CN105779804B - A kind of foam framework structure enhancing metal-base composites and preparation method - Google Patents
A kind of foam framework structure enhancing metal-base composites and preparation method Download PDFInfo
- Publication number
- CN105779804B CN105779804B CN201610161232.4A CN201610161232A CN105779804B CN 105779804 B CN105779804 B CN 105779804B CN 201610161232 A CN201610161232 A CN 201610161232A CN 105779804 B CN105779804 B CN 105779804B
- Authority
- CN
- China
- Prior art keywords
- foam
- diamond
- deposition
- graphene
- framework
- 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.)
- Active
Links
Classifications
-
- 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
- C22C1/08—Alloys with open or closed pores
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
- C23C16/27—Diamond only
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Carbon And Carbon Compounds (AREA)
- Laminated Bodies (AREA)
- Chemical Vapour Deposition (AREA)
Abstract
A kind of foam framework enhancing metal-base composites and preparation method thereof, the composite is made up of foam framework, surface consolidation material with matrix, and foam framework is foam metal or foamed ceramics or foamy carbon.Surface consolidation material is the highly heat-conductive materials such as diamond film, graphene film, CNT.Metal matrix material is copper, aluminium, copper alloy, aluminium alloy etc..Composite enhancing produced by the present invention mutually keeps continuously distributed with matrix phase in three dimensions, form network blackboard, influence of the compound interface to material thermal property can effectively be weakened, neither reduce the good plasticity and toughness of metallic matrix, and can makes enhancing mutually turn into an entirety, the heat transfer efficiency of reinforcement is played to greatest extent, and thermal conductivity, conductance and the mechanical strength conventional composite materials that compare of composite are greatly improved, are a kind of very promising multifunctional composites.
Description
Technical field
The invention discloses a kind of foam framework structure to strengthen metal-base composites, belongs to composite technology of preparing neck
Domain.
Background technology
Diamond has the excellent physical property such as high thermal conductivity (room temperature is up to 2200W/mK), superhard, wear-resisting.Carbon nanometer
Pipe, graphene are the Novel Carbon Nanomaterials being found in recent years, are respectively provided with the property such as high heat conductance and excellent electricity, mechanics
Energy.Therefore, using diamond, graphene, CNT single-phase or mixed phase as enhancing phase and metal composite, can obtain more
Excellent heat conduction, conductive and mechanical properties, meet the needs of different field is to heat conduction, conductive and mechanical properties.
Main Research Thinking is to increase diamond particle content and improve the compound of diamond particles/metal both at home and abroad at present
Interface, achieve preferable effect.However, the diamond particles (thermal conductivity 1800-2200W/mK) in such a composite construction
Just as many heat conduction isolated islands connected by metal (Al-237W/mK, Cu-398W/mK), two-phase interface quantity was both added, again
The raw synergy of difficult labour, the heat conductivility for making diamond excellent are difficult to give full play to.Network blackboard, i.e. enhancing phase and matrix
Mutually all keep continuously distributed in space, so as to weaken compound interface significantly affecting on material thermal property, can fully send out
The high enhancing efficiency of enhancing phase is waved, and does not reduce the good plasticity and toughness of metallic matrix in the composite.However, for traditional
Particle reinforced composite, the preparation difficulty of network blackboard is very big, the system of especially nonmetallic enhancing phase network structure
Standby, high fragility, high modulus and hardness causes it to be difficult machine-shaping.
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 the diamond heat-conducting effect in existing diamond particles enhancing metal-base composites
This not high defect of rate, high heat conducting foam skeleton structure reinforcement, and and metallic matrix are built by chemical vapour deposition technique
Compound, change high heat conduction isolated island significantly lifts the heat transfer efficiency of highly heat-conductive material in the composite into high heat conduction passage.
A kind of foam framework structure enhancing metal-base composites of the present invention, the composite include foam framework, base
Body material, the foam framework are selected from foam metal skeleton or foamed ceramics skeleton or foam carbon skeleton, the choosing of described matrix material
From metal material.
A kind of present invention foam framework structure enhancing metal-base composites, the metallic matrix be selected from metallic copper, aluminium,
Magnesium, silver, titanium, cobalt, nickel, tungsten, molybdenum, tantalum, one kind of niobium or acid bronze alloy, acieral, magnesium base alloy, silver-base alloy, titanium-based are closed
One kind in gold, cobalt-base alloys, nickel-base alloy, tungsten-bast alloy, molybdenum-base alloy, tantalum-base alloy, niobium-base alloy.
A kind of present invention foam framework structure enhancing metal-base composites, the foam metal skeleton be selected from nickel foam,
One kind in foam copper, titanium foam, foam cobalt, foam tungsten, foamed molybdenum, foam chromium, foam iron-nickel, foamed aluminium；The foam pottery
Porcelain body frame is selected from foam A12O3, foam ZrO2, foam SiC, foam Si3N4, foam BN, foam B4C, foam AlN, foam WC, bubble
Foam Cr7C3In one kind.
A kind of foam framework structure enhancing metal-base composites of the present invention, foam aperture 0.01-10mm, porosity
40-99%, foam cells are uniformly distributed or random distribution；Foam framework is planar structure or 3-D solid structure.
A kind of foam framework structure enhancing metal-base composites of the present invention, the foam framework surface is provided with strengthening layer.
A kind of foam framework structure enhancing metal-base composites of the present invention, the strengthening layer are selected from diamond film, graphite
Alkene film, carbon nano-tube film, diamond/graphene film, diamond/carbon nanotube films, graphene/carbon nano-tube film, diamond/stone
One kind in black alkene/carbon nano-tube film, strengthening layer thickness are 0.34nm-800 microns.
A kind of present invention foam framework structure enhancing metal-base composites, in strengthening layer, diamond/graphene film refers to
In diamond surface growth in situ graphene, and graphene forms graphene wall perpendicular to diamond surface；
Diamond/carbon nanotube films refer in diamond surface catalytic growth CNT, and CNT is perpendicular to gold
Hard rock surface forms CNT woods；
Graphene/carbon nano-tube film refers in graphenic surface catalytic growth CNT, and CNT is perpendicular to stone
Black alkene surface forms CNT woods；
Diamond/graphene/carbon nano-tube film refers to after diamond surface growth in situ graphene film catalytic growth again
CNT woods, and graphene sprawls film forming in diamond surface, CNT is formed perpendicular to diamond and graphenic surface
CNT woods.
A kind of foam framework structure of the present invention strengthens metal-base composites, and reinforcing particle is also added with matrix material,
Reinforcing particle is selected from least one of high heat conduction particle, hard abrasive particles, conductive particle；The high heat conduction particle is selected from gold
Emery, graphene, CNT, graphene coated diamond microspheres, CNT cladding diamond microballoon, CNT bag
Cover at least one of graphene；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.
A kind of present invention foam framework structure enhancing metal-base composites, in composite, the volume basis of each component
Content is：Matrix material 10-90%, foam framework reinforcement 5-80%, reinforcing particle volume fraction are 0-30%, and each group divides it
With for 100%.
In foam framework reinforcement, strengthening layer volume fraction is 0.1-80%, and foam framework volume fraction is 0.1-20%.
A kind of foam framework structure enhancing metal-base composites of the present invention, in the base, foam framework is strengthened with monomer
Or more volume array enhancings, more volume array enhancings refer to foam framework with the parallel distribution of lamellar or are distributed in so that column is parallel
In matrix.
A kind of preparation method of present invention foam framework enhancing metal-base composites, be by the cleaning of foam framework substrate,
It is using pressure infiltration technology that foam framework is compound with metallic matrix after drying.
A kind of preparation method of present invention foam framework enhancing metal-base composites, after foam framework is cleaned, dry,
Using chemical vapor deposition after foam framework superficial growth strengthening layer diamond film, graphene film, carbon nano-tube film, with metal
Matrix is compound；Deposition parameter is：
Diamond CVD deposition parameter is：Carbonaceous gas mass flow percentage is 0.5-10%；Growth temperature is 600-
1000 DEG C, growth air pressure is 103-104Pa。
Graphene CVD deposition parameter is：Carbonaceous gas mass flow percentage is 0.5-80%；Growth temperature is 400-
1200 DEG C, growth air pressure is 5-105Pa；Plasma electric current density 0-50mA/cm2；Magnetic field intensity is 100 Gausses in deposition region
To 30 teslas.
CNT CVD deposition parameter is：Carbonaceous gas mass flow percentage is 5-50%；Growth temperature is 400-
1300 DEG C, growth air pressure is 103-105Pa；Plasma electric current density is 0-30mA/cm2；Magnetic field intensity is 100 in deposition region
Gauss is to 30 teslas；
Or
After the cleaning of foam framework substrate, drying, using chemical vapor deposition in foam framework superficial growth strengthening layer gold
After hard rock/graphene film, diamond/carbon nanotube films, graphene/carbon nano-tube film, diamond/graphene/carbon nano-tube film,
It is compound with metallic matrix；
Apply plasma asistance growth in deposition process on foam framework substrate, and by adding magnetic field in substrate bottom
Plasma confinement in foam framework near surface, bombardment of the reinforcing plasma to foam framework surface, raising chemical vapor deposition
Product speed simultaneously controls deposit growth direction；Depositing operation is：
Diamond/carbon nanotube films：First, using chemical vapour deposition technique in substrate surface depositing diamond, deposition
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, it is in diamond surface deposition of carbon nanotubes, deposition parameter：Carbonaceous gas mass flow percentage is 5-
50%；Growth temperature is 400-1300 DEG C, and growth air pressure is 103-105Pa；Plasma electric current density is 0-30mA/cm2；Deposition
Magnetic field intensity is 100 Gausses to 30 teslas in region.
Depositing diamond/graphene film：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：Carbonaceous gas mass flow percentage is 0.5-80%；Growth temperature is 400-1200 DEG C, grows air pressure
For 5-105Pa；Plasma electric current density is 0-50mA/cm2；Magnetic field intensity is 100 Gausses to 30 teslas in deposition region.
Deposited graphite alkene/carbon nano-tube film：First, using chemical vapour deposition technique in substrate surface deposited graphite alkene
Wall, deposition parameter are：Deposition parameter is：Carbonaceous gas mass flow percentage is 0.5-80%；Growth temperature is 400-1200
DEG C, growth air pressure is 5-105Pa；Plasma electric current density is 0-50mA/cm2；In deposition region magnetic field intensity be 100 Gausses extremely
30 teslas；Then, it is in graphene wall surface deposition of carbon nanotubes, deposition parameter：Carbonaceous gas mass flow percentage is
5-80%；Growth temperature is 400-1200 DEG C, and growth air pressure is 5-105Pa；Plasma electric current density is 0-50mA/cm2；Deposition
Magnetic field intensity is 100 Gausses to 30 teslas in region.
Depositing diamond/graphene/carbon nano-tube film：First, deposited using chemical vapour deposition technique in substrate surface
Diamond, deposition parameter are：Carbonaceous gas mass flow percentage is 0.5-10%；Growth temperature is 600-1000 DEG C, growth
Air pressure is 103-104Pa；Then, it is in diamond surface deposited graphite alkene film, deposition parameter：Carbonaceous gas mass flow percentage
Than for 0.5-80%；Growth temperature is 400-1200 DEG C, and growth air pressure is 0.5-105Pa；Plasma electric current density 0-50mA/
cm2；Magnetic field intensity is 100 Gausses to 30 teslas in deposition region；In deposition region magnetic field intensity be 100 Gausses to 30 it is special this
Draw；Finally, it is in graphenic surface deposition of carbon nanotubes woods, deposition parameter：Carbonaceous gas mass flow percentage is 5-80%；
Growth temperature is 400-1200 DEG C, and growth air pressure is 5-105Pa；Plasma electric current density 0-50mA/cm2。
A kind of preparation method of foam framework enhancing metal-base composites of the present invention, the cleaning of foam framework substrate, drying
Afterwards, first steeped using a kind of method in plating, chemical plating, evaporation, magnetron sputtering, chemical vapor deposition, physical vapour deposition (PVD)
Foam skeleton surface deposition nickel, copper, tungsten, molybdenum, titanium, silver, one kind in chromium or complex metal layer, then, are placed in nanocrystalline and micron
Shake, be uniformly dispersed in ultrasonic wave in the suspension of diamond hybrid particles, obtain inlaying among mesh it is a large amount of nanocrystalline and
After the foam framework substrate of micron diamond particle；To foam framework using chemical vapor deposition in foam framework surface or gold
Hard rock particle surface grows strengthening layer.
A kind of preparation method of foam framework enhancing metal-base composites of the present invention, changes strengthening one layer of layer surface preparation
After property 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 alloy, evanohm, titanium alloy, nickel alloy, copper alloy, aluminium alloy, platinum
At least one of alloy；Using in plating, chemical plating, evaporation, magnetron sputtering, chemical vapor deposition, physical vapour deposition (PVD)
A kind of method prepares modified layer on reinforcement surface.
A kind of preparation method of foam framework enhancing enhancing metal-base composites of the present invention, before deposition of carbon nanotubes,
A kind of method in plating, chemical plating, evaporation, magnetron sputtering, chemical vapor deposition, physical vapour deposition (PVD) need to be used in substrate table
Face deposition nickel, copper, one kind of cobalt or composite catalytic layer.
This patent from foam metal that is easily prepared and being seamlessly connected or foamed ceramics or foam carbon skeleton as substrate,
High heat conduction film layer (such as diamond, graphene, CNT) is prepared on its surface using chemical vapour deposition technique, constructs height
Heat conduction three-dimensional network skeleton, then it is compound with metallic matrix, make highly heat-conductive material and the logical three-dimensional network of metal formation doubly-linked mutual
Structure is worn, enhancing phase and matrix phase is all kept continuously distributed in space, forms continuous passage of heat, produces parallel lead
Heat, so as to weaken negative effect of the compound interface to material thermal property, enhancing can be made mutually to be given full play to as an entirety
Heat transfer efficiency, and the good plasticity and toughness of metallic matrix in the composite are not reduced.High heat-conductive diamond can also be added simultaneously
Powder, graphene, CNT 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.Similarly, using corresponding highly conductive or high hard wear-resisting strengthening layer and enhancing
Particle can also realize the composite of this foam framework structure enhancing Metal Substrate or polymer matrix in fields such as electricity, mechanics
Application.
The structure of foam metal can be intactly replicated by composite made from this method, highly heat-conductive material is with seamless
The mode of connection forms the entirety of a full-mesh, is uniformly distributed in the form of three-dimensional network in composite, has excellent
The continuous capacity of heat transmission, charge-conduction ability and extra-low density so that thermal conductivity, conductance and the mechanical strength phase of composite
Compare conventional composite materials to be greatly improved, it will be a kind of very promising novel and multifunctional composite, can answer extensively
For 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 3 is foam framework in the present invention in the base with the structural representation of the parallel distribution enhancing of column.
When accompanying drawing 4 is strengthened with the parallel distribution of column in the base for foam framework in the present invention, foam framework is in the base
Distribution schematic diagram.
Embodiment
Technical scheme is further described below by specific embodiment.
The embodiment of the present invention is carried out by following technique or step：The present invention is further described below by specific embodiment
Technical scheme.
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 strengthening layer, the strengthening layer are deposited in metal substrate surface using hot-wire chemical gas-phase deposition
For selected from diamond film, graphene film, carbon nano-tube film, graphene coated diamond, CNT cladding diamond, carbon nanometer
One kind in pipe coated graphite alkene, carbon nano tube/graphene composite membrane cladding diamond；
(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 the foam framework reinforcement after surface-modified processing in the base can be divided into following three kinds of sides
Formula:A. foam framework is compound as overall reinforcement and matrix, and diamond/metallic matrix network interpenetrating is integrally formed in composite
Structure；B. foam framework is compound as flake reinforcement body and matrix, and the arragement direction of reinforcement in the base is parallel arrangement；c.
Foam framework is compound as strip reinforcement and matrix, and the arragement direction of reinforcement in the base is parallel arrangement；
(7) it is using pressure infiltration technology that the foam framework with strengthening layer and metallic matrix is compound.
Embodiment one:Foam diamond framework strengthens silver-based composite material
Foam diamond framework strengthens silver-based composite material, use in this example aperture be 0.2mm foam coppers as substrate, steep
Foam diamond reinforcement accounts for composite volume fraction 20%, is first according to step (1) and foam copper three-dimensional network substrate is carried out
Cleaning, uses molybdenum of the magnetron sputtering technique in foam copper three-dimensional network skeleton surface deposit thickness for 50nm by step (2) afterwards
Film is as intermediate layer；Then obtain inlaying a large amount of nanocrystalline and micron diamond particles among mesh according to step (3)
Foam framework substrate；Step (4) uses HF CVD depositing diamond film, deposition process parameters：Heated filament distance 6mm, matrix temperature
800 DEG C of degree, 2200 DEG C of hot-wire temperature, deposition pressure 3KPa, CH4/H2Volume flow ratio 1:99, by controlling sedimentation time to obtain
60 μm of diamond film thickness, that is, obtain foam copper substrate diamond three-dimensional network skeleton；Afterwards according to step (5) with matrix material
Expect it is compound before, layer of metal tungsten film is deposited in foam diamond framework surface in situ using the method for vacuum evaporation and carries out surface
It is modified, tungsten film thickness 200nm；(6) the foam diamond framework that surface is plated to tungsten is placed in mould, is employed as flake reinforcement
Body be arranged in parallel in the base carry out it is compound；(7) 2 times of silver alloy of diamond framework volume are placed on above skeleton, then
It is put into heating furnace, 950 DEG C of insulation 30min under high pure nitrogen protection, you can foam diamond framework enhancing silver-based is made and answers
Condensation material, heat conductivity are respectively 862W/ (mK).
Embodiment two:Foamy graphite alkene skeleton strengthens Cu-base composites
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 200nm 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 850 DEG C, deposition pressure 5.0kPa, CH4/H2Volume flow
Measure ratio 10:90, plasma electric current density 5mA/cm2, magnetic field intensity is 500 Gausses in deposition region；Make simultaneously under extra electric field
With the orientation of growth of lower control graphene, them is vertically formed graphene wall with substrate surface, obtain foamed alumina substrate
Graphene three-dimensional network skeleton；Afterwards according to step (5) before compound with matrix material, the method using magnetron sputtering is being steeped
Foam graphene skeleton electroplating surface layer of metal tungsten-copper alloy film carries out surface modification, and tungsten-copper alloy film thickness is 200nm；(6)
The foamy graphite alkene skeleton that surface is coated with to tungsten-copper alloy film is placed in mould, be employed as the laying mode of overall reinforcement with
Matrix carries out compound；(7) 2 times of cupro silicons of high heat conducting foam graphene skeleton volume are placed on above skeleton, wherein Si
Mass content be 15%, be then placed in heating furnace, high pure nitrogen protection under 1350 DEG C insulation 30min, you can be made bubble
Foam graphene skeleton strengthens copper alloy composite material, and heat conductivity is respectively 770W/ (mK).
Embodiment three:Graphene/diamond foam framework enhancing Cu-base composites
Foam diamond framework strengthens Cu-base composites, and it is 0.3mm nickel foam as substrate that aperture is used in this example,
Foam diamond reinforcement accounts for composite volume fraction 30%, is first according to step (1) and foam copper three-dimensional network substrate is entered
Row cleaning, is first according to step (1) and nickel foam three-dimensional network substrate (aperture 0.05mm) surface is pre-processed, press afterwards
Step (2) uses the method for evaporation to be used as middle mistake in nickel foam three-dimensional network skeleton surface deposit thickness for 300nm chromium film
Cross layer；Then obtain inlaying a large amount of nanocrystalline and foam frameworks of micron diamond particle linings among mesh according to step (3)
Bottom；(4) HF CVD depositing diamond film, deposition process parameters are used：Heated filament distance 6mm, 850 DEG C of substrate temperature, hot-wire temperature
2200 DEG C, deposition pressure 3KPa, CH4/H2Volume flow ratio 1:99, by controlling sedimentation time to obtain the μ of diamond film thickness 300
M, nickel foam substrate diamond three-dimensional network skeleton is obtained, then existed in diamond surface using plasma-assisted chemical vapour deposition
Diamond surface growth in situ graphene, apply plasma asistance growth in deposition process on foam framework substrate, and pass through
Plasma confinement is banged foam framework surface in foam framework near surface, reinforcing plasma in substrate bottom addition magnetic field
Hit, graphene is grown perpendicular to diamond surface, obtain in mesh and contain a large amount of graphene coated diamond high heat conduction particles
Looked unfamiliar with Skeleton Table and grow the foam framework of a large amount of graphene walls, deposition parameter is：Substrate temperature is 900 DEG C, and deposition pressure is
5.0kPa, CH4/H2 volume flow ratio 15:85, plasma electric current density 5mA/cm2, magnetic field intensity is 300 high in deposition region
This；The orientation of growth of lower control graphene is acted under extra electric field simultaneously, them is vertically formed graphene with diamond surface
Wall, the strengthening layer of graphene coated diamond film is obtained, obtain 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 electroplating surface one
Layer crome metal film carries out surface modification, and chromium film thickness is 500nm；(6) the foamy graphite alkene skeleton of chrome-faced is placed in mould
In, be employed as strip reinforcement be arranged in parallel in the base carry out it is compound；(7) there will be graphite using vacuum die casting method
The foam framework of alkene strengthening layer and aluminium base bluk recombination, specific process parameter are as follows：Foamy graphite alkene prefabricated skeleton part is heated to
1020 DEG C of constant temperature 1h, mould are heated to 840 DEG C of constant temperature 1h, and copper alloy (trade mark T1) fusing is heated to 1160 DEG C of constant temperature 0.5h
Degasification is removed slag afterwards；Copper alloy liquid pours into a mould matched moulds and drift with die casting vacuum machine behind sprue gate to die cavity more than being vacuumized, and works as die cavity
When vacuum is less than 1000Pa, drift continues to pressurize, and final casting pressure is 80MPa, and pressurize is stripped after 2 minutes and obtains foam stone
Black alkene skeleton strengthens copper alloy composite material.The performance test results：Heat conductivity is 954W/ (mK).
Example IV：CNT/diamond foam framework enhancing Al alloy composite
Foam diamond framework strengthens Al alloy composite, use in this example aperture be 1mm foam tungstens as substrate, steep
Foam diamond reinforcement accounts for composite volume fraction 40%, is first according to step (1) and foam tungsten three-dimensional network substrate is carried out
Cleaning, is not added with intermediate layer, directly utilizes chemical vapor deposition growth in situ graphene film afterwards；Then according to step (3)
Obtain inlaying a large amount of nanocrystalline and foam framework substrates of micron diamond particle among mesh；Step (4) uses HF CVD
Depositing diamond film, deposition process parameters：Heated filament distance 6mm, 900 DEG C of substrate temperature, 2300 DEG C of hot-wire temperature, deposition pressure
3KPa, CH4/H2Volume flow ratio 1:99, it is 400 μm to control diamond film thickness, that is, obtains foam tungsten substrate diamond three dimensional network
Network skeleton, then magnetron sputtering deposit one layer of nickel in diamond surface, then using plasma-assisted chemical vapour deposition in nickel table
Surface catalysis grows CNT, while the orientation of growth of lower control CNT is acted under extra electric field, makes them vertically and stone
Black alkene surface forms CNT woods, obtains the strengthening layer of CNT coated graphite alkene film, deposition parameter is：Methane, hydrogen
Mass flow percentage is 25:75；Growth temperature is 600 DEG C, growth air pressure 3000Pa；Plasma electric current density 5mA/cm2；It is heavy
Magnetic field intensity is 350 Gausses in product region, and sedimentation time obtains foam tungsten substrate CNT cladding diamond three-dimensional for 40 minutes
Network skeleton；Afterwards according to step (5) before compound with matrix material, using electric plating method in the carbon nanometer with setting
The foam diamond framework electroplating surface layer of metal copper film of pipe woods array, copper film thickness 500nm；(6) by copper coating
Foam diamond framework is placed in mould, and laying mode and the matrix progress for being employed as overall reinforcement are compound；(7) using true
Air presses casting, and specific process parameter is such as by the foam framework with diamond/carbon nanotube strengthening layer and aluminium base bluk recombination
Under：Vacuum chamber pressure 5Pa, 720 DEG C of constant temperature 2h of network skeleton and mould heating-up temperature, aluminium alloy (trade mark 6063) fusing add
Hot 760 DEG C of temperature constant temperature 1 hour, it is 8MPa to be impregnated into pressure, and pressurize is cooled to 400 DEG C of releases, and the demoulding obtains composite.Bubble
Foam graphene skeleton strengthens Al alloy composite.The performance test results：Composite overall thermal conductivity is 976W/ (mK).
Embodiment five:Carbon nano tube/graphene foam framework strengthens composite material of magnesium alloy
Foamy graphite alkene skeleton strengthens magnesium-based composite material, and it is 1mm foam tungstens as substrate, foam that aperture is used in this example
Graphene reinforcement accounts for composite volume fraction 7%, 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：In H2With 950 DEG C of (H in heating process are heated in Ar atmosphere2It is respectively 200 Hes with Ar flow velocitys
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、H2With Ar mixed gas (gas flow rate is respectively methane 5mL/min, hydrogen 200mL/min and argon gas 500mL/min),
Start to grow graphene, 100 DEG C/min of cooling velocity, it is 1.7nm to obtain graphene film average thickness, that is, obtains foam tungsten lining
Bottom graphene three-dimensional network skeleton；Magnetron sputtering deposits one layer of nickel in graphenic surface again, then utilizes plasma-assisted chemical
The growth that vapour deposition acts on lower control CNT in graphenic surface catalytic growth CNT, while under extra electric field takes
To, them is vertically formed CNT woods with graphenic surface, obtain the strengthening layer of CNT coated graphite alkene film, deposition
Parameter is：Methane, hydrogen mass flow percentage is 10%；Growth temperature is 600 DEG C, growth air pressure 3000Pa；Plasma current
Density 5mA/cm2；Magnetic field intensity is 500 Gausses in deposition region, sedimentation time, 30min, obtains foam tungsten substrate CNT
Coated graphite alkene three-dimensional network skeleton；Afterwards according to step (5) before compound with matrix material, using the method for vacuum evaporation
On foamy graphite alkene skeleton surface, evaporation layer of metal titanium film carries out surface modification, and titanium film thickness is 500nm；(6) surface is plated
The nanotube coated graphite alkene foam framework of titanium is placed in mould, and the laying mode and matrix for being employed as overall reinforcement are carried out
It is compound；(7) it is using vacuum pressure casting that the foam framework with graphene strengthening layer and magnesium alloy substrate is compound, specific work
Skill parameter is as follows：Vacuum chamber pressure 5Pa, 700 DEG C of constant temperature 2h of network skeleton and mould heating-up temperature, magnesium alloy fusing heating
750 DEG C of temperature constant temperature 1 hour, it is 8MPa to be impregnated into pressure, and pressurize is cooled to 400 DEG C of releases, and the demoulding obtains composite.Foam
CNT coated graphite alkene skeleton strengthens composite material of magnesium alloy.The performance test results：Composite overall thermal conductivity is
540W/(m·K)。
Embodiment six:Foam diamond/graphene/carbon nano-tube skeleton enhancing silver-based composite material
Foam diamond/graphene/carbon nano-tube skeleton strengthens silver-based composite material, and aperture is used as 0.3mm in this example
Foam copper accounts for composite volume fraction 10% as substrate, foam diamond reinforcement, is first according to step (1) to foam copper
Three-dimensional network substrate is cleaned, and is sunk afterwards by step (2) using magnetron sputtering technique on foam copper three-dimensional network skeleton surface
Product thickness is 50nm molybdenum 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；Step (4) uses HF CVD depositing diamond film, deposition process parameters：Heat
Flight lead is from 6mm, 800 DEG C of substrate temperature, 2200 DEG C of hot-wire temperature, deposition pressure 3KPa, CH4/H2Volume flow ratio 1:99, pass through
Control sedimentation time obtains 60 μm of diamond film thickness, that is, obtains foam copper substrate diamond three-dimensional network skeleton；Again using heat
Wall CVD is specially in diamond surface in-situ deposition graphene film：950 DEG C of (heating processes are heated in H2 and Ar atmosphere
Middle H2 and Ar flow velocitys are respectively 200 and 500mL/min, and programming rate is 33 DEG C/min), it is heat-treated after furnace temperature rises to 950 DEG C
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
200mL/min and argon gas 500mL/min), start grow graphene, 100 DEG C/min of cooling velocity, growth time 50 minutes, i.e.,
Obtain foam copper diamond/graphene three-dimensional network skeleton；Magnetron sputtering deposits one layer of nickel in graphenic surface again, then utilizes
Plasma-assisted chemical vapour deposition acts on lower control carbon in graphenic surface catalytic growth CNT, while under extra electric field
The orientation of growth of nanotube, them is vertically formed CNT woods with graphenic surface, obtain foam copper diamond/graphite
Alkene/carbon nano tube three-dimensional network skeleton, deposition parameter are：Methane, hydrogen mass flow percentage is 10%；Growth temperature is 600
DEG C, growth air pressure 3000Pa；Plasma electric current density 5mA/cm2；Magnetic field intensity is 30 teslas in deposition region, growth time
60 minutes.Afterwards according to step (5) before compound with matrix material, using the method for vacuum evaporation in foam diamond framework
Surface in situ evaporation layer of metal tungsten film carries out surface modification, tungsten film thickness 150nm；(6) surface is plated to the foam Buddha's warrior attendant of tungsten
Stone skeleton is placed in mould, be employed as flake reinforcement body be arranged in parallel in the base carry out it is compound；(7) by diamond framework body
2 times of long-pending silver alloy are placed on above skeleton, are then placed in heating furnace, 950 DEG C of insulation 30min under high pure nitrogen protection,
Foam diamond framework enhancing silver-based composite material is can be prepared by, heat conductivity is respectively 697W/ (mK).
Embodiment seven:Foamy graphite alkene skeleton strengthens titanium matrix composite
Foamy graphite alkene skeleton strengthens Cu-base composites, and aperture is used as 2mm porous ceramics carborundum conducts in this example
Substrate, foamy graphite alkene reinforcement account for composite volume fraction 15%, are first according to step (1) to foam silicon carbon 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 200nm 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 contain a large amount of graphene coated diamond high heat conduction particles and skeleton superficial growth.
The foam framework of a large amount of graphene walls, deposition parameter are：Substrate temperature is 850 DEG C, deposition pressure 5.0kPa,
CH4/H2Volume flow ratio 10:90, plasma electric current density 5mA/cm2, magnetic field intensity is 500 Gausses in deposition region, during growth
Between 1 hour；The orientation of growth of lower control graphene is acted under extra electric field simultaneously, them is vertically formed graphite with substrate surface
Alkene wall, obtain foamy graphite alkene 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
200nm；(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 titanium alloys of high heat conducting foam graphene skeleton volume are placed on above skeleton, so
After be put into heating furnace, 1750 DEG C of insulation 30min under high pure nitrogen protection, you can foamy graphite alkene skeleton enhancing titanium is made and closes
Metal/composite material, heat conductivity are respectively 728W/ (mK).
Embodiment eight:Foam diamond framework strengthens magnesium-based composite material
Foam diamond framework strengthens magnesium-based composite material, and it is 0.35mm foamy carbons as substrate that aperture is used in this example,
Foam diamond reinforcement accounts for composite volume fraction 30%, is first according to step (1) and foamy carbon three-dimensional network substrate is entered
Row cleaning, uses magnetron sputtering technique in foamy carbon three-dimensional network skeleton surface deposit thickness for 50nm's by step (2) afterwards
Molybdenum film is as intermediate layer；Then obtain inlaying a large amount of nanocrystalline and micron diamonds among mesh according to step (3)
The foam framework substrate of grain；Step (4) uses HF CVD depositing diamond film, deposition process parameters：Heated filament distance 6mm, matrix
800 DEG C of temperature, deposition pressure 3KPa, CH4/H2Volume flow ratio 1:99, by controlling sedimentation time to obtain diamond film thickness
300 μm, that is, obtain foamy carbon substrate diamond three-dimensional network skeleton；Afterwards according to step (5) before compound with matrix material,
Surface modification is carried out in foam diamond framework surface in situ evaporation layer of metal tungsten film using the method for vacuum evaporation, tungsten film is thick
Spend for 100nm；(6) the foam diamond framework that surface is plated to tungsten is placed in mould, is employed as flake reinforcement body in the base
Be arrangeding in parallel, it is compound to carry out；(7) will have foam diamond framework and magnesium-based bluk recombination, specific work using vacuum pressure casting
Skill parameter is as follows：Vacuum chamber pressure 5Pa, 700 DEG C of constant temperature 2h of network skeleton and mould heating-up temperature, magnesium alloy fusing heating
750 DEG C of temperature constant temperature 1 hour, it is 8MPa to be impregnated into pressure, and pressurize is cooled to 400 DEG C of releases, and the demoulding obtains composite, foam
Carbon substrate diamond framework strengthens magnesium-based composite material.The performance test results：Composite overall thermal conductivity is 875W/ (m
K)。
It was found from the thermal conductivity and mechanical performance data that above example obtains, foam framework enhancing prepared by the present invention is golden
The thermal conductivity of metal-matrix composite material obtains tremendous increase, and thermal conductivity is up to 976W/mK, composite enhancing produced by the present invention
Mutually keep continuously distributed in three dimensions with matrix phase, form network blackboard, can effectively weaken compound interface to material
The influence of thermal property, neither reduces the good plasticity and toughness of metallic matrix, and and can makes enhancing mutually turn into an entirety, sent out to greatest extent
The heat transfer efficiency of reinforcement is waved, makes thermal conductivity, conductance and the mechanical strength conventional composite materials that compare of composite have pole
Big to improve, combination property is a kind of very promising multi-functional apparently higher than traditional Metal Substrate or polymer matrix composite
Composite.
Claims (11)
1. a kind of foam framework structure strengthens metal-base composites, it is characterised in that the composite include foam framework,
Matrix material, the foam framework are selected from foam metal skeleton or foamed ceramics skeleton or foam carbon skeleton, described matrix material
Selected from metal material；
The foam framework surface is provided with strengthening layer；The strengthening layer is selected from diamond film, graphene film, carbon nano-tube film, gold
In hard rock/graphene film, diamond/carbon nanotube films, graphene/carbon nano-tube film, diamond/graphene/carbon nano-tube film
One kind；
After the cleaning of foam framework substrate, drying, first using one in plating, chemical plating, chemical vapor deposition, physical vapour deposition (PVD)
Kind method deposits one kind or complex metal layer in nickel, copper, tungsten, molybdenum, titanium, silver, chromium on foam framework surface, then, is placed in and receives
In the suspension of meter Jing and micron diamond hybrid particles, after being heated to boiling, shake, be uniformly dispersed in ultrasonic wave, obtain
After a large amount of nanocrystalline and foam framework substrates of micron diamond particle are inlayed among to mesh, to foam framework using chemistry
Vapour deposition grows strengthening layer in foam framework surface in situ；Apply plasma asistance on foam framework substrate in deposition process
Growth, and by adding magnetic field plasma confinement in foam framework near surface in substrate bottom, strengthen plasma to foam
The bombardment on skeleton surface, improve chemical vapor deposition speed and control deposit growth direction.
A kind of 2. foam framework structure enhancing metal-base composites according to claim 1, it is characterised in that Metal Substrate
Body be selected from metallic copper, aluminium, magnesium, silver, titanium, cobalt, nickel, tungsten, molybdenum, tantalum, one kind of niobium or acid bronze alloy, acieral, magnesium base alloy,
One in silver-base alloy, titanium-base alloy, cobalt-base alloys, nickel-base alloy, tungsten-bast alloy, molybdenum-base alloy, tantalum-base alloy, niobium-base alloy
Kind.
A kind of 3. foam framework structure enhancing metal-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 4. foam framework structure enhancing metal-base composites according to claim 3, it is characterised in that foam hole
Footpath is 0.01-10mm, porosity 40-99%, and foam cells are uniformly distributed or random distribution；Foam framework is planar structure or three
Tie up stereochemical structure.
5. foam framework structure according to claim 1 strengthens metal-base composites, it is characterised in that in strengthening layer,
Diamond/graphene film refers in diamond surface growth in situ graphene, and graphene forms stone perpendicular to diamond surface
Black alkene wall；
Diamond/carbon nanotube films refer in diamond surface catalytic growth CNT, and CNT is perpendicular to diamond
Surface forms CNT woods；
Graphene/carbon nano-tube film refers in graphenic surface catalytic growth CNT, and CNT is perpendicular to graphene
Surface forms CNT woods；
Diamond/graphene/carbon nano-tube film refers to after diamond surface growth in situ graphene catalytic growth carbon nanometer again
Guan Lin, and graphene sprawls film forming in diamond surface, CNT forms carbon nanometer perpendicular to diamond and graphenic surface
Guan Lin.
6. the foam framework structure enhancing metal-base composites according to claim 1-5 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.
7. foam framework structure according to claim 6 strengthens metal-base composites, it is characterised in that composite
In, the volumn concentration of each component is：Matrix material 10-90%, foam framework reinforcement 5-80%, reinforcing particle volume integral
Number 0-30%, each component volume basis sum are 100%.
8. foam framework structure according to claim 5 strengthens metal-base composites, it is characterised in that in the base,
Foam framework is strengthened with monomer or more volume arrays strengthen, and more volume array enhancings refer to foam framework with the parallel distribution of lamellar
Or it is distributed in so that column is parallel in matrix.
A kind of 9. preparation method of foam framework enhancing metal-base composites, it is characterised in that：Foam framework is cleaned, dried
Afterwards, adopted using chemical vapor deposition after foam framework superficial growth strengthening layer diamond film, graphene film, carbon nano-tube film
It is with pressure infiltration technology that foam framework is compound with metallic matrix；Deposition parameter is：
Diamond CVD deposition parameter is：Carbonaceous gas mass flow percentage is 0.5-10%；Growth temperature is 600-1000 DEG C,
Grow air pressure 103-104Pa；
Graphene CVD deposition parameter is：Carbonaceous gas mass flow percentage is 0.5-80%；Growth temperature is 400-1200 DEG C,
Grow air pressure 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；
CNT CVD deposition parameter is：Carbonaceous gas mass flow percentage is 5-50%；Growth temperature is 400-1300 DEG C,
Grow air pressure 103-105Pa；Plasma electric current density 0-30mA/cm2；In deposition region magnetic field intensity be 100 Gausses to 30 it is special this
Draw；
Or
By foam framework substrate cleaning, drying after, using chemical vapor deposition foam framework superficial growth strengthening layer diamond/
After graphene film, diamond/carbon nanotube films, graphene/carbon nano-tube film, diamond/graphene/carbon nano-tube film, use
Pressure infiltration technology by foam framework with it is compound with metallic matrix；
Apply plasma asistance growth in deposition process on foam framework substrate, and by adding magnetic field handle etc. in substrate bottom
Plasma confinement is in foam framework near surface, bombardment of the reinforcing plasma to foam framework surface, raising chemical vapor deposition speed
Spend and control deposit growth direction；Depositing operation is：
Diamond/carbon nanotube films：First, using chemical vapour deposition technique in substrate surface depositing diamond, deposition parameter
For：Carbonaceous gas mass flow percentage is 0.5-10.0%；Growth temperature is 600-1000 DEG C, and growth air pressure is 103-104Pa；
Then, diamond surface using plating, chemical plating, chemical vapor deposition, a kind of method in physical vapour deposition (PVD) deposit nickel,
Copper, one kind of cobalt or composite catalytic layer, finally, deposition of carbon nanotubes, deposition parameter is：Carbonaceous gas mass flow percentage is
5-50%；Growth temperature is 400-1300 DEG C, and growth air pressure is 103-105Pa；Plasma electric current density is 0-30mA/cm2；Deposition
Magnetic field intensity is 100 Gausses to 30 teslas in region；
Depositing diamond/graphene film：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：Carbonaceous gas mass flow percentage is 0.5-80%；Growth temperature is 400-1200 DEG C, and growth air pressure is 5-
105Pa；Plasma electric current density is 0-50mA/cm2；Magnetic field intensity is 100 Gausses to 30 teslas in deposition region；
Deposited graphite alkene/carbon nano-tube film：First, using chemical vapour deposition technique in substrate surface deposited graphite alkene wall, sink
Accumulating parameter is：Carbonaceous gas mass flow percentage is 5-80%；Growth temperature is 400-1200 DEG C, and growth air pressure is 5-
105Pa；Plasma electric current density 0-50mA/cm2；Magnetic field intensity is 100 Gausses to 30 teslas in deposition region；Then, in stone
Black alkene wall surface deposits nickel, copper, cobalt using a kind of method in plating, chemical plating, chemical vapor deposition, physical vapour deposition (PVD)
A kind of or composite catalytic layer, finally, deposition of carbon nanotubes, deposition parameter is：Carbonaceous gas mass flow percentage is 5-80%；
Growth temperature is 400-1200 DEG C, and growth air pressure is 5-105Pa；Plasma electric current density is 0-50mA/cm2；Magnetic in deposition region
Field intensity is 100 Gausses to 30 teslas；
Depositing diamond/graphene/carbon nano-tube film：First, Buddha's warrior attendant is deposited in substrate surface using chemical vapour deposition technique
Stone, deposition parameter are：Carbonaceous gas mass flow percentage is 0.5-10%；Growth temperature is 600-1000 DEG C, and growth air pressure is
103-104Pa；Then, it is in diamond surface deposited graphite alkene film, deposition parameter：Carbonaceous gas mass flow percentage is 5-
80%；Growth temperature is 400-1200 DEG C, and growth air pressure is 5-105Pa；Plasma electric current density is 0-50mA/cm2；Deposition region
Middle magnetic field intensity is 100 Gausses to 30 teslas；Finally, graphenic surface using plating, chemical plating, chemical vapor deposition,
After a kind of method deposition nickel, copper, one kind of cobalt or composite catalytic layer in physical vapour deposition (PVD), deposition of carbon nanotubes woods, deposition
Parameter is：Carbonaceous gas mass flow percentage is 5-80%；Growth temperature is 400-1200 DEG C, and growth air pressure is 5-105Pa；
Plasma electric current density is 0-50mA/cm2；
The foam framework is selected from foam metal skeleton or foamed ceramics skeleton or foam carbon skeleton.
10. a kind of preparation method of foam framework enhancing metal-base composites according to claim 9, its feature exist
In：After the cleaning of foam framework substrate, drying, first using one in plating, chemical plating, chemical vapor deposition, physical vapour deposition (PVD)
Kind method deposits one kind or complex metal layer in nickel, copper, tungsten, molybdenum, titanium, silver, chromium on foam framework surface, then, is placed in and receives
In the suspension of meter Jing and micron diamond hybrid particles, after being heated to boiling, shake, be uniformly dispersed in ultrasonic wave, obtain
After a large amount of nanocrystalline and foam framework substrates of micron diamond particle are inlayed among to mesh；To foam framework using chemistry
Vapour deposition is in foam framework surface or diamond particle surfaces growth in situ strengthening layer.
11. a kind of preparation method of foam framework enhancing metal-base composites according to claim 9 or 10, its feature
It is：After strengthening layer surface and preparing one layer of modified layer, 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 chemical vapor deposition, physical vapour deposition (PVD) prepares modified layer on reinforcement surface.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610161232.4A CN105779804B (en) | 2016-03-21 | 2016-03-21 | A kind of foam framework structure enhancing metal-base composites and preparation method |
| PCT/CN2017/074397 WO2017161993A1 (en) | 2016-03-21 | 2017-02-22 | Foam skeleton reinforced composite, preparation method therefor, and application thereof |
| US16/086,608 US10995192B2 (en) | 2016-03-21 | 2017-02-22 | Composite material reinforced by foamed skeleton and preparation method and uses thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610161232.4A CN105779804B (en) | 2016-03-21 | 2016-03-21 | A kind of foam framework structure enhancing metal-base composites and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105779804A CN105779804A (en) | 2016-07-20 |
| CN105779804B true CN105779804B (en) | 2018-01-02 |
Family
ID=56394243
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610161232.4A Active CN105779804B (en) | 2016-03-21 | 2016-03-21 | A kind of foam framework structure enhancing metal-base composites and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105779804B (en) |
Families Citing this family (45)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106497522A (en) * | 2016-10-21 | 2017-03-15 | 中南大学 | A kind of foam diamond strengthens paraffin wax phase change energy storage material and preparation method |
| CN106637111B (en) * | 2016-10-21 | 2019-02-01 | 中南大学 | A kind of niobium base boron-doped diamond foam electrode and the preparation method and application thereof |
| WO2017161993A1 (en) * | 2016-03-21 | 2017-09-28 | 中南大学 | Foam skeleton reinforced composite, preparation method therefor, and application thereof |
| WO2018072367A1 (en) * | 2016-10-21 | 2018-04-26 | 中南大学 | Boron-doped diamond electrode and preparation method and application of same |
| CN106756316B (en) * | 2016-11-29 | 2019-06-14 | 宁波瑞铭机械有限公司 | A kind of sewing machine needle bar support body |
| CN106346100B (en) * | 2016-11-30 | 2019-02-19 | 哈尔滨工业大学 | A kind of method of carbon nanotube enhancing three-dimensional structure middle layer assistant brazing |
| CN106699185A (en) * | 2016-11-30 | 2017-05-24 | 潘云清 | Aluminum alloy composite material |
| CN106400062B (en) * | 2016-12-01 | 2018-07-31 | 贵州木易精细陶瓷有限责任公司 | Copper carbon composite and preparation method thereof and device |
| CN106884159B (en) * | 2017-01-16 | 2018-12-25 | 哈尔滨工业大学 | The method that carbon-coating coats the preparation method and its assistant brazing C/C composite material and metal of foam carbon/carbon-copper composite material |
| CN106893881B (en) * | 2017-03-28 | 2018-06-29 | 宜春学院 | A kind of method of zirconium oxide modified graphene enhancing magnesium-based composite material |
| CN106861596B (en) * | 2017-04-27 | 2019-05-17 | 山东金城石墨烯科技有限公司 | A kind of preparation method and applications of grapheme foam rectifying tower packing |
| CN108866369B (en) * | 2017-05-08 | 2020-03-17 | 清华大学 | Three-dimensional porous composite material |
| CN108872338B (en) * | 2017-05-08 | 2021-08-03 | 清华大学 | Biosensor microelectrode and biosensor |
| CN108878768B (en) * | 2017-05-08 | 2020-12-04 | 清华大学 | Lithium ion battery cathode and lithium ion battery |
| CN108878895B (en) * | 2017-05-08 | 2021-01-05 | 清华大学 | Fuel cell electrode and fuel cell |
| CN107217178A (en) * | 2017-05-13 | 2017-09-29 | 安徽省鸣新材料科技有限公司 | A kind of foamed aluminium material of high energy absorption ability |
| CN109030595B (en) * | 2017-06-09 | 2023-09-26 | 清华大学 | Biosensor electrode and biosensor |
| CN109309200B (en) | 2017-07-26 | 2021-02-26 | 中能中科（天津）新能源科技有限公司 | Metal lithium-framework carbon composite material with hydrophobic coating layer, and preparation method and application thereof |
| CN109309203A (en) | 2017-07-26 | 2019-02-05 | 中能中科（天津）新能源科技有限公司 | Nano carbon particle-stephanoporate framework composite material, its lithium metal compound, their preparation method and application |
| CN107552796B (en) * | 2017-09-26 | 2019-06-21 | 成都新柯力化工科技有限公司 | A method of foam metal is prepared by resin microsphere accumulation |
| CN107794399B (en) * | 2017-10-13 | 2022-03-15 | 浙江福达合金材料科技有限公司 | Preparation method of superfine high-dispersion silver-tungsten electrical contact material |
| CN107917160B (en) * | 2017-11-13 | 2019-08-20 | 宁波海瑞时新材料有限公司 | A kind of brake disc and preparation method thereof |
| CN108146232B (en) * | 2017-12-22 | 2021-03-26 | 赛克思液压科技股份有限公司 | Sealed oil tank |
| CN108554413B (en) * | 2018-04-11 | 2020-10-02 | 北京化工大学 | Three-dimensional multi-stage structure high-dispersion nickel-based electro-catalytic material and preparation method thereof |
| CN110396616B (en) * | 2018-04-25 | 2020-11-20 | 比亚迪股份有限公司 | Composite material and preparation method and application thereof |
| CN108796397A (en) * | 2018-07-11 | 2018-11-13 | 兰州交通大学 | A kind of preparation method of graphene/carbon SiClx/aluminium composite material |
| CN109274051B (en) * | 2018-08-28 | 2020-04-24 | 宁波盈泰电气有限公司 | Compact bus duct |
| CN112335344B (en) * | 2018-09-28 | 2024-02-09 | 株式会社Lg化学 | Composite material |
| CN111195723B (en) * | 2018-11-20 | 2022-05-27 | 有研工程技术研究院有限公司 | Design and preparation method of high-thermal-conductivity system with fractal structure of thermal-conductivity phase |
| CN109680257A (en) * | 2019-02-19 | 2019-04-26 | 中国铝业股份有限公司 | A kind of preparation method of nano material |
| CN110076325A (en) * | 2019-04-19 | 2019-08-02 | 苏州宏久航空防热材料科技有限公司 | A kind of carbon foam-silicon carbide-metallic composite preparation method |
| CN110358508B (en) * | 2019-08-02 | 2021-02-26 | 太原理工大学 | Diamond-containing composite heat dissipation material and preparation method thereof |
| CN111471978B (en) * | 2020-05-11 | 2023-02-21 | 中南大学 | High-volume diamond-reinforced metal-based composite material and preparation method and application thereof |
| CN111778506B (en) * | 2020-05-11 | 2023-10-03 | 中南大学 | Gradient boron doped diamond reinforced metal matrix composite material and preparation method and application thereof |
| CN111876625B (en) * | 2020-07-16 | 2021-07-20 | 陕西迈特瑞科技有限公司 | AlNMg composite material and preparation method thereof |
| CN112226704A (en) * | 2020-10-19 | 2021-01-15 | 西安工程大学 | Preparation method of whisker particle hybrid reinforced copper-based composite material |
| CN112897646B (en) * | 2021-01-19 | 2022-07-01 | 山东欣远新材料科技有限公司 | Preparation method of boron-doped diamond film electrode foam metal matrix |
| CN112919923B (en) * | 2021-01-21 | 2022-07-12 | 周煜 | Metal matrix composite material and preparation method and application thereof |
| CN112981443B (en) * | 2021-02-22 | 2022-04-19 | 吉林大学 | Foam nickel with nano silver film deposited on surface, preparation method and application thereof |
| CN115141964A (en) * | 2021-03-30 | 2022-10-04 | 西安邦导新材料有限公司 | High-thermal-conductivity copper-diamond electronic packaging material with double-through structure and preparation method thereof |
| CN113122757B (en) * | 2021-04-16 | 2022-05-17 | 绍兴恒驰材料科技有限公司 | Foam iron reinforced aluminum-based composite material with high-temperature wear resistance and preparation method thereof |
| CN114235923A (en) * | 2021-12-09 | 2022-03-25 | 清华大学 | Bioelectrochemical sensing electrode, device and electrode preparation method |
| CN114990487B (en) * | 2022-06-10 | 2023-05-05 | 吉林大学 | Boron fiber reinforced copper-based precursor wire, continuous boron fiber reinforced copper-based composite material, preparation method and application |
| CN117199601B (en) * | 2023-11-01 | 2024-01-23 | 深圳汇能储能材料工程研究中心有限公司 | Regeneration method of waste nickel-cobalt-manganese ternary cathode material and cathode material |
| CN117286364B (en) * | 2023-11-24 | 2024-04-12 | 中铝科学技术研究院有限公司 | Graphene reinforced metal matrix composite material with three-dimensional network structure and preparation method thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1480542A (en) * | 2002-09-02 | 2004-03-10 | 北京有色金属研究总院 | Porous body of composite metal and its preparing method |
| CN2698810Y (en) * | 2003-08-28 | 2005-05-11 | 北京有色金属研究总院 | Composite metal porous aluminium |
| JP2006169094A (en) * | 2004-11-16 | 2006-06-29 | Sumitomo Electric Ind Ltd | Diamond-coated porous composite substrate and liquid treatment apparatus and liquid treatment method using same |
| CN1896171A (en) * | 2006-04-05 | 2007-01-17 | 中国科学院金属研究所 | Bi-continuous-phase composite friction material of foaming silicon carbide/metal, its member and preparation |
| CN1986490A (en) * | 2005-12-23 | 2007-06-27 | 中国科学院金属研究所 | High strength and high toughness foamed SiC/Al material and its preparing method |
| CN1986491A (en) * | 2005-12-23 | 2007-06-27 | 中国科学院金属研究所 | High heat conductivity and high strength dense heterogeneous foamed SiC/Cu material and its preparing method |
| CN103434207A (en) * | 2013-08-19 | 2013-12-11 | 南京航空航天大学 | Foam metal-carbon nanotube composite material and preparation method thereof |
| CN103436939A (en) * | 2013-08-19 | 2013-12-11 | 南京航空航天大学 | Foam metal-graphene composite material and preparation method thereof |
| CN104962771A (en) * | 2015-05-25 | 2015-10-07 | 西安交通大学 | Directional porous SiC and diamond reinforced Al base composite material and preparation method thereof |
| CN104975200A (en) * | 2014-04-04 | 2015-10-14 | 中国科学院苏州纳米技术与纳米仿生研究所 | High-performance aluminum/carbon composite material and preparation method thereof |
| CN105112754A (en) * | 2015-10-12 | 2015-12-02 | 中南大学 | Metal-based composite material enhanced by three-dimensional networked diamond framework as well as preparation method |
-
2016
- 2016-03-21 CN CN201610161232.4A patent/CN105779804B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1480542A (en) * | 2002-09-02 | 2004-03-10 | 北京有色金属研究总院 | Porous body of composite metal and its preparing method |
| CN2698810Y (en) * | 2003-08-28 | 2005-05-11 | 北京有色金属研究总院 | Composite metal porous aluminium |
| JP2006169094A (en) * | 2004-11-16 | 2006-06-29 | Sumitomo Electric Ind Ltd | Diamond-coated porous composite substrate and liquid treatment apparatus and liquid treatment method using same |
| CN1986490A (en) * | 2005-12-23 | 2007-06-27 | 中国科学院金属研究所 | High strength and high toughness foamed SiC/Al material and its preparing method |
| CN1986491A (en) * | 2005-12-23 | 2007-06-27 | 中国科学院金属研究所 | High heat conductivity and high strength dense heterogeneous foamed SiC/Cu material and its preparing method |
| CN1896171A (en) * | 2006-04-05 | 2007-01-17 | 中国科学院金属研究所 | Bi-continuous-phase composite friction material of foaming silicon carbide/metal, its member and preparation |
| CN103434207A (en) * | 2013-08-19 | 2013-12-11 | 南京航空航天大学 | Foam metal-carbon nanotube composite material and preparation method thereof |
| CN103436939A (en) * | 2013-08-19 | 2013-12-11 | 南京航空航天大学 | Foam metal-graphene composite material and preparation method thereof |
| CN104975200A (en) * | 2014-04-04 | 2015-10-14 | 中国科学院苏州纳米技术与纳米仿生研究所 | High-performance aluminum/carbon composite material and preparation method thereof |
| CN104962771A (en) * | 2015-05-25 | 2015-10-07 | 西安交通大学 | Directional porous SiC and diamond reinforced Al base composite material and preparation method thereof |
| CN105112754A (en) * | 2015-10-12 | 2015-12-02 | 中南大学 | Metal-based composite material enhanced by three-dimensional networked diamond framework as well as preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105779804A (en) | 2016-07-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105779804B (en) | A kind of foam framework structure enhancing metal-base composites and preparation method | |
| CN105603265B (en) | Foamy graphite alkene skeleton reinforced aluminum matrix composites and preparation method thereof | |
| CN105671354B (en) | A kind of foam diamond framework reinforced aluminum matrix composites and preparation method thereof | |
| CN105603248B (en) | A kind of foamy graphite alkene skeleton enhancing Cu-base composites and preparation method | |
| CN105779805B (en) | Foam diamond framework strengthens Cu-base composites and preparation method | |
| WO2017161993A1 (en) | Foam skeleton reinforced composite, preparation method therefor, and application thereof | |
| CN105733192B (en) | A kind of foam framework enhancing polymer matrix composite and preparation method thereof | |
| Zhang et al. | Thermal conductivity enhancement of phase change materials with 3D porous diamond foam for thermal energy storage | |
| CN105112754B (en) | Three-dimensional network diamond framework strengthens metal-base composites and preparation method | |
| Zhang et al. | Construction of 3D interconnected diamond networks in Al-matrix composite for high-efficiency thermal management | |
| CN105803242B (en) | A kind of sheet couples enhancing composite and preparation method with wire Heat Conduction Material | |
| CN105818476A (en) | Surface-modification three-dimensional-network-carbon-fiber-reinforced composite material and preparing method | |
| CN105220049B (en) | A kind of lamellar diamond reinforced metal-base composite material and preparation method | |
| CN106497522A (en) | A kind of foam diamond strengthens paraffin wax phase change energy storage material and preparation method | |
| CN105755307A (en) | Reinforced composite adopting honeycomb structure and preparation method | |
| CN105733191A (en) | Different-dimensionality high-heat-conductivity material enhanced and polymer based composite and preparation method thereof | |
| CN113443928B (en) | Preparation method of zirconium and/or tungsten-based multiphase ceramic coating | |
| CN111471978B (en) | High-volume diamond-reinforced metal-based composite material and preparation method and application thereof | |
| CN107267984A (en) | The preparation method of diamond-coated tools | |
| CN107381555A (en) | A kind of three-dimensional grapheme of structure-controllable and its preparation method of composite | |
| CN107649688A (en) | A kind of diamond heat-conducting composite of easy processing and its preparation method and application | |
| CN105803241A (en) | Spiral-body-enhanced metal-based or polymer-based composite and preparation method | |
| CN113716552B (en) | Preparation method of highly-oriented high-thermal-conductivity graphene/copper composite material | |
| CN111778506A (en) | Gradient boron-doped diamond enhanced metal matrix composite material and preparation method and application thereof | |
| CN110241325A (en) | A kind of titanium fossil ink sheet reinforced aluminum matrix composites and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |