
The Particle reinforced composite of system, the preparation difficulty of network blackboard are very big.
Chinese invention patent CN105112754A proposes a kind of three-dimensional network diamond framework enhancing metal-based compound material
Material and preparation method, wherein metal three-dimensional network skeleton substrate using machining process prepare or using metal wire braiding and
Into.However, traditional machining process belongs to multidimensional processing, manufacturing procedure is more, and cost is higher.In addition, machining is restricted
In the constraint of tradition machinery manufacturing process and equipment, to three-dimensional porous skeleton internal holes footpath, connectivity precise controlling difficulty compared with
Greatly.The method woven using metal wire, exist and contain gap between three-dimensional pore space, and the problems such as technological process complexity.
The content of the invention
It is an object of the invention to overcome prior art deficiency and to provide a kind of enhancing of foamy graphite alkene skeleton copper-based compound
Material and preparation method, the present invention are replicated the structure of foam metal by chemical vapour deposition technique, make highly heat-conductive material with nothing
The mode of seam connection forms the entirety of a full-mesh, forms network blackboard with aluminium base, has composite excellent
The continuous capacity of heat transmission, charge-conduction ability and extremely low density.
Foamy graphite alkene skeleton of the present invention strengthens Cu-base composites, and the composite includes reinforcement, matrix material,
The reinforcement includes foam framework substrate, graphene strengthening layer, and the foam framework substrate surface is provided with graphene strengthening layer；
The foam framework substrate is selected from least one of foam metal skeleton, foamed ceramics skeleton, foam carbon skeleton, described matrix
Material is selected from copper and its alloy.
Foamy graphite alkene skeleton of the present invention strengthens Cu-base composites, and the foam metal skeleton is selected from nickel foam, foam
One kind in copper, titanium foam, foam cobalt, foam tungsten, foamed molybdenum, foam chromium, foam iron-nickel, foamed aluminium；The foamed ceramics bone
Frame is selected from foam A12O3, foam ZrO2, foam SiC, foam Si3N4, foam BN, foam B4C, foam AlN, foam WC, foam
Cr7C3In one kind.
Foamy graphite alkene skeleton of the present invention strengthens Cu-base composites, and in the foam framework substrate, foam aperture is
0.01-10mm, percent opening 40-99.9%, foam cells are uniformly distributed or random distribution；Foam framework is planar structure or three-dimensional
Stereochemical structure.
Foamy graphite alkene skeleton of the present invention strengthens Cu-base composites, and the graphene strengthening layer is selected from graphene film, stone
One kind in black alkene wall, graphene coated diamond, CNT coated graphite alkene.
Foamy graphite alkene skeleton of the present invention strengthens Cu-base composites, in graphene strengthening layer, graphene coated diamond
Refer in diamond surface growth in situ graphene, and graphene forms graphene wall perpendicular to diamond surface；
CNT coated graphite alkene refers in graphenic surface catalytic growth CNT, and CNT is perpendicular to stone
Black alkene surface forms CNT woods.
Foamy graphite alkene skeleton of the present invention strengthens Cu-base composites, and reinforcing particle is also added with matrix material, strengthens
Particle is selected from least one of high heat conduction particle, hard abrasive particles, conductive particle；The high heat conduction particle is selected from diamond
Powder, graphene, CNT, graphene coated diamond microspheres, CNT cladding diamond microballoon, CNT cladding stone
At least one of black alkene；Hard abrasive particles are selected from bortz powder, SiC, TiC, TiN, AlN, Si3N4、Al2O3、BN、WC、
MoC、Cr7C3At least one of；Conductive particle is selected from least one of graphite, CNT, graphene.
Foamy graphite alkene skeleton of the present invention strengthens Cu-base composites, in composite, the volumn concentration of each component
For：Matrix material 40-99.9%, reinforcement 0.01-60%, reinforcing particle volume fraction are 0-30%.
Foamy graphite alkene skeleton of the present invention strengthens Cu-base composites, and in hardening constituent, graphene strengthening layer volume fraction is
0.01-80%, foam framework volume fraction are 0.1-20%.
Foamy graphite alkene skeleton of the present invention strengthens Cu-base composites, and in the base, reinforcement is strengthened with monomer or more bodies
Array strengthens, and more volume array enhancings refer to reinforcement with the parallel distribution of lamellar or are distributed in so that column is parallel in matrix.
A kind of preparation method of foamy graphite alkene skeleton enhancing Cu-base composites, comprises the steps：
The first step：The preparation of reinforcement
After the cleaning of foam framework substrate, drying, graphite is grown in foam framework surface in situ using chemical vapor deposition
Alkene film, obtains reinforcement；Deposition parameter is：
Deposited graphite alkene film：It is 0.5-80.0% that carbonaceous gas, which accounts for all gas mass flow percentage in stove,；Growth temperature
Spend for 400-1200 DEG C, growth air pressure is 5-105Pa；
Or
After the cleaning of foam framework substrate, drying, graphite is grown in foam framework surface in situ using chemical vapor deposition
Alkene wall, graphene coated diamond, CNT coated graphite alkene, apply plasma on foam framework substrate in deposition process
Assisting growth, and by adding magnetic field in substrate bottom plasma confinement in foam framework near surface, reinforcing plasma pair
The bombardment on foam framework surface, graphene is set to form graphene wall perpendicular to foam framework superficial growth, obtain reinforcement；It is heavy
Accumulating technique is：
Deposited graphite alkene wall：It is 0.5-80% that carbonaceous gas, which accounts for all gas mass flow percentage in stove,；Growth temperature
For 400-1200 DEG C, growth air pressure is 5-105Pa；Plasma electric current density is 0-50mA/cm2；Magnetic field intensity is in deposition region
100 Gausses to 30 teslas；
Deposited graphite alkene cladding diamond：First, using chemical vapour deposition technique in substrate surface depositing diamond, sink
Accumulating parameter is：Carbonaceous gas mass flow percentage is 0.5-10%；Growth temperature is 600-1000 DEG C, and growth air pressure is 103-
104Pa；Then, then in diamond surface deposited graphite alkene wall, graphene grown perpendicular to diamond surface, form graphene
Wall, deposition parameter are：It is 0.5-80% that carbonaceous gas, which accounts for all gas mass flow percentage in stove,；Growth temperature is 400-
1200 DEG C, growth air pressure is 5-105Pa；Plasma electric current density is 0-50mA/cm2；Magnetic field intensity is 100 high in deposition region
This is to 30 teslas；
Deposition of carbon nanotubes coated graphite alkene：First, using chemical vapour deposition technique in substrate surface deposited graphite alkene
Film, deposition parameter are：It is 0.5-80% that carbonaceous gas, which accounts for all gas mass flow percentage in stove,；Growth temperature is 400-
1200 DEG C, growth air pressure is 5-105Pa；Then, it is in graphene wall surface deposition of carbon nanotubes woods, deposition parameter：Carbon containing gas
Weight flow percentage is 5-50%；Growth temperature is 400-1300 DEG C, and growth air pressure is 103-105Pa；Plasma current is close
Spend for 0-30mA/cm2；Magnetic field intensity is 100 Gausses to 30 teslas in deposition region；
Second step：Using pressure infiltration technology by the reinforcement with graphene strengthening layer and copper-based bluk recombination.
A kind of preparation method of foamy graphite alkene skeleton enhancing Cu-base composites, in the first step, foam framework substrate is clear
After washing, drying, first using one kind side in plating, chemical plating, evaporation, magnetron sputtering, chemical vapor deposition, physical vapour deposition (PVD)
The one kind or complex metal layer of method in substrate surface deposits nickel, copper, tungsten, molybdenum, titanium, silver, chromium, then, are placed in nanocrystalline and micro-
In the suspension of rice diamond hybrid particles, after being heated to boiling, shake, be uniformly dispersed in ultrasonic wave, obtain in mesh
Between inlay a large amount of nanocrystalline and foam framework substrates of micron diamond particle；Chemical vapor deposition is used to bubble facial bone frame substrate
Product is in foam framework surface or diamond particle surfaces growth in situ graphene film, graphene wall, graphene coated diamond, carbon
Nanotube coated graphite alkene, obtains reinforcement.
A kind of preparation method of foamy graphite alkene skeleton enhancing Cu-base composites, one layer of modification is prepared on reinforcement surface
After layer, using pressure infiltration technology and copper-based bluk recombination；The modified layer is selected from tungsten, tungsten carbide, molybdenum, molybdenum carbide, chromium, carbonization
Chromium, titanium, titanium carbide, nickel, copper, aluminium, platinum, tungsten alloy, molybdenum-base alloy, chromium-base alloy, titanium-base alloy, nickel-base alloy, acid bronze alloy,
At least one of acieral, platinum base alloy；Using plating, chemical plating, evaporation, magnetron sputtering, chemical vapor deposition, physics
A kind of method in vapour deposition prepares modified layer on reinforcement surface.
A kind of preparation method of foamy graphite alkene skeleton enhancing Cu-base composites, before deposition of carbon nanotubes, needs to use
A kind of method in plating, chemical plating, evaporation, magnetron sputtering, chemical vapor deposition, physical vapour deposition (PVD) deposits in substrate surface
Nickel, copper, one kind of cobalt or composite catalytic layer.
CVD is most possibly to realize preparation of industrialization high quality, the method for large-area graphene at present.This patent is from easy
In the foam metal or foamed ceramics or foam carbon skeleton for preparing and being seamlessly connected as substrate, chemical vapour deposition technique is utilized
High heat conduction graphene film layer is prepared on its surface, constructs high heat conduction graphene three-dimensional network skeleton, then by itself and metallic matrix
It is compound, high heat conduction graphene and metal is formed doubly-linked and lead to three-dimensional network interpenetrating structure, make enhancing phase and matrix phase in space all
Keep continuously distributed, form continuous passage of heat, produce parallel heat conduction, so as to weaken compound interface to material thermal property
Negative effect, enhancing can be made mutually to give full play to heat transfer efficiency as an entirety, and do not reduce metallic matrix in composite wood
Good plasticity and toughness in material.High thermal conductive diamond stone flour, graphene, CNT can also be added simultaneously or reduce thermal coefficient of expansion
High heat-conducting ceramic particle such as SiC, AlN in one or more, realize the further lifting of calorifics and mechanical property.
The structure of foam metal can be intactly replicated by composite made from this method, highly heat-conductive material is with nothing
The mode of seam connection forms the entirety of a full-mesh, is distributed evenly in composite, had in the form of three-dimensional network
The excellent continuous capacity of heat transmission, charge-conduction ability and extra-low density so that thermal conductivity, conductance and the machinery of composite are by force
The degree conventional composite materials that compare are greatly improved, it will and it is a kind of very promising novel and multifunctional composite, Ke Yiguang
It is general to be applied in the national economy such as heat management, electronics, the energy, traffic field.
Brief description of the drawings
The structural representation that accompanying drawing 1 is strengthened with monomer in the base for foam framework in the present invention.
Accompanying drawing 2 is foam framework in the present invention in the base with the structural representation of the parallel distribution enhancing of lamellar.
Accompanying drawing 3a, accompanying drawing 3b are the structural representation that foam framework is strengthened with the parallel distribution of column in the base in the present invention
Figure.
Embodiment
Technical scheme is further described below by specific embodiment.
The embodiment of the present invention is carried out by following technique or step：
(1) foam framework substrate is put into progress ultrasonic vibration cleaning in ethanol, it is stand-by takes out drying；
(2) using one kind side in plating, chemical plating, evaporation, magnetron sputtering, chemical vapor deposition, physical vapour deposition (PVD)
Method prepares intermediate layer on foam framework surface, and described intermediate layer includes one in nickel, copper, tungsten, molybdenum, titanium, silver, chromium
Kind or complex metal layer；
(3) nanocrystalline and micron diamond hybrid particles, foam framework substrate, solvent are mixed, is heated to seething with excitement, so
Afterwards, it is placed in high-power ultrasonics after shaking 30min, being uniformly dispersed, takes out the drying of foam framework substrate, obtain inlaying among mesh
Embedding a large amount of nanocrystalline and foam framework substrates of micron diamond particle；
(4) continuous fine and close graphene strengthening layer is deposited in metal substrate surface using hot-wire chemical gas-phase deposition, it is described
Graphene strengthening layer is selected from least one of graphene film, graphene coated diamond, CNT coated graphite alkene；
(5) before the foam framework with graphene strengthening layer and matrix material are compound, to improve strengthening layer and matrix material
The binding ability of material, surface modification treatment need to be carried out to strengthening layer, using plating, chemical plating, evaporation, magnetron sputtering, chemical gas
Mutually deposition, a kind of method in physical vapour deposition (PVD) prepared on the foam framework surface with graphene strengthening layer tungsten, tungsten carbide,
Molybdenum, molybdenum carbide, chromium, chromium carbide, titanium, titanium carbide, nickel, copper, aluminium, platinum, tungsten alloy, molybdenum alloy, evanohm, titanium alloy, nickel alloy,
At least one of copper alloy, aluminium alloy, platinum alloy modified layer；
(6) the laying mode of foamy graphite alkene skeleton reinforcement in the base after surface-modified processing can be divided into as follows
Three kinds of modes:A. foamy graphite alkene skeleton is compound as overall reinforcement and matrix, and diamond/copper net is integrally formed in composite
Network interpenetrating structure；B. foamy graphite alkene skeleton is compound as flake reinforcement body and matrix, the arragement direction of reinforcement in the base
For parallel arrangement；C. foamy graphite alkene skeleton is compound as strip reinforcement and matrix, the arragement direction of reinforcement in the base
For parallel arrangement；
(7) pressure infiltration technology is used by the foam framework with graphene strengthening layer and copper-based bluk recombination.
Embodiment one：
Foamy graphite alkene skeleton strengthens Cu-base composites, use in this example aperture be 0.2mm titanium foams as substrate, steep
Foam graphene reinforcement accounts for composite volume fraction 8%, is first according to step (1) and titanium foam three-dimensional network substrate is carried out clearly
Wash, use molybdenum film of the magnetron sputtering technique in titanium foam three-dimensional network skeleton surface deposit thickness for 50nm by step (2) afterwards
As intermediate layer；Then obtain inlaying among mesh according to step (3) a large amount of nanocrystalline and micron diamond particle
Foam framework substrate；(4) hot-wall cvd deposited graphite alkene film is used, is specially：950 DEG C are heated in H2 and Ar atmosphere (to add
H2 and Ar flow velocitys are respectively 200 and 500mL/min in thermal process, and programming rate is 33 DEG C/min), after furnace temperature rises to 950 DEG C
It is heat-treated 10min；CH4, H2 and Ar mixed gas is passed through after the completion of heat treatment, and (gas flow rate is respectively methane 5mL/min, hydrogen
Gas 200mL/min and argon gas 500mL/min), start grow graphene, cooling velocity 100 DEG C/min, growth time 1h, i.e.,
Obtain titanium foam substrate graphene three-dimensional network skeleton；Afterwards according to step (5) before compound with matrix material, using vacuum
The method of evaporation carries out surface modification in foamy graphite alkene skeleton surface in situ evaporation layer of metal copper film, and copper film thickness is
100nm；(6) the foamy graphite alkene skeleton of surface copper tungsten is placed in mould, it is parallel in the base is employed as flake reinforcement body
Set progress compound；(7) vacuum press casting is used by the foam framework with graphene strengthening layer and copper-based bluk recombination, tool
Body technology parameter is as follows：Foamy graphite alkene prefabricated skeleton part is heated to 1000 DEG C of constant temperature 1h, and mould is heated to 800 DEG C of constant temperature
1h, fine copper fusing be heated to 1250 DEG C of constant temperature 1h after degasification remove slag；Now network skeleton prefabricated component is placed in by copper liquid cast again quiet
On mould, the descending matched moulds of dynamic model, die cavity is vacuumized with die casting vacuum machine after matched moulds, when mold cavity vacuum degree is less than 1000Pa, squeezed
Pressure head starts to pressurize, and final casting pressure is 120MPa, after pressurize 2 minutes the demoulding it is copper-based multiple to obtain the enhancing of foamy graphite alkene skeleton
Condensation material.The performance test results：Thermal conductivity is 615W/ (mK).
Embodiment two:
Foamy graphite alkene skeleton strengthens Cu-base composites, use in this example aperture be 0.3mm nickel foams as substrate, steep
Foam graphene reinforcement accounts for composite volume fraction 20%, is first according to step (1) and nickel foam three-dimensional network substrate is carried out
Cleaning, use chromium film of the method for evaporation in nickel foam three-dimensional network skeleton surface deposit thickness for 300nm by step (2) afterwards
As intermediate layer；Then obtain inlaying among mesh according to step (3) a large amount of nanocrystalline and micron diamond particle
Foam framework substrate；(4) HF CVD depositing diamond film, deposition process parameters are used：Heated filament distance 6mm, substrate temperature 850
DEG C, 2200 DEG C of hot-wire temperature, deposition pressure 3KPa, CH4/H2Volume flow ratio 1:99, control sedimentation time obtains diamond thickness
200 μm of degree, obtains nickel foam substrate diamond three-dimensional network skeleton, then utilize plasma enhanced chemical vapor in diamond surface
Diamond surface growth in situ graphene is deposited on, applies plasma asistance growth on foam framework substrate in deposition process,
And by adding magnetic field plasma confinement in foam framework near surface in substrate bottom, strengthen plasma to foam framework table
The bombardment in face, graphene is grown perpendicular to diamond surface, obtain and led in mesh containing a large amount of graphene coated diamond height
Hot particle and Skeleton Table, which are looked unfamiliar, grows the foam framework of a large amount of graphene walls, and deposition parameter is：Substrate temperature is 800 DEG C, deposition gas
Press as 5.0kPa, CH4/H2 volume flow ratios 23:77, plasma electric current density 15mA/cm2；Acted under extra electric field simultaneously under
The orientation of growth of graphene is controlled, them is vertically formed graphene wall with diamond surface, obtains graphene coated diamond
Magnetic field intensity is 600 Gausses in the strengthening layer of film, wherein deposition region, obtains nickel foam substrate graphene coated diamond three-dimensional
Network skeleton；Afterwards according to step (5) before compound with matrix material, using electric plating method in foamy graphite alkene Skeleton Table
Face plating layer of metal chromium film carries out surface modification, and chromium film thickness is 400nm；(6) by the foamy graphite alkene skeleton of chrome-faced
Be placed in mould, be employed as strip reinforcement be arranged in parallel in the base carry out it is compound；(7) use vacuum die casting method will
Foam framework and copper-based bluk recombination, specific process parameter with graphene strengthening layer are as follows：Foamy graphite alkene prefabricated skeleton part
1020 DEG C of constant temperature 1h are heated to, mould is heated to 840 DEG C of constant temperature 1h, and copper alloy (trade mark T1) fusing is heated to 1260 DEG C of perseverances
Degasification is removed slag after warm 0.5h；Copper alloy liquid cast matched moulds and drift are vacuumized after exceeding sprue gate with die casting vacuum machine to die cavity,
When mold cavity vacuum degree is less than 1000Pa, drift continues to pressurize, and final casting pressure is 80MPa, and pressurize is stripped after 2 minutes and obtained
Foamy graphite alkene skeleton strengthens copper alloy composite material.The performance test results：Axial thermal conductivity is 925W/ (mK).
Embodiment three:
Foamy graphite alkene skeleton strengthens Cu-base composites, and it is 1mm foam tungstens as substrate, foam that aperture is used in this example
Graphene reinforcement accounts for composite volume fraction 10%, is first according to step (1) and foam tungsten three-dimensional network substrate is carried out clearly
Wash, be not added with intermediate layer afterwards, directly utilize chemical vapor deposition growth in situ graphene film；Then obtained according to step (3)
A large amount of nanocrystalline and foam framework substrates of micron diamond particle are inlayed among to mesh；(4) using hot-wall cvd deposition stone
Black alkene film, it is specially：950 DEG C are heated in H2 and Ar atmosphere, and (H2 and Ar flow velocitys are respectively 200 Hes in heating process
500mL/min, programming rate are 33 DEG C/min), it is heat-treated 10min after furnace temperature rises to 950 DEG C；It is passed through after the completion of heat treatment
CH4, H2 and Ar mixed gas (gas flow rate is respectively methane 5mL/min, hydrogen 200mL/min and argon gas 500mL/min),
Start to grow graphene, growth time 1h, 100 DEG C/min of cooling velocity, that is, obtain foam tungsten substrate graphene three-dimensional network
Skeleton；Magnetron sputtering deposits one layer of nickel in graphenic surface again, then using plasma-assisted chemical vapour deposition in graphene
Surface catalysis grows CNT, while the orientation of growth of lower control CNT is acted under extra electric field, make they vertically with
Graphenic surface forms CNT woods, obtains the strengthening layer of CNT coated graphite alkene film, deposition parameter is：Methane, hydrogen
Makings amount flow percentage is 5:95；Growth temperature is 600 DEG C, growth air pressure 3000Pa；Plasma electric current density 5mA/cm2；
Magnetic field intensity is 500 Gausses in deposition region, deposits 2h, obtains foam tungsten substrate CNT coated graphite alkene three-dimensional network bone
Frame；Afterwards according to step (5) before compound with matrix material, using the method for vacuum evaporation on foamy graphite alkene skeleton surface
Layer of metal titanium film is deposited and carries out surface modification, titanium film thickness is 350nm；(6) the foam diamond framework of ti coat on diamond is put
In mould, laying mode and the matrix progress for being employed as overall reinforcement are compound；(7) will be had using vacuum pressure casting
There are foam framework and copper-based bluk recombination, the specific process parameter of graphene strengthening layer as follows：Vacuum chamber pressure 5Pa, network skeleton
With 840 DEG C of constant temperature 2h of mould heating-up temperature, copper alloy (trade mark H96) fusing 1300 DEG C of heating-up temperature constant temperature 1 hour, infiltration
It is 8MPa to enter pressure, and pressurize is cooled to 400 DEG C of releases, and the demoulding obtains composite.Foamy graphite alkene skeleton enhancing copper alloy is answered
Condensation material.The performance test results：Composite overall thermal conductivity is 815W/ (mK).
Example IV：
Foamy graphite alkene skeleton strengthens Cu-base composites, and aperture is used as 2mm porous ceramics aluminum oxide conducts in this example
Substrate, foamy graphite alkene reinforcement account for composite volume fraction 10%, are first according to step (1) to foamed alumina three dimensional network
Network substrate is cleaned, and is sunk afterwards by step (2) using the technology of magnetron sputtering on foamed alumina three-dimensional network skeleton surface
Product thickness is 500nm tungsten film as intermediate layer；Then according to step (3) obtain inlaying among mesh it is a large amount of nanocrystalline and
The foam framework substrate of micron diamond particle；(4) it is in situ raw in substrate surface using plasma-assisted chemical vapour deposition
Long graphene, apply plasma asistance growth in deposition process on foam framework substrate, and by adding magnetic in substrate bottom
Plasma confinement in foam framework near surface, bombardment of the reinforcing plasma to foam framework surface, make graphene vertical
Grown in diamond surface, obtain in mesh and look unfamiliar and grow up containing a large amount of graphene coated diamond high heat conduction particles and Skeleton Table
The foam framework of graphene wall is measured, deposition parameter is：Substrate temperature is 800 DEG C, deposition pressure 5.0kPa, CH4/H2Volume flow
Measure ratio 35:65, plasma electric current density 5mA/cm2, magnetic field intensity is 700 Gausses in deposition region, deposits 5h；It is simultaneously outer to power up
The orientation of growth of the lower control graphene of effect off field, makes them vertically form graphene wall with substrate surface, obtains foam oxidation
Aluminium substrate graphene three-dimensional network skeleton；Afterwards according to step (5) before compound with matrix material, using the side of magnetron sputtering
Method carries out surface modification in foamy graphite alkene skeleton electroplating surface layer of metal tungsten-copper alloy film, and tungsten-copper alloy film thickness is
250nm；(6) the foamy graphite alkene skeleton of surface tungsten-copper alloy film is placed in mould, is employed as the laying of overall reinforcement
Mode carries out compound with matrix；(7) 2 times of cupro silicons of high heat conducting foam graphene skeleton volume are placed on above skeleton,
Wherein Si mass content is 15%, is then placed in heating furnace, 1300 DEG C of insulation 30min under high pure nitrogen protection, you can
Foamy graphite alkene skeleton enhancing copper alloy composite material is made, heat conductivity is respectively 772W/ (mK).
Embodiment five:
Foam diamond/carbon nanotube framework strengthens Cu-base composites, and aperture is used as 0.15mm foamy carbons in this example
As substrate, foam diamond reinforcement accounts for composite volume fraction 30%, is first according to step (1) to foamy carbon three dimensional network
Network substrate is cleaned, and uses magnetron sputtering technique in foam copper three-dimensional network skeleton surface deposit thickness by step (2) afterwards
For 50nm chromium film as intermediate layer；Then obtain inlaying a large amount of nanocrystalline and microns crystalline substances among mesh according to step (3)
The foam framework substrate of diamond particles；Step (4) uses HF CVD depositing diamond film, deposition process parameters：Heated filament distance
6mm, 800 DEG C of substrate temperature, 2200 DEG C of hot-wire temperature, deposition pressure 3KPa, CH4/H2Volume flow ratio 1:99, it is heavy by controlling
The product time obtains 300 μm of diamond film thickness, that is, obtains foamy carbon substrate diamond three-dimensional network skeleton；Magnetron sputtering is in gold again
Hard rock surface deposits one layer of nickel, then using plasma-assisted chemical vapour deposition in nickel surface catalytic growth CNT, together
When extra electric field under act on the orientation of growth of lower control CNT, them is vertically formed CNT with graphenic surface
Woods, obtains foamy carbon substrate diamond/carbon nanotube three-dimensional network skeleton, and deposition parameter is：Methane, hydrogen mass flow percentage
Than for 10%；Growth temperature is 600 DEG C, growth air pressure 3000Pa；Plasma electric current density 5mA/cm2；Magnetic field in deposition region
Intensity is 500 Gausses, deposits 1h.Existed afterwards according to step (5) before compound with matrix material using the method for vacuum evaporation
Foam diamond framework surface in situ evaporation layer of metal carbonization tungsten film carries out surface modification, and carbonization tungsten film thickness is 150nm；
(6) the foam diamond framework that surface is plated to carbonization tungsten film is placed in mould, and it is parallel in the base to be employed as flake reinforcement body
Set progress compound；(7) there will be foamy carbon substrate diamond/carbon nanotube three-dimensional network skeleton using vacuum pressure casting
It is as follows with copper-based bluk recombination, specific process parameter：Vacuum chamber pressure 5Pa, 840 DEG C of perseverances of network skeleton and mould heating-up temperature
Warm 2h, copper alloy (trade mark H96) fusing 1260 DEG C of heating-up temperature constant temperature 1 hour, it is 8MPa to be impregnated into pressure, and pressurize is cooled to
400 DEG C of releases, the demoulding obtain composite.Foam diamond/graphene/carbon nano-tube skeleton enhancing Cu-base composites.Property
Can test result：Composite overall thermal conductivity is 1262W/ (mK).
It was found from the thermal conductivity data that above example obtains, foamy graphite alkene skeleton enhancing prepared by the present invention is copper-based multiple
The thermal conductivity of condensation material obtains tremendous increase, and thermal conductivity is up to 1262W/mK, and composite produced by the present invention is intactly multiple
The structure of foam framework is made, highly heat-conductive material forms the entirety of a full-mesh, enhancing phase and base in a seamless fashion
Body phase keeps continuously distributed in three dimensions, forms network blackboard, can effectively weaken compound interface to material calorifics
The influence of energy, neither reduces the good plasticity and toughness of Copper substrate, and and can makes enhancing mutually turn into an entirety, plays reinforcement to greatest extent
Heat transfer efficiency, make composite have the excellent continuous capacity of heat transmission, charge-conduction ability and extra-low density, combination property bright
It is aobvious to be better than traditional Cu-base composites, it is a kind of very promising multifunctional composite, can be widely applied in heat pipe
The national economy such as reason, electronics, machinery, the energy, traffic field.
Claims (9)
1. a kind of foamy graphite alkene skeleton strengthens Cu-base composites, it is characterised in that the composite includes reinforcement, base
Body material, the reinforcement include foam framework substrate, graphene strengthening layer, and the foam framework substrate surface is provided with graphene
Strengthening layer；The foam framework substrate is selected from least one of foam metal skeleton, foamed ceramics skeleton, foam carbon skeleton,
Described matrix material is selected from copper or copper alloy；
The graphene strengthening layer is selected from graphene film, graphene wall, graphene coated diamond, CNT coated graphite alkene
In one kind；
After the cleaning of foam framework substrate, drying, first using plating, chemical plating, evaporation, magnetron sputtering, chemical vapor deposition, physics
The one kind or complex metal layer of a kind of method in substrate surface deposits nickel, copper, tungsten, molybdenum, titanium, silver, chromium in vapour deposition, so
Afterwards, it is placed in the nanocrystalline and suspension of micron diamond hybrid particles, after being heated to boiling, shakes, divides in ultrasonic wave
Dissipate uniformly, obtain inlaying a large amount of nanocrystalline and foam framework substrates of micron diamond particle among mesh；To foam framework
Substrate using chemical vapor deposition foam framework surface in situ grow graphene film, graphene wall, graphene coated diamond,
CNT coated graphite alkene, obtains reinforcement.
A kind of 2. foamy graphite alkene skeleton enhancing Cu-base composites according to claim 1, it is characterised in that the bubble
Foam metallic framework is selected from nickel foam, foam copper, titanium foam, foam cobalt, foam tungsten, foamed molybdenum, foam chromium, foam iron-nickel, foam
One kind in aluminium；The foamed ceramics skeleton is selected from foam A12O3, foam ZrO2, foam SiC, foam Si3N4, foam BN, foam
B4C, foam AlN, foam WC, foam Cr7C3In one kind.
A kind of 3. foamy graphite alkene skeleton enhancing Cu-base composites according to claim 1, it is characterised in that the bubble
In foam skeleton substrate, foam aperture 0.01-10mm, percent opening 40- ~ 99.9%, foam cells are uniformly distributed or random distribution；
Foam framework is planar structure or 3-D solid structure.
4. foamy graphite alkene skeleton according to claim 3 strengthens Cu-base composites, it is characterised in that graphene is strengthened
In layer, graphene coated diamond refers in diamond surface growth in situ graphene, and graphene is perpendicular to diamond surface
Form graphene wall；
CNT coated graphite alkene refers in graphenic surface catalytic growth CNT, and CNT is perpendicular to graphene
Surface forms CNT woods.
5. the foamy graphite alkene skeleton enhancing Cu-base composites according to claim 1-4 any one, it is characterised in that
Also be added with reinforcing particle in matrix material, reinforcing particle in high heat conduction particle, hard abrasive particles, conductive particle extremely
Few one kind；The high heat conduction particle is selected from bortz powder, graphene, CNT, graphene coated diamond microspheres, carbon nanometer
At least one of pipe cladding diamond microballoon, CNT coated graphite alkene；Hard abrasive particles be selected from bortz powder, SiC,
TiC、TiN、AlN、Si3N4、Al2O3、BN、WC、MoC、Cr7C3At least one of；Conductive particle be selected from graphite, CNT,
At least one of graphene.
6. foamy graphite alkene skeleton according to claim 5 strengthens Cu-base composites, it is characterised in that composite
In, the volumn concentration of each component is：Matrix material 40-99.9%, reinforcement 0.01-60%, reinforcing particle volume fraction
For 0-30%, each component volume basis sum is 100%.
7. foamy graphite alkene skeleton according to claim 6 strengthens Cu-base composites, it is characterised in that in the base,
Reinforcement is strengthened with monomer or more volume arrays strengthen, the more volume arrays enhancing refer to reinforcement with the parallel distribution of lamellar or with
Column is parallel to be distributed in matrix.
8. a kind of preparation method of foamy graphite alkene skeleton enhancing Cu-base composites, comprises the steps：
The first step：The preparation of reinforcement
After the cleaning of foam framework substrate, drying, first using plating, chemical plating, evaporation, magnetron sputtering, chemical vapor deposition, thing
The one kind or complex metal layer of a kind of method in substrate surface deposits nickel, copper, tungsten, molybdenum, titanium, silver, chromium in physical vapor deposition,
Then, it is placed in the nanocrystalline and suspension of micron diamond hybrid particles, after being heated to boiling, shaken in ultrasonic wave,
It is uniformly dispersed, obtains inlaying a large amount of nanocrystalline and foam framework substrates of micron diamond particle among mesh；To foam bone
Frame substrate grows graphene film using chemical vapor deposition in foam framework surface in situ, obtains reinforcement；Deposition parameter is：
Deposited graphite alkene film：It is 0.5-80% that carbonaceous gas, which accounts for all gas mass flow percentage in stove,；Growth temperature is 400-
1200 DEG C, growth air pressure is 5-105Pa；
Or
After the cleaning of foam framework substrate, drying, first using plating, chemical plating, evaporation, magnetron sputtering, chemical vapor deposition, thing
The one kind or complex metal layer of a kind of method in substrate surface deposits nickel, copper, tungsten, molybdenum, titanium, silver, chromium in physical vapor deposition,
Then, it is placed in the nanocrystalline and suspension of micron diamond hybrid particles, after being heated to boiling, shaken in ultrasonic wave,
It is uniformly dispersed, obtains inlaying a large amount of nanocrystalline and foam framework substrates of micron diamond particle among mesh；To foam bone
Frame substrate is using chemical vapor deposition in foam framework surface in situ growth graphene wall, graphene coated diamond, carbon nanometer
Pipe coated graphite alkene, apply plasma asistance growth in deposition process on foam framework substrate, and by adding in substrate bottom
Add magnetic field plasma confinement in foam framework near surface, strengthen bombardment of the plasma to foam framework surface, make graphene
Perpendicular to foam framework superficial growth, graphene wall is formed, obtains reinforcement；Depositing operation is：
Deposited graphite alkene wall：It is 0.5-80% that carbonaceous gas, which accounts for all gas mass flow percentage in stove,；Growth temperature is 400-
1200 DEG C, growth air pressure is 5-105Pa；Plasma electric current density is 0-50mA/cm2；Magnetic field intensity is 100 high in deposition region
This is to 30 teslas；
Deposited graphite alkene cladding diamond：First, using chemical vapour deposition technique in substrate surface depositing diamond, deposition ginseng
Number is：Carbonaceous gas mass flow percentage is 0.5-10%；Growth temperature is 600-1000 DEG C, and growth air pressure is 103-104Pa；
Then, then in diamond surface deposited graphite alkene wall, graphene grown perpendicular to diamond surface, form graphene wall, deposition
Parameter is：It is 0.5-80% that carbonaceous gas, which accounts for all gas mass flow percentage in stove,；Growth temperature is 400-1200 DEG C, raw
Long air pressure is 5-105Pa；Plasma electric current density 0-50mA/cm2；In deposition region magnetic field intensity be 100 Gausses to 30 it is special this
Draw；
Deposition of carbon nanotubes coated graphite alkene：First, using chemical vapour deposition technique in substrate surface deposited graphite alkene film, sink
Accumulating parameter is：It is 0.5-80% that carbonaceous gas, which accounts for all gas mass flow percentage in stove,；Growth temperature is 400-1200 DEG C,
Growth air pressure is 5-105Pa；Then, in graphene membrane surface using plating, chemical plating, evaporation, magnetron sputtering, chemical vapor deposition
A kind of method in product, physical vapour deposition (PVD) deposits carbon after substrate surface deposits nickel, copper, one kind of cobalt or composite catalytic layer
Nanotube woods, deposition parameter are：Carbonaceous gas mass flow percentage is 5-50%；Growth temperature is 400-1300 DEG C, grows gas
Press as 103-105Pa；Plasma electric current density is 0-30mA/cm2；In deposition region magnetic field intensity be 100 Gausses to 30 it is special this
Draw；
Second step：Using pressure infiltration technology by the reinforcement with graphene strengthening layer and copper-based bluk recombination.
9. a kind of preparation method of foamy graphite alkene skeleton enhancing Cu-base composites according to claim 8, its feature
It is：After preparing one layer of modified layer on reinforcement surface, using pressure infiltration technology and copper-based bluk recombination；The modified layer is selected from
Tungsten, tungsten carbide, molybdenum, molybdenum carbide, chromium, chromium carbide, titanium, titanium carbide, nickel, copper, aluminium, platinum, tungsten-bast alloy, molybdenum-base alloy, chromium base close
At least one of gold, titanium-base alloy, nickel-base alloy, acid bronze alloy, acieral, platinum base alloy；Using plating, chemical plating,
A kind of method in evaporation, magnetron sputtering, chemical vapor deposition, physical vapour deposition (PVD) prepares modified layer on reinforcement surface.
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