CN105733192A - Foam framework enhanced polymer composite material and preparation method thereof - Google Patents
Foam framework enhanced polymer composite material and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
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Abstract
Disclosed are a foam framework enhanced polymer composite material and a preparation method thereof. The composite material is composed of a foam framework, a surface strengthening material and a base material, or strengthening particles are added. The foam framework can be foam metal, foam ceramic or foam carbon, the surface strengthening material is one of or a combination of high-heat-conductivity materials like a diamond film, a graphene film and a carbon nano tube, the base material is a polymer material, and the strengthening particles are high-heat-conductivity diamond powder, graphene, the carbon nano tube, graphene coated diamond microspheres, carbon nano tube coated diamond microspheres or high-heat-conductivity ceramic particles improving mechanical strength of the composite material and lowering heat balance coefficient. With the help of high heat conductivity, high electroconductivity and excellent mechanical excellent of the foam framework with the surface modified, heat conductivity, electroconductivity and mechanical strength of the composite material are greatly improved when compared with conventional composite materials, and the composite material is a novel multifunctional composite material having a lot of potential.
Description
Technical field
The invention discloses a kind of foam framework and strengthen polymer matrix composite and preparation method thereof, belong to technical field of composite preparation.
Background technology
Along with the frequency of electronic device is more and more higher, power is increasing, and caloric value is more and more higher, proposes challenge to the performance of electronic package material and electronic substrate, and Development of New Generation height heat conduction encapsulating material has become as imperative research work.Existing most efficient method is to add high heat conduction inorganic filler in capsulation material, and existing many foreign study team obtain the thermal conductivity capsulation material more than 4W/m K, compares pottery and metal material yet suffers from sizable gap.Comprehensive existing research data, almost all of process is all the mode adopting material directly to mix filling, although the intrinsic thermal conductivity of packing material is significantly high, and some inorganic filler thermal conductivities even can reach the 10 of organic material4Times, but to the modified effect of organic material heat conductivility inconspicuous, it is typically only capable to reach tens to the hundred times of organic material.
It is that effective heat conduction network is difficult to be formed that conductive particle is filled into the greatest problem that polymer runs at random, therefore generally requires bigger loading, the heat conductivity of material can be made to have raising by a small margin, and last heat conductivity is far below pure conductive materials.The main cause causing this improved thermal conductivity poor effect is the high thermal contact resistance between particle.If composite can be formed between the conductive particle of these interpolations the network structure of three-dimensional communication, then its heat transfer efficiency will be improved largely.
Chinese invention patent CN102786756A discloses three-dimensional continuous graphite alkene net composites and preparation method thereof, but Graphene thickness thin (nanoscale), the scale of construction are little, therefore, single Graphene network is difficult to meet high-power, low thermal coefficient of expansion dissipation from electronic devices demand.Additionally, Graphene hardness is little, single Graphene network is difficult to the Effective Regulation to mechanical properties such as composite hardness, intensity, thermal coefficient of expansions.
Summary of the invention
It is an object of the invention to overcome the deficiency of prior art, it is provided that a kind of foam framework strengthens polymer matrix composite and preparation method thereof.The composite that the present invention prepares can intactly replicate the structure of foam metal, strengthening layer constitutes the entirety of a full-mesh in a seamless fashion, it is uniformly distributed in composite with the form of three-dimensional network, there is the continuous capacity of heat transmission of excellence, charge-conduction ability and extra-low density, be effectively improved the thermal conductivity of composite, conductivity and mechanical strength.
One foam framework of the present invention strengthens polymer matrix composite, and described composite includes foam framework, matrix material, and described foam framework substrate is selected from foam metal skeleton or foamed ceramics skeleton or foamy carbon skeleton；Described matrix material is selected from polymer.
One foam framework of the present invention strengthens polymer matrix composite, and described polymer is selected from thermoplastic polymer or thermosetting polymer；Described thermoplastic polymer one in polyethylene, polypropylene, polystyrene, polrvinyl chloride, politef, nylon, Merlon, polymethyl methacrylate, glycol ester, poly terephthalic acid, polyformaldehyde, polyamide, polysulfones；Described thermosetting polymer one in epoxy resin, phenolic resin, Lauxite, amino resins, melmac, unsaturated polyester resin, organic siliconresin, silicone rubber, expanded polystyrene (EPS), polyurethane.
One foam framework of the present invention strengthens polymer matrix composite, described foam metal skeleton one in nickel foam, foam copper, titanium foam, foam cobalt, foam tungsten, foamed molybdenum, foam chromium, foam iron-nickel, foamed aluminium；Described 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.
One foam framework of the present invention strengthens polymer matrix composite, and foam aperture is 0.01-10mm, percent opening 40-99.9%, and foam cells is uniformly distributed or random distribution；Foam framework is planar structure or 3-D solid structure.
One foam framework of the present invention strengthens polymer matrix composite, and described foam framework surface is provided with strengthening layer.
One foam framework of the present invention strengthens polymer matrix composite, described strengthening layer one in diamond film, graphene film, carbon nano-tube film, graphene coated diamond film, CNT cladding diamond film, carbon nano tube/graphene cladding diamond film.
One foam framework of the present invention strengthens polymer matrix composite, and in strengthening layer, graphene coated diamond film refers at diamond surface growth in situ Graphene, and Graphene is perpendicular to diamond surface and forms Graphene wall；
CNT cladding diamond film refers at diamond surface in-situ growing carbon nano tube, and CNT is perpendicular to diamond surface and forms CNT woods；
Graphene/carbon nano-tube film refers at graphenic surface in-situ growing carbon nano tube, and CNT is perpendicular to graphenic surface and forms CNT woods；
Carbon nano tube/graphene cladding diamond film refers at diamond surface growth in situ Graphene, CNT, and Graphene, CNT are perpendicular to diamond surface and form Graphene wall and CNT woods.
One foam framework of the present invention strengthens polymer matrix composite, has been also added with reinforcing particle in matrix material, reinforcing particle at least one in high heat conduction particle, hard abrasive particles, conductive particle；Described high heat conduction particle at least one in bortz powder, Graphene, CNT, graphene coated diamond microspheres, CNT cladding diamond microsphere, CNT coated graphite alkene；Hard abrasive particles is selected from bortz powder, SiC, TiC, TiN, AlN, Si3N4、Al2O3、BN、WC、MoC、Cr7C3In at least one；Conductive particle at least one in graphite, CNT, Graphene.
One foam framework of the present invention strengthens polymer matrix composite, and in composite, the volumn concentration of each component is: matrix material 10-95%, foam framework 5-80%, and reinforcing particle volume fraction is 0-30%.
One foam framework of the present invention strengthens polymer matrix composite, and in hardening constituent, strengthening layer volume fraction is 2-80%, and foam framework volume fraction is 0.1-20%.
One foam framework of the present invention strengthens polymer matrix composite, and in the base, foam framework strengthens with monomer or many volume arrays strengthen, and described many volume arrays strengthen and refer to that foam framework is distributed in matrix with the parallel distribution of lamellar or so that column is parallel.
The preparation method that a kind of foam framework of the present invention strengthens polymer matrix composite, is by after the cleaning of foam framework substrate, drying, mixes with polymer, reinforcing particle, coupling agent, antioxygen auxiliary agent and processing aid；Heat the mixture within the scope of more than melting point polymer, degradation temperature temperature below, by impregnating a kind of method molding in curing molding, injection moulding, compressing, injection mo(u)lding, rotation molding, extrusion moulding, laminated into type, flow casting molding, obtain foam framework and strengthen polymer matrix composite.
The preparation method that a kind of foam framework of the present invention strengthens polymer matrix composite, after foam framework cleaning, drying, adopt chemical vapour deposition (CVD) after foam framework surface in situ grows strengthening layer diamond film, graphene film, carbon nano-tube film, with polymer-matrix bluk recombination；Deposition parameter is:
Depositing diamond film: it is 0.5-10% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 600-1000 DEG C, grows air pressure 103-104Pa；
Deposited graphite alkene film: it is 0.5-80% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 400-1200 DEG C, grows air pressure 5-105Pa；
Deposition of carbon nanotubes film: it is 5-50% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 400-1300 DEG C, grows air pressure 103-105Pa；
Or
After the cleaning of foam framework substrate, drying, adopt chemical vapour deposition (CVD) after foam framework superficial growth strengthening layer diamond/graphene film, diamond/carbon nanotube films, graphene/carbon nano-tube film, diamond/graphene/carbon nano-tube film, with polymer-matrix bluk recombination；
Deposition process applies plasma asistance growth on foam framework substrate, and by adding magnetic field bottom substrate plasma confinement on the nearly surface of foam framework, the strengthening plasma bombardment to foam framework surface, improves chemical vapour deposition (CVD) speed and controls deposit growth direction；Depositing operation is:
Deposited graphite alkene cladding diamond:
First, adopting chemical vapour deposition technique at substrate surface depositing diamond, deposition parameter is: it is 0.5-10.0% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 600-1000 DEG C, and growth air pressure is 103-104Pa；Then, then at diamond surface deposited graphite alkene wall, Graphene is perpendicular to diamond surface growth, forms Graphene wall, and deposition parameter is: it is 0.5-80% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 400-1200 DEG C, and growth air pressure is 5-105Pa；Plasma electric current density 0-50mA/cm2；In deposition region, magnetic field intensity is 100 Gausses to 30 teslas；
Deposition of carbon nanotubes cladding diamond:
First, adopting chemical vapour deposition technique at substrate surface depositing diamond, deposition parameter is: it is 0.5-10.0% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 600-1000 DEG C, and growth air pressure is 103-104Pa；Then, a kind of method in plating, chemical plating, evaporation, magnetron sputtering, chemical vapour deposition (CVD), physical vapour deposition (PVD) is adopted to deposit nickel, copper, the one of cobalt or composite catalytic layer at deposition surface at diamond surface；Deposition of carbon nanotubes again, deposition parameter is: it is 5-50% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 400-1300 DEG C, and growth air pressure is 103-105Pa；Plasma electric current density 0-30mA/cm2；In deposition region, magnetic field intensity is 100 Gausses to 30 teslas；
Deposition of carbon nanotubes/graphene coated diamond:
First, adopting chemical vapour deposition technique at substrate surface depositing diamond, deposition parameter is: it is 0.5-10.0% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 600-1000 DEG C, and growth air pressure is 103-104Pa；Then, a kind of method in plating, chemical plating, evaporation, magnetron sputtering, chemical vapour deposition (CVD), physical vapour deposition (PVD) is adopted to deposit nickel, copper, the one of cobalt or composite catalytic layer at deposition surface in diamond surface deposition；Again deposition of carbon nanotubes woods, Graphene wall；CNT woods deposition parameter is: it is 5-50% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 400-1300 DEG C, and growth air pressure is 103-105Pa；Plasma electric current density 0-30mA/cm2；In deposition region, magnetic field intensity is 100 Gausses to 30 teslas；Graphene wall deposition parameter is: it is 0.5-80% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 400-1200 DEG C, and growth air pressure is 5-105Pa；Plasma electric current density 0-50mA/cm2；In deposition region, magnetic field intensity is 100 Gausses to 30 teslas；
Deposited graphite alkene/carbon nano-tube film:
First, adopting chemical vapour deposition technique at substrate surface deposited graphite alkene wall, deposition parameter is: it is 0.5-80% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 400-1200 DEG C, and growth air pressure is 0.5-105Pa；Then, a kind of method in plating, chemical plating, evaporation, magnetron sputtering, chemical vapour deposition (CVD), physical vapour deposition (PVD) is adopted to deposit nickel, copper, the one of cobalt or composite catalytic layer at deposition surface on Graphene wall surface at diamond surface；Deposition of carbon nanotubes again, deposition parameter is: it is 5-50% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 400-1300 DEG C, grows air pressure 103-105Pa；Plasma electric current density 0-30mA/cm2；In deposition region, magnetic field intensity is 100 Gausses to 30 teslas.
The preparation method that a kind of foam framework of the present invention strengthens polymer matrix composite, foam framework substrate cleans, after drying, first adopt plating, chemical plating, evaporation, magnetron sputtering, chemical vapour deposition (CVD), a kind of method in physical vapour deposition (PVD) deposits nickel on foam framework surface, copper, tungsten, molybdenum, titanium, silver, one in chromium or complex metal layer, then, it is placed in nanocrystalline and the suspension of micron diamond hybrid particles, heating is to boiling, shake in ultrasound wave, it is uniformly dispersed, after obtaining inlaying in the middle of mesh nanocrystalline in a large number and the foam framework substrate of micron diamond granule；Adopt chemical vapour deposition (CVD) at foam framework surface or diamond particle surfaces growth in situ strengthening layer foam framework.
Diamond is one of material that in nature, thermal conductivity is the highest (room temperature is up to 2200W/mK), and its thermal coefficient of expansion and density are only 0.8 × 10 simultaneously-6/ K and 3.52g/cm3, and there is ultrahigh hardness characteristic, therefore, diamond/polymer matrix composite has the mechanical properties such as good heat conduction, impact resistance.
Chemical vapour deposition (CVD) (CVD) diamond film can realize the preparation of big thickness (micron order or grade), diamond membrane with large area.Additionally, cvd diamond is in deposition process, it is also possible to carry out boron doping, by regulating and controlling boron doped concentration, it is possible to the electric conductivity of regulation and control diamond, pass through heavy doping, it might even be possible to reach superconductivity.Therefore, diamond and polymer-matrix bluk recombination can realize highly thermally conductive performance, height is tough, the excellent combination property of high connductivity, low thermal coefficient of expansion etc..
The present invention selects the foam metal of easily prepared and seamless link or foamed ceramics or foamy carbon skeleton as substrate, CVD technology is utilized to prepare high heat-conductive diamond rete on its surface, construct high heat-conductive diamond three-dimensional network skeleton, again by itself and polymer-matrix bluk recombination, high heat-conductive diamond and polymer is made to form the logical three-dimensional network interpenetrating structure of doubly-linked, enhancing and matrix is made all to keep continuous distribution in space, constitute continuous print passage of heat, produce parallel heat conduction, thus weakening the compound interface negative effect to material thermal property.At the same time it can also be one or more interpolation in high heat-conducting ceramic granule such as SiC, AlN etc. of high thermal conductive diamond stone powder, Graphene, CNT or reduction thermal balance coefficient, it is achieved the further lifting of calorifics and mechanical property.
The composite that the present invention prepares can intactly replicate the structure of foam metal, strengthening layer constitutes the entirety of a full-mesh in a seamless fashion, it is uniformly distributed in composite with the form of three-dimensional network, there is the continuous capacity of heat transmission of excellence, charge-conduction ability and extra-low density, the thermal conductivity of composite, conductivity and mechanical strength conventional composite materials of comparing is made to have very big raising, would is that the very potential Multifunction composite of one, it is possible to be widely used in national economy fields such as heat management, electronics, the energy, traffic.
Accompanying drawing explanation
Accompanying drawing 1 is the structural representation that in the present invention, foam framework strengthens with monomer in the base.
Accompanying drawing 2 is the structural representation that in the present invention, foam framework strengthens with the parallel distribution of lamellar in the base.
Accompanying drawing 3a, Fig. 3 b is the structural representation that in the present invention, foam framework strengthens with the parallel distribution of column in the base.
Detailed description of the invention
Technical scheme is further described below by specific embodiment.
The embodiment of the present invention is undertaken by following technique or step:
(1) foam framework substrate put into carry out ultrasonic vibration cleaning in ethanol, take out dry stand-by；
(2) adopting a kind of method in plating, chemical plating, evaporation, magnetron sputtering, chemical vapour deposition (CVD), physical vapour deposition (PVD) to prepare intermediate layer on foam framework surface, described intermediate layer includes the one in nickel, copper, tungsten, molybdenum, titanium, silver, chromium or complex metal layer；
(3) by nanocrystalline and micron diamond hybrid particles, foam framework substrate, solvent mixing, heating is to seething with excitement, then, be placed in high-power ultrasonics shake 30min, be uniformly dispersed after, take out foam framework substrate to dry, obtain in the middle of mesh, inlaying nanocrystalline in a large number and micron diamond granule foam framework substrate；
(4) adopting hot-wire chemical gas-phase deposition at the strengthening layer of metal substrate surface deposition densification continuously, described strengthening layer is at least one in diamond film, graphene film, carbon nano-tube film, graphene coated diamond, CNT cladding diamond, CNT coated graphite alkene, carbon nano tube/graphene cladding diamond；
(5) the laying mode in the base of the foam framework reinforcement after surface-modified process can be divided into following three kinds of modes: a. foam framework is as overall enhanced body and matrix compound, and composite is integrally formed high heat conduction strengthening layer/polymer network interpenetrating structure；B. foam framework is as flake reinforcement body and matrix compound, and reinforcement arragement direction in the base is parallel arrangement；C. foam framework is as strip reinforcement and matrix compound, and reinforcement arragement direction in the base is parallel arrangement；
(6) technology such as dipping solidification are adopted will to have foam framework and the polymer-matrix bluk recombination of strengthening layer.
Embodiment one: (diamond)
Foam diamond framework reinforced epoxy composite, adopting aperture in this example is that 0.2mm foam copper is as substrate, foam diamond reinforcement accounts for composite volume fraction 20%, it is first according to step (1) foam copper three-dimensional network substrate is carried out, adopts magnetron sputtering technique to be that the molybdenum film of 50nm is as intermediate layer at foam copper three-dimensional network skeleton surface deposit thickness by step (2) afterwards；Then according to step (3) obtains inlaying nanocrystalline in a large number and micron diamond granule foam framework substrate in the middle of mesh；Step (4) adopts HF CVD depositing diamond film, deposition process parameters: heated filament distance 6mm, substrate temperature 800 DEG C, hot-wire temperature 2200 DEG C, deposition pressure 3KPa, CH4/H2Volume flow ratio 1:99, controlling diamond film thickness is 160 μm, namely obtains foam copper substrate diamond three-dimensional network skeleton；Afterwards according to step (5) with matrix material compound before, adopt vacuum evaporation method foam diamond framework surface in situ be deposited with layer of metal tungsten film carry out surface modification, tungsten film thickness is 200nm；(6) the foam diamond framework of plated surface tungsten is placed in mould, is adopted as flake reinforcement body and be arranged in parallel in the base and carry out compound；(7) at 80 DEG C, bisphenol F epoxy resin precursor liquid (diaminodiphenyl-methane (DDM) is firming agent) is instilled according to volume ratio 1:1 toward foam diamond framework, make it permeate and fully infiltrate foam diamond framework, obtain mixture, above-mentioned mixture is carried out application of vacuum 2h, get rid of bubble therein, resin precursor liquid is made to be filled into better in the hole of diamond network, gradient increased temperature solidifies, 2h it is incubated at 100 DEG C, then 160 DEG C are risen to, insulation 4h, finally it is down to room temperature and obtains that there is foam diamond framework enhancing bisphenol F epoxy resin composite, heat conductivity respectively 349W/ (m K).
Embodiment two: (Graphene wall)
Foamy graphite alkene skeleton strengthens silicon rubber composite material, adopting aperture in this example is that 2mm porous ceramics aluminium oxide is as substrate, foamy graphite alkene reinforcement accounts for composite volume fraction 10%, it is first according to step (1) foamed alumina three-dimensional network substrate is carried out, adopts the technology of magnetron sputtering to be that the tungsten film of 200nm is as intermediate layer at foamed alumina three-dimensional network skeleton surface deposit thickness by step (2) afterwards；Then according to step (3) obtains inlaying nanocrystalline in a large number and micron diamond granule foam framework substrate in the middle of mesh；(4) utilize plasma-assisted chemical vapour deposition at substrate surface growth in situ Graphene, deposition process applies plasma asistance growth on foam framework substrate, and by adding magnetic field bottom substrate plasma confinement on the nearly surface of foam framework, the strengthening plasma bombardment to foam framework surface, Graphene is made to be perpendicular to diamond surface growth, obtain the foam framework of the amount of growing up Graphene wall of looking unfamiliar in mesh containing a large amount of graphene coated diamond height heat conduction particles and Skeleton Table, deposition parameter is: substrate temperature is 800 DEG C, deposition pressure is 5.0kPa, CH4/H2Volume flow ratio 30:70, plasma electric current density 5mA/cm2, in deposition region, magnetic field intensity is 500 Gausses, and sedimentation time is 1h；The lower orientation of growth controlling Graphene of effect under extra electric field simultaneously, makes them vertical and substrate surface forms Graphene wall, obtain foamed alumina substrate Graphene three-dimensional network skeleton；Afterwards according to step (5) with matrix material compound before, adopt magnetron sputtering method carry out surface modification at foamy graphite alkene skeleton electroplating surface layer of metal tungsten-copper alloy film, tungsten-copper alloy film thickness is 200nm；(6) being placed in mould by the foamy graphite alkene skeleton of surface tungsten-copper alloy film, the laying mode being adopted as overall enhanced body carries out compound with matrix；(7) instill silicone rubber precursor solution according to volume ratio 1:2 so that it is infiltration fully infiltration foamy graphite alkene skeleton, obtain mixture；Above-mentioned mixture is carried out application of vacuum 2h, remove solvent therein and bubble, silicone rubber precursor liquid is made to be filled into better in the hole of diamond network, heating is to 80 DEG C, and heat preservation solidification 4h, obtain foamy graphite alkene skeleton and strengthen silicon rubber composite material, heat conductivity respectively 278W/ (m K).
Embodiment three: (graphene coated diamond)
Foam diamond framework strengthens poly-methyl methacrylate vinegar (PMMA) composite, adopting aperture in this example is that the nickel foam of 0.3mm is as substrate, foam diamond reinforcement accounts for composite volume fraction 30%, it is first according to step (1) foam copper three-dimensional network substrate is carried out, it is first according to step (1) and nickel foam three-dimensional network substrate (aperture is 0.05mm) surface is carried out pretreatment, adopt the method for evaporation to be that the chromium film of 300nm is as intermediate layer at nickel foam three-dimensional network skeleton surface deposit thickness by step (2) afterwards；Then according to step (3) obtains inlaying nanocrystalline in a large number and micron diamond granule foam framework substrate in the middle of mesh；(4) HF CVD depositing diamond film, deposition process parameters: heated filament distance 6mm, substrate temperature 850 DEG C, hot-wire temperature 2200 DEG C, deposition pressure 3KPa, CH are adopted4/H2Volume flow ratio 1:99, controlling diamond film thickness is 280 μm, obtain nickel foam substrate diamond three-dimensional network skeleton, utilize plasma-assisted chemical vapour deposition at diamond surface growth in situ Graphene at diamond surface again, deposition process applies plasma asistance growth on foam framework substrate, and by adding magnetic field bottom substrate plasma confinement on the nearly surface of foam framework, the strengthening plasma bombardment to foam framework surface, Graphene is made to be perpendicular to diamond surface growth, obtain the foam framework of the amount of growing up Graphene wall of looking unfamiliar in mesh containing a large amount of graphene coated diamond height heat conduction particles and Skeleton Table, deposition parameter is: substrate temperature is 800 DEG C, deposition pressure is 5.0kPa, CH4/H2Volume flow ratio 25:75, plasma electric current density 15mA/cm2, in deposition region, magnetic field intensity is 500 Gausses, sedimentation time 30min；The lower orientation of growth controlling Graphene of effect under extra electric field simultaneously, makes them vertical and diamond surface forms Graphene wall, obtain the strengthening layer of graphene coated diamond film, obtain nickel foam substrate graphene coated diamond three-dimensional network skeleton；Afterwards according to step (5) with matrix material compound before, adopt electric plating method carry out surface modification at foamy graphite alkene skeleton electroplating surface layer of metal chromium film, chromium film thickness is 500nm；(6) chrome faced foamy graphite alkene skeleton is placed in mould, is adopted as strip reinforcement and be arranged in parallel in the base and carry out compound；(7) instill the chloroformic solution of PMMA according to volume ratio 1:5 so that it is infiltration fully infiltration foam diamond framework, obtain mixture；Above-mentioned mixture is placed in vacuum drying oven and steams chloroform solvent in 60 DEG C of vacuum drying 24h, it is then heated to 110 DEG C, after insulation 1h, is down to room temperature, finally give foam diamond framework reinforced PMMA composite, heat conductivity respectively 408W/ (m K).
Embodiment four: CNT/diamond
Foam diamond/carbon nanotube framework reinforced epoxy composite, adopting aperture in this example is that 1mm foam tungsten is as substrate, foam diamond reinforcement accounts for composite volume fraction 50%, it is first according to step (1) foam tungsten three-dimensional network substrate is carried out, it is not added with intermediate layer afterwards, directly utilizes chemical vapour deposition (CVD) growth in situ graphene film；Then according to step (3) obtains inlaying nanocrystalline in a large number and micron diamond granule foam framework substrate in the middle of mesh；Step (4) adopts HF CVD depositing diamond film, deposition process parameters: heated filament distance 6mm, substrate temperature 900 DEG C, hot-wire temperature 2300 DEG C, deposition pressure 3KPa, sedimentation time 200 hours, CH4/H2Volume flow ratio 1:99, obtain diamond film thickness 500 μm, namely foam tungsten substrate diamond three-dimensional network skeleton is obtained, magnetron sputtering deposits one layer of nickel at diamond surface again, then utilize plasma-assisted chemical vapour deposition at nickel surface catalytic growth CNT, the lower orientation of growth controlling CNT of effect under extra electric field simultaneously, make them vertical and graphenic surface forms CNT woods, obtaining the strengthening layer of CNT coated graphite alkene film, deposition parameter is: methane, hydrogen quality flow percentage are 25:75；Growth temperature is 600 DEG C, grows air pressure 3000Pa；Plasma electric current density 5mA/cm2；In deposition region, magnetic field intensity is 350 Gausses, obtains foam tungsten substrate CNT cladding diamond three-dimensional network skeleton；Afterwards according to step (5) with matrix material compound before, adopt electric plating method at the foam diamond framework electroplating surface layer of metal copper film of the CNT woods array with setting, copper film thickness is 500nm；(6) being placed in mould by the foam diamond framework of copper coating, the laying mode being adopted as overall enhanced body carries out compound with matrix；(7) at 80 DEG C, bisphenol F epoxy resin precursor liquid (diaminodiphenyl-methane (DDM) is firming agent) is instilled according to volume ratio 1:1 toward foam diamond framework, make it permeate and fully infiltrate foam diamond framework, obtain mixture, above-mentioned mixture is carried out application of vacuum 2h, get rid of bubble therein, resin precursor liquid is made to be filled into better in the hole of diamond network, gradient increased temperature solidifies, 2h it is incubated at 100 DEG C, then 160 DEG C are risen to, insulation 4h, finally it is down to room temperature and obtains that there is foam diamond/carbon nanotube framework enhancing bisphenol F epoxy resin composite, heat conductivity respectively 536W/ (m K).
Embodiment five: carbon nano tube/graphene
Foamy graphite alkene/CNT skeleton strengthens silicon rubber composite material, adopting aperture in this example is that 1mm foam ferronickel is as substrate, foamy graphite alkene reinforcement accounts for composite volume fraction 7%, it is first according to step (1) foam ferronickel three-dimensional network substrate is carried out, it is not added with intermediate layer afterwards, directly utilizes chemical vapour deposition (CVD) growth in situ graphene film；Then according to step (3) obtains inlaying nanocrystalline in a large number and micron diamond granule foam framework substrate in the middle of mesh；(4) hot-wall cvd deposited graphite alkene film is adopted, particularly as follows: heat in the atmosphere of H2 and Ar to 950 DEG C of (H in heating process2With Ar flow velocity respectively 200 and 500mL/min, programming rate is 33 DEG C/min), treat that furnace temperature rises to 950 DEG C of after-baking 10min；Heat treatment passes into CH after completing4、H2Mixing gas (gas flow rate respectively methane 5mL/min, hydrogen 200mL/min and argon 500mL/min) with Ar, start to grow Graphene, 100 DEG C/min of rate of cooling, sedimentation time 2 hours, namely obtain foam ferronickel substrate Graphene three-dimensional network skeleton；Magnetron sputtering deposits one layer of nickel at graphenic surface again, then utilize plasma-assisted chemical vapour deposition at graphenic surface catalytic growth CNT, the lower orientation of growth controlling CNT of effect under extra electric field simultaneously, make them vertical and graphenic surface forms CNT woods, obtaining the strengthening layer of CNT coated graphite alkene film, deposition parameter is: methane, hydrogen mass flow percentage ratio is 8%；Growth temperature is 600 DEG C, grows air pressure 3000Pa；Plasma electric current density 5mA/cm2；In deposition region, magnetic field intensity is 500 Gausses, sedimentation time, 30min, obtains foam ferronickel substrate CNT coated graphite alkene three-dimensional network skeleton；Afterwards according to step (5) with matrix material compound before, adopt vacuum evaporation method foamy graphite alkene skeleton surface be deposited with layer of metal titanium film carry out surface modification, titanium film thickness is 500nm；(6) being placed in mould by the nanotube coated graphite alkene foam framework of ti coat on diamond, the laying mode being adopted as overall enhanced body carries out compound with matrix；(7) dipping solidification is adopted to carry out compound: a) to prepare silicone rubber precursor liquid: weigh 209 silicone rubber presomas, it is mixed by the mass ratio of 10:1 with the firming agent being furnished with when buying, gained mixture and organic solvent acetic acid ethyl ester more in mass ratio 1:9 mix, it is vigorously agitated again about 5 minutes, mixture is carried out evacuation process and within 5 minutes, removes wherein bubble, the final acetic acid ethyl ester solution obtaining silicone rubber presoma；B) mixing: diamond three-dimensional network skeleton is put in mould, then according to volume ratio 1:2 instills silicone rubber precursor solution so that it is infiltration fully infiltration diamond macroscopic body, obtains mixture；C) application of vacuum: above-mentioned mixture is carried out application of vacuum 2h, removes solvent therein and bubble, makes silicone rubber precursor liquid be filled into better in the hole of diamond network；D) heating is to 80 DEG C, and heat preservation solidification 4h, obtains foamy graphite alkene/CNT skeleton and strengthens silicon rubber composite material, and the thermal conductivity of composite is 254W/mK.
Embodiment six: foam diamond/graphene/carbon nano-tube skeleton reinforced PMMA composite
Foam diamond/graphene/carbon nano-tube skeleton strengthens poly-methyl methacrylate vinegar (PMMA) composite, adopting aperture in this example is that 0.3mm foam copper is as substrate, foam diamond reinforcement accounts for composite volume fraction 40%, it is first according to step (1) foam copper three-dimensional network substrate is carried out, adopts magnetron sputtering technique to be that the molybdenum film of 50nm is as intermediate layer at foam copper three-dimensional network skeleton surface deposit thickness by step (2) afterwards；Then according to step (3) obtains inlaying nanocrystalline in a large number and micron diamond granule foam framework substrate in the middle of mesh；Step (4) adopts HF CVD depositing diamond film, deposition process parameters: heated filament distance 6mm, substrate temperature 800 DEG C, hot-wire temperature 2200 DEG C, deposition pressure 3KPa, CH4/H2Volume flow ratio 1:99, obtains diamond film thickness 800 μm by controlling sedimentation time, namely obtains foam copper substrate diamond three-dimensional network skeleton；Adopt hot-wall cvd at diamond surface in-situ deposition graphene film again, particularly as follows: at H2With the atmosphere of Ar heats to 950 DEG C (in heating processes H2 and Ar flow velocity respectively 200 and 500mL/min, programming rate is 33 DEG C/min), treat that furnace temperature rises to 950 DEG C of after-baking 10min；Heat treatment passes into CH after completing4、H2Mixing gas (gas flow rate respectively methane 5mL/min, hydrogen 200mL/min and argon 500mL/min) with Ar, start to grow Graphene, 100 DEG C/min of rate of cooling, growth time is 3 hours, namely obtains foam copper diamond/Graphene three-dimensional network skeleton；Magnetron sputtering deposits one layer of nickel at graphenic surface again, then utilize plasma-assisted chemical vapour deposition at graphenic surface catalytic growth CNT, the lower orientation of growth controlling CNT of effect under extra electric field simultaneously, make them vertical and graphenic surface forms CNT woods, obtaining foam copper diamond/graphene/carbon nano-tube three-dimensional network skeleton, deposition parameter is: methane, hydrogen mass flow percentage ratio is 10%；Growth temperature is 600 DEG C, grows air pressure 3000Pa；Plasma electric current density 5mA/cm2；In deposition region, magnetic field intensity is 500 Gausses, growth time 2 hours.Afterwards according to step (5) with matrix material compound before, adopt vacuum evaporation method foam diamond framework surface in situ be deposited with layer of metal tungsten film carry out surface modification, tungsten film thickness is 150nm；(6) the foam diamond framework of plated surface tungsten is placed in mould, is adopted as flake reinforcement body and be arranged in parallel in the base and carry out compound；(7) instill the chloroformic solution of PMMA according to volume ratio 1:5 so that it is infiltration fully infiltration foam diamond framework, obtain mixture；Above-mentioned mixture is placed in vacuum drying oven and steams chloroform solvent in 60 DEG C of vacuum drying 24h, it is then heated to 110 DEG C, after insulation 1h, it is down to room temperature, finally give foam diamond/graphene/carbon nano-tube skeleton reinforced PMMA composite, heat conductivity respectively 567W/ (m K).
The thermal conductivity obtained from above example and mechanical performance data, foam framework prepared by the present invention strengthens the thermal conductivity of polymer matrix composite and obtains tremendous increase, thermal conductivity is up to 567W/mK, the composite enhancing that the present invention prepares keeps continuous distribution with matrix in three dimensions, form network blackboard, can effectively weaken the compound interface impact on material thermal property, neither reduce the good plasticity and toughness of polymeric matrix, enhancing can be made to coordinate again as a whole, play the heat transfer efficiency of reinforcement to greatest extent, the thermal conductivity making composite conventional composite materials of comparing with mechanical strength has very big raising, combination property is apparently higher than traditional polymer matrix composite, it it is the very potential multifunctional composite of one.
Claims (13)
1. a foam framework strengthens polymer matrix composite, it is characterised in that described composite includes foam framework, matrix material, and described foam framework substrate is selected from foam metal skeleton or foamed ceramics skeleton or foamy carbon skeleton；Described matrix material is selected from polymer.
2. a kind of foam framework structure reinforced polymer based composites according to claim 1, it is characterised in that described polymer is selected from thermoplastic polymer or thermosetting polymer；Described thermoplastic polymer one in polyethylene, polypropylene, polystyrene, polrvinyl chloride, politef, nylon, Merlon, polymethyl methacrylate, glycol ester, poly terephthalic acid, polyformaldehyde, polyamide, polysulfones；Described thermosetting polymer one in epoxy resin, phenolic resin, Lauxite, amino resins, melmac, unsaturated polyester resin, organic siliconresin, silicone rubber, expanded polystyrene (EPS), polyurethane.
3. a kind of foam framework structure reinforced polymer based composites according to claim 1, it is characterized in that, described foam metal skeleton one in nickel foam, foam copper, titanium foam, foam cobalt, foam tungsten, foamed molybdenum, foam chromium, foam iron-nickel, foamed aluminium；Described 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.
4. a kind of foam framework structure reinforced polymer based composites according to claim 3, it is characterised in that foam aperture is 0.01-10mm, percent opening 40-99.9%, and foam cells is uniformly distributed or random distribution；Foam framework is planar structure or 3-D solid structure.
5. a kind of foam framework structure reinforced polymer based composites according to claim 1, it is characterised in that described foam framework surface is provided with strengthening layer.
6. a kind of foam framework structure reinforced polymer based composites according to claim 5, it is characterized in that, described strengthening layer one in diamond film, graphene film, carbon nano-tube film, graphene coated diamond film, CNT cladding diamond film, carbon nano tube/graphene cladding diamond film.
7. foam framework structure reinforced polymer based composites according to claim 6, it is characterised in that in strengthening layer, graphene coated diamond film refers at diamond surface growth in situ Graphene, and Graphene is perpendicular to diamond surface and forms Graphene wall；
CNT cladding diamond film refers at diamond surface in-situ growing carbon nano tube, and CNT is perpendicular to diamond surface and forms CNT woods；
Graphene/carbon nano-tube film refers at graphenic surface in-situ growing carbon nano tube, and CNT is perpendicular to graphenic surface and forms CNT woods；
Carbon nano tube/graphene cladding diamond film refers at diamond surface growth in situ Graphene, CNT, and Graphene, CNT are perpendicular to diamond surface and form Graphene wall and CNT woods.
8. the foam framework structure reinforced polymer based composites according to claim 1-7 any one, it is characterized in that, matrix material is also added with reinforcing particle, reinforcing particle at least one in high heat conduction particle, hard abrasive particles, conductive particle；Described high heat conduction particle at least one in bortz powder, Graphene, CNT, graphene coated diamond microspheres, CNT cladding diamond microsphere, CNT coated graphite alkene；Hard abrasive particles is selected from bortz powder, SiC, TiC, TiN, AlN, Si3N4、Al2O3、BN、WC、MoC、Cr7C3In at least one；Conductive particle at least one in graphite, CNT, Graphene.
9. foam framework structure reinforced polymer based composites according to claim 8, it is characterised in that in composite, the volumn concentration of each component is: matrix material 10-95%, foam framework 5-80%, and reinforcing particle volume fraction is 0-30%.
10. foam framework according to claim 7 strengthens polymer matrix composite, it is characterized in that, in the base, foam framework strengthens with monomer or many volume arrays strengthen, and described many volume arrays strengthen and refer to that foam framework is distributed in matrix with the parallel distribution of lamellar or so that column is parallel.
11. the preparation method that foam framework strengthens polymer matrix composite, it is by after the cleaning of foam framework substrate, drying, mixes with polymer, reinforcing particle, coupling agent, antioxygen auxiliary agent and processing aid；Heat the mixture within the scope of more than melting point polymer, degradation temperature temperature below, by impregnating a kind of method molding in curing molding, injection moulding, compressing, injection mo(u)lding, rotation molding, extrusion moulding, laminated into type, flow casting molding, obtain foam framework and strengthen polymer matrix composite.
12. the preparation method that a kind of foam framework according to claim 11 strengthens polymer matrix composite, it is characterised in that:
After foam framework cleaning, drying, adopt chemical vapour deposition (CVD) after foam framework superficial growth strengthening layer diamond film, graphene film, carbon nano-tube film, with polymer-matrix bluk recombination；Deposition parameter is:
Depositing diamond film: it is 0.5-10% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 600-1000 DEG C, and growth air pressure is 103-104Pa；
Deposited graphite alkene film: it is 0.5-80% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 400-1200 DEG C, and growth air pressure is 5-105Pa；
Deposition of carbon nanotubes film: it is 5-50% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 400-1300 DEG C, and growth air pressure is 103-105Pa；
Or
After the cleaning of foam framework substrate, drying, adopt chemical vapour deposition (CVD) after foam framework superficial growth strengthening layer diamond/graphene film, diamond/carbon nanotube films, graphene/carbon nano-tube film, diamond/graphene/carbon nano-tube film, with polymer-matrix bluk recombination；
Deposition process applies plasma asistance growth on foam framework substrate, and by adding magnetic field bottom substrate plasma confinement on the nearly surface of foam framework, the strengthening plasma bombardment to foam framework surface, improves chemical vapour deposition (CVD) speed and controls deposit growth direction；Depositing operation is:
Deposited graphite alkene cladding diamond:
First, adopting chemical vapour deposition technique at substrate surface depositing diamond, deposition parameter is: it is 0.5-10.0% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 600-1000 DEG C, and growth air pressure is 103-104Pa；Then, then at diamond surface deposited graphite alkene wall, Graphene is perpendicular to diamond surface growth, forms Graphene wall, and deposition parameter is: it is 0.5-80% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 400-1200 DEG C, and growth air pressure is 5-105Pa；Plasma electric current density is 0-50mA/cm2；In deposition region, magnetic field intensity is 100 Gausses to 30 teslas；
Deposition of carbon nanotubes cladding diamond:
First, adopting chemical vapour deposition technique at substrate surface depositing diamond, deposition parameter is: it is 0.5-10.0% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 600-1000 DEG C, and growth air pressure is 103-104Pa；Then, a kind of method in plating, chemical plating, evaporation, magnetron sputtering, chemical vapour deposition (CVD), physical vapour deposition (PVD) is adopted to deposit nickel, copper, the one of cobalt or composite catalytic layer at deposition surface at diamond surface；Deposition of carbon nanotubes again, deposition parameter is: it is 5-50% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 400-1300 DEG C, and growth air pressure is 103-105Pa；Plasma electric current density is 0-30mA/cm2；In deposition region, magnetic field intensity is 100 Gausses to 30 teslas；
Deposition of carbon nanotubes/graphene coated diamond:
First, adopting chemical vapour deposition technique at substrate surface depositing diamond, deposition parameter is: it is 0.5-10% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 600-1000 DEG C, and growth air pressure is 103-104Pa；Then, a kind of method in plating, chemical plating, evaporation, magnetron sputtering, chemical vapour deposition (CVD), physical vapour deposition (PVD) is adopted to deposit nickel, copper, the one of cobalt or composite catalytic layer at deposition surface in diamond surface deposition；Again deposition of carbon nanotubes woods, Graphene wall；CNT woods deposition parameter is: it is 5-50% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 400-1300 DEG C, and growth air pressure is 103-105Pa；Plasma electric current density 0-30mA/cm2；In deposition region, magnetic field intensity is 100 Gausses to 30 teslas；Graphene wall deposition parameter is: it is 0.5-80% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 400-1200 DEG C, and growth air pressure is 5-105Pa；Plasma electric current density 0-50mA/cm2；In deposition region, magnetic field intensity is 100 Gausses to 30 teslas；
Deposited graphite alkene/carbon nano-tube film:
First, adopting chemical vapour deposition technique at substrate surface deposited graphite alkene wall, deposition parameter is: it is 0.5-80% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 400-1200 DEG C, and growth air pressure is 5-105Pa；Then, a kind of method in plating, chemical plating, evaporation, magnetron sputtering, chemical vapour deposition (CVD), physical vapour deposition (PVD) is adopted to deposit nickel, copper, the one of cobalt or composite catalytic layer at deposition surface on Graphene wall surface at diamond surface；Deposition of carbon nanotubes again, deposition parameter is: it is 5-50% that carbonaceous gas accounts for all gas mass flow percentage ratio in stove；Growth temperature is 400-1300 DEG C, and growth air pressure is 103-105Pa；Plasma electric current density is 0-30mA/cm2；In deposition region, magnetic field intensity is 100 Gausses to 30 teslas.
13. the preparation method that a kind of foam framework according to claim 12 strengthens polymer matrix composite, it is characterized in that: foam framework substrate cleans, after drying, first adopt plating, chemical plating, evaporation, magnetron sputtering, chemical vapour deposition (CVD), a kind of method in physical vapour deposition (PVD) deposits nickel on foam framework surface, copper, tungsten, molybdenum, titanium, silver, one in chromium or complex metal layer, then, it is placed in nanocrystalline and the suspension of micron diamond hybrid particles, heating is to boiling, shake in ultrasound wave, it is uniformly dispersed, after obtaining inlaying in the middle of mesh nanocrystalline in a large number and the foam framework substrate of micron diamond granule；Adopt chemical vapour deposition (CVD) at foam framework surface or diamond particle surfaces growth in situ strengthening layer foam framework.
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