CN105220049A - A kind of sheet diamond reinforced metal-base composite material and preparation method - Google Patents
A kind of sheet diamond reinforced metal-base composite material and preparation method Download PDFInfo
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Abstract
A kind of sheet diamond reinforced metal-base composite material and preparation method, described matrix material is provided with diamond wafers in matrix metal, and diamond wafers and matrix metal are metallurgical binding; Its preparation method, adopt a kind of technique in founding, infiltration, cold-rolled sintered, hot pressed sintering, plasma agglomeration, by matrix metal or the matrix metal and the diamond wafers compound that comprise surface modified diamond particle, obtain the sheet diamond reinforced metal-base composite material of diamond wafers and matrix metal metallurgical binding.The present invention is by the sheet diamond framework that distributes in metallic matrix, and in metallic matrix, add a certain amount of diamond particles, diamond wafers adopts the sandwich clamping graphene layer between underlying metal film and facing metal film to form to carry out surface modification, this matrix material is made to have excellent heat conductivility, this matrix material can be used as Electronic Packaging and heat sink material etc., solves the encapsulation problem of high temperature, high frequency, high-power electronic device.
Description
Technical field
The invention discloses a kind of preparation method of sheet diamond reinforced metal-base composite material, belong to composite diamond technical field of material.
Background technology
Along with developing rapidly of hyundai electronics information technology, integrated level and the power consumption of electronic devices and components improve constantly, and heat dissipation problem becomes one of key factor affecting electronic product reliability.The thermal conductivity of traditional electronic package material has been difficult to the needs meeting modern electronic devices heat radiation task.Meanwhile, electronic product is also had higher requirement to electronic package material to miniaturization, lightweight, complicated development.
In recent years, take diamond as the metal-base composites of wild phase, by means of the thermal conductivity of its superelevation, adjustable thermal expansivity, being described as is forth generation New Materials for Electric Packing.But from existing market situation, do not obtain large-scale application.
The greatest problem that diamond particles enhancing metal-base composites runs into is the difficulty of the formation of effective heat conduction network, and be confined to interface resistance high between diamond particles, therefore often need to fill a large amount of diamond particles, material thermal conductivity can be made to have improve by a small margin, and last thermal conductivity is well below adamantine heat conductivility.Such as: the thermal conductivity of bortz powder/carbon/carbon-copper composite material mostly is 200 ~ 600W/ (mK), far below diamond.According to heat conduction theory, there are series and parallel connections two kinds of distributions between matrix and reinforcement in matrix material, diamond particle reinforced copper-based composite material belongs to series model, and bortz powder content in the composite needs very high (usually more than 70%) could obtain higher heat conductivility.2008, the people such as Russia Ekimov reach the limiting condition of 90 ~ 95% at diamond particles massfraction under, High Temperature High Pressure sintering has prepared a kind of novel bortz powder/carbon/carbon-copper composite material, the matrix of this composite shape matl is bortz powder (particle size range is 0 ~ 500 μm), the continuous skeleton structure that copper makes diamond be formed at high temperature under high pressure as binding agent, the thermal conductivity of this matrix material reaches as high as 920W/ (mK).This series model is described, even if diamond content is up to more than 90%, because intercrystalline exists copper Binder Phase, between diamond, continuous passage of heat cannot be formed, make its thermal conductivity far below diamond.
Germany scientist ThomasHutsch has been set forth in the literature and has been mixed with copper by graphite flakes by powder metallurgic method, uses plasma discharge sintering to prepare the method for graphite flakes/carbon/carbon-copper composite material.Prepared matrix material is anisotropy, has shown higher thermal conductivity in the plane in vertical pressure direction.When the volume fraction of graphite flakes is 50%, the thermal conductivity of prepared matrix material in the plane in vertical pressure direction is 550W/ (mK).WeidenfellerB etc. find when studying thermal conductance filler filled polypropylene, and the thermal conductivity of matrix material is relevant with the distribution of filler.Stratiform mica is easily directed, and when its content is 30%, the thermal conductivity of matrix material can be increased to 2.7W/mk fast by 0.27W/mk.The matrix material thermal conductivity of doped graphene only has 0.4W/mk, and the continuous print graphene sheet layer thermal conductivity utilizing Raman spectrometer to record can reach 5000W/mk.
Research shows, the thermal conductivity of High Quality Diamond Film on its lamella direction can reach 1000 ~ 2000W/ (mK), lower thermal expansivity (1.0 ~ 2.0) × 10
-6k.Therefore diamond wafers is used to be hopeful as the metallic matrix matrix material carried out prepared by compound of wild phase and high thermal conductance the thermal conductivity obtaining superelevation.Chemistry for gas phase depositing diamond film is grown continuously by carbonaceous active group to form, and combines closely between diamond crystals.If adopt cvd diamond thin slice and high-thermal conductive metal compound to prepare diamond/metal-base composites, cvd diamond thin slice will form continuous print passage of heat, produce parallel heat conduction.The matrix material of this parallel-connection structure can eliminate thermal resistance interface when traditional diamond/metal-base composites conducts heat in a large number, is expected to significantly improve its thermal conductivity.
The present inventor seminar patent of invention CN102244051A in earlier stage discloses a kind of high-performance directional heat conduction copper-base diamond composite material and preparation method thereof: 1) insert in the columnar through holes of Copper substrate by diamond rod, and make Copper substrate generation viscous deformation by extruding, thus make copper and diamond rod contact coupling completely; 2) diamond rod is inserted in the columnar through holes of Copper substrate, then by electro-deposition techniques at copper sheet along diamond rod direction deposited copper, make the complete cladding diamond rod of copper, contact coupling complete in diamond.The standby copper base diamond matrix material of this legal system has good directed heat conductivility, but due to wettability extreme difference between its diamond rod and matrix metal, two-phase interface combines not tight, interface between diamond rod and matrix metal defines very large thermal resistance, and its thermal conductivity need further to optimize.
Summary of the invention
First technical problem to be solved by this invention is to provide a kind of sheet diamond reinforced metal-base composite material that can realize super-high heat-conductive.
Second technical problem to be solved by this invention provides a kind of preparation method realizing this super-high heat-conductive sheet diamond reinforced metal-base composite material.
For solving above-mentioned first technical problem, a kind of sheet diamond reinforced metal-base composite material of the present invention, described matrix material is provided with diamond wafers in matrix metal, and diamond wafers and matrix metal are metallurgical binding.
A kind of sheet diamond reinforced metal-base composite material of the present invention, described diamond wafers is arranged in parallel in matrix metal, and relative position is evenly arranged or random arrangement.
A kind of sheet diamond reinforced metal-base composite material of the present invention, described diamond wafers be selected from tabular, wave tabular, drum any one; Described diamond wafers is atresia thin slice or porous web plate.
A kind of sheet diamond reinforced metal-base composite material of the present invention, described diamond wafers is that self-supporting diamond thin slice or the lining comprising substrate support diamond wafers;
The substrate single or double that described lining supports diamond wafers is coated with diamond film fine and close continuously, substrate is metal, metal substrate cross sectional thickness is 0.005 ~ 1mm, the one that sheet metal substrate material is selected from a kind of in tungsten, molybdenum, copper, titanium, silver, gold or is selected from tungstenalloy, molybdenum alloy, copper alloy, titanium alloy, silver alloys, au-alloy.
A kind of sheet diamond reinforced metal-base composite material of the present invention, described diamond wafers is surface modified diamond thin slice; Described surface modified diamond thin slice is that diamond wafers surface is provided with composite membrane, and the effect of composite membrane is the wettability improving diamond and matrix metal; Described composite membrane between underlying metal film and facing metal film, has clamped graphene layer form; Described graphene film adopts chemical gaseous phase depositing process preparation, described underlying metal film or facing metal film are selected from the one in Ni film, Cu film, NiCu alloy film, wherein: underlying metal film thickness is 30 ~ 100nm, facing metal film thickness is 3 ~ 10 μm, and graphene layer thickness is 0 ~ 10nm.
A kind of sheet diamond reinforced metal-base composite material of the present invention, described matrix metal is high conduction light heat metallic substance, specifically refers to the one in a kind of or aluminium alloy in metallic aluminium, copper, silver, copper alloy, silver alloys.
A kind of sheet diamond reinforced metal-base composite material of the present invention, in described metallic matrix, be also distributed with diamond particles, diamond particles granularity is 1 ~ 200 μm; Described diamond particles and metallic matrix are metallurgical binding;
Described diamond particles is surface modified diamond, and the percentage composition that described diamond particles accounts for total composite volume is 0 ~ 50%; Described surface modified diamond is at diamond particle surfaces metal lining rete; Described metallic diaphragm is the metallic film good with diamond wettability, is specifically selected from a kind of metallic film in chromium metal, tungsten, molybdenum, nickel, titanium; Or
Described metallic diaphragm is composite membrane, and described composite membrane is made up of bottom and surface layer, and described bottom is the metallic film good with diamond wettability, is specifically selected from a kind of metallic film in chromium metal, tungsten, molybdenum, nickel, titanium; Described surface layer is metallic membrane, and according to metallic matrix and underlying metal characteristic, the metallic membrane forming surface layer selects unitary film or multilayer film; The material of metallic membrane is selected from and the unitary film of at least one metal in matrix metal and/or the good vanadium metal of underlying metal wettability, tungsten, copper, titanium, molybdenum, nickel, cobalt, aluminium, silver or multilayer film.
For solving above-mentioned second technical problem, first the arrangement of surface modified diamond thin slice is the stochastic distribution that is parallel to each other or equally distributed diamond framework by the preparation method of a kind of sheet diamond reinforced metal-base composite material of the present invention; Then adopt a kind of technique in founding, infiltration, cold-rolled sintered, hot pressed sintering, plasma agglomeration, by matrix metal and diamond framework compound, obtain the sheet diamond reinforced metal-base composite material of diamond wafers and matrix metal metallurgical binding; Or
Adopt a kind of technique in founding, infiltration, cold-rolled sintered, hot pressed sintering, plasma agglomeration, to matrix metal and the diamond framework compound of surface modified diamond particle be comprised, obtain the sheet diamond reinforced metal-base composite material of diamond wafers and matrix metal metallurgical binding.
The preparation method of a kind of sheet diamond reinforced metal-base composite material of the present invention, surface modified diamond thin slice is that self-supporting diamond sheet or the lining comprising substrate support diamond chip;
Described self-supporting diamond sheet adopts chemical gaseous phase depositing process at a side depositing diamond of sheet metal substrate, and after etched substrate, obtain self-supporting diamond sheet, self-supporting diamond sheet thickness is 0.005 ~ 1.0mm; Or
Described lining supports diamond chip and adopts chemical gaseous phase depositing process at a side of sheet metal substrate or both sides depositing diamond, obtains lining and supports diamond chip, and it is 0.005 ~ 1.0mm that lining supports diamond film layer thickness in diamond chip;
Described chemical gaseous phase depositing process is selected from the one in heated filament auxiliary law, microwave plasma enhancing method, flame combustion process, direct-current discharge method, DC arc plasma jet, low pressure radio frequency method, normal-pressure radio-frequency method, electron cyclotron resonace method.
The preparation method of a kind of sheet diamond reinforced metal-base composite material of the present invention, described lining supports diamond chip, and before chemical vapour deposition diamond, carry out pre-treatment to metal substrate surface, pretreatment technology is:
For the sheet metal substrate that can form strong carbide, after the oil removing of sheet metal substrate, scale removal, electrochemical etching, be directly soaked in fine diamond powder suspension liquid, carry out the pre-treatment of ultrasonic oscillation plantation seed crystal;
The sheet metal substrate material that can form strong carbide is selected from the one in W, Mo, Ti, Cr, Ta, Si, Nb; Or
For the sheet metal substrate that can not form strong carbide, for improving the interface cohesion of diamond and core, after the oil removing of sheet metal substrate, scale removal, electrochemical etching, adopt physical vapor deposition or electro-deposition techniques can form the film (as films such as W, Mo, Ti, Cr, Ta, Si, Nb) of strong carbide in metal substrate surface preparation, and select individual layer, multilayer or alloy film according to the characteristic of substrate, then, be directly soaked in fine diamond powder suspension liquid and carry out the pre-treatment of ultrasonic oscillation plantation seed crystal;
The metal substrate material that can not form strong carbide is selected from the one in Cu, Ag, Au, Ni, Al, Co.
The preparation method of a kind of sheet diamond reinforced metal-base composite material of the present invention, surface modification lamellar gold hard rock and surface modified diamond particle adopt at least one plating mode in magnetron sputtering, vacuum-evaporation, plating, electroless plating to realize surface modification.
The preparation method of a kind of sheet diamond reinforced metal-base composite material of the present invention, described founding is by containing modification diamond particles or do not put into graphite jig in the lump containing the matrix metal of modification diamond particles and diamond framework, then put it in vacuum melting furnace or atmosphere protection smelting furnace and be heated to 400 ~ 1300 DEG C of meltings of more than matrix metal fusing point, cooling and demolding, obtains sheet diamond reinforced metal-base composite material; Or
First matrix metal is heated in crucible more than matrix metal fusing point 400 ~ 1300 DEG C, obtain melting matrix metal, directly diamond framework leaching is placed in liquid matrix metal, or after adding modification diamond particles in melting matrix metal, stirring, diamond framework leaching is placed in liquid matrix metal, cooling, obtains sheet diamond reinforced metal-base composite material.
The preparation method of a kind of sheet diamond reinforced metal-base composite material of the present invention, described infiltration is that diamond framework is placed in infiltration mould, carry out preheating, under vacuum or protective atmosphere environment, to modification diamond particles be contained or not pressurize infiltration in infiltration mould containing the matrix metal of the molten state of modification diamond particles, compound is carried out with diamond framework, the preheating temperature of diamond framework controls 400 ~ 1100 DEG C of scopes, infiltration pressure is 8 ~ 30MPa, infiltrating temperature to control more than matrix metal fusing point 400 ~ 1300 DEG C, infiltration soaking time is 0.5 ~ 4 hour, obtain sheet diamond reinforced metal-base composite material.
The preparation method of a kind of sheet diamond reinforced metal-base composite material of the present invention; describedly cold-rolled sinteredly be by matrix metal powder or add in diamond framework containing the matrix metal powder of modification diamond particles; put into mould coldmoulding; pressure is 400 ~ 800Mpa; then sinter under vacuum or protective atmosphere; sintering temperature to control near matrix metal fusing point 375 ~ 1083 DEG C on the lower side; the sintered heat insulating time is 0.5 ~ 4 hour; cooling and demolding, obtains sheet diamond reinforced metal-base composite material.
The preparation method of a kind of sheet diamond reinforced metal-base composite material of the present invention; described hot pressed sintering is by matrix metal powder or adds in diamond framework containing the matrix metal powder of modification diamond particles; put into vacuum hotpressing stove or protective atmosphere hot pressing furnace hot pressed sintering; pressure is 30 ~ 200Mpa; sintering temperature to control near matrix metal fusing point 375 ~ 1083 DEG C on the lower side; the sintered heat insulating time is 0.5 ~ 4 hour, and cooling and demolding obtains sheet diamond reinforced metal-base composite material.，
The preparation method of a kind of sheet diamond reinforced metal-base composite material of the present invention, described plasma agglomeration is by matrix metal powder or adds in diamond framework containing the matrix metal powder of modification diamond particles, after compacting, after compacting, put into plasma agglomeration stove, vacuum, pressing pressure is sinter under 30 ~ 70MPa, sintering temperature to control below matrix metal fusing point 375 ~ 1080 DEG C, and the sintered heat insulating time is 5 ~ 30 minutes.
Contriver according to occurring in nature " water pump " to the effect of current, dexterously " heat pump " concept is incorporated in diamond/metal composite, by diamond chip of arranging in a metal, make diamond chip and metal realize metallurgical junction to merge and form parallel-connection structure, as " water pump ", hot-fluid is constantly extracted out, heat in surrounding metal matrix is constantly sucked in the diamond chip of nearest neighbour and is quickly drawn out.The present invention is based on above-mentioned thinking, select diamond wafers, diamond particles and high heat conduction metal matrix compound, each diamond wafers is all equivalent to countless diamond wire laid out in parallel, and therefore, adamantine volume content increases greatly; Prepare diamond thin at sheet metal substrate surface, belong to one-body molded, preparation efficiency is higher; Can according to practical situation, design heat transfer efficiency and heat conduction direction, handiness is high; Sheet metal substrate can be designed to the mesh of different-shape, then at the continuous fine and close diamond film of its surface deposition, namely obtains being with meshed diamond wafers, thus improve the combination of diamond chip and metallic matrix further; By at the good metallic film of diamond wafers coating surface one or more layers and diamond wettability, and then there is at its most top layer preparation and metal base one or more layers film of good wettability, again by different sintering and densification process, the metal of diamond surface or carbide etc. are to diamond and metallic matrix generation interfacial diffusion or reaction, compound interface bonding strength can be made obviously to be strengthened, and the thermal conductivity of material can obtain improvement in various degree; In matrix material preparation process, diamond particles after surface modification treatment is joined in high-thermal conductive metal material (as aluminium, copper, silver and alloy thereof etc.), by densified sintering product metallization processes, make its Dispersed precipitate in metallic matrix, the thermal conductivity that sheet diamond framework strengthens metal-base composites can be promoted further.In other words, this patent no matter in composite structure and composition, or has all made huge innovation and improvement in preparation method.
Compared with the prior art, a kind of sheet diamond reinforced metal-base composite material, select diamond wafers, diamond particles and high heat conduction metal matrix compound, there is following advantage:
(1) each diamond wafers is all equivalent to countless diamond wire laid out in parallel, and therefore, adamantine volume content increases greatly;
(2) prepare diamond thin at sheet metal substrate surface, belong to one-body molded, preparation efficiency is higher;
(3) can according to practical situation, design heat transfer efficiency and heat conduction direction, handiness is high;
(4) sheet metal substrate can be designed to the mesh of different-shape, then at the continuous fine and close diamond film of its surface deposition, namely obtains being with meshed diamond wafers, thus improve the combination of diamond chip and metallic matrix further;
(5) diamond wafers adopts the sandwich clamping high thermal conductivity graphene layer between underlying metal film and facing metal film to form to carry out surface modification, make this matrix material have the heat conductivility of excellence;
(6) in matrix material preparation process, diamond particles after surface modification treatment is joined in high-thermal conductive metal material (as aluminium, copper, silver and alloy thereof etc.), by densified sintering product metallization processes, make its Dispersed precipitate in metallic matrix, the thermal conductivity that sheet diamond framework strengthens metal-base composites can be promoted further.
Accompanying drawing explanation
Accompanying drawing 1a is the even arrangement schematic diagram of tabular two dimension diamond wafers.
Accompanying drawing 1b is tabular two dimension diamond wafers random arrangement structural representation.
Accompanying drawing 2a is diamond chip after lining support single sided deposition surface modification.
Accompanying drawing 2b is diamond chip after lining support double-sided deposition surface modification.
Accompanying drawing 2c is diamond chip after self-supporting surface modification.
Accompanying drawing 3 is porous web plate metal substrat structure schematic diagram.
Accompanying drawing 4 is wave-shape board structural metal substrate schematic cross-sectional view.
Accompanying drawing 5 is round tube type porous web plate metal substrate schematic diagram.
Accompanying drawing 6a is cylindric concentric shafts structural porous web plate metal substrate schematic cross-sectional view.
Accompanying drawing 6b is drum concentric shafts structural porous web plate metal substrate schematic cross-sectional view.
Accompanying drawing 6c is another kind of drum concentric shafts structural porous web plate metal substrate schematic cross-sectional view.
Accompanying drawing 7a, accompanying drawing 7b, accompanying drawing 7c are the diamond thin preparation method schematic diagram with cylindrical metal substrate in embodiment 2.
In accompanying drawing 2,1---metal substrate, 2---diamond film, 3---surface modification of metals film;
In accompanying drawing 7,4---cylindrical metal substrate, 5---linear pattern heated filament, 6---spiral type heated filament or be the hot paper tinsel of tubular;
Accompanying drawing 7 (b) shows, and adopts hot-wire chemical gas-phase deposition technology at cylindric outer substrate surface and internal surface depositing high-quality diamond, makes diamond cover all surface inside and outside substrate, forms continuous print diamond film.Metal substrate can carry out continuous rotation.
Embodiment
Technical scheme of the present invention is further described below by specific embodiment.
The embodiment of the present invention is undertaken by following technique or step:
(1) process in early stage is carried out to sheet metal substrate
Process according to the following steps: (1) uses 800# abrasive paper for metallograph to polish, and then carries out ultrasonic vibration cleaning in acetone; (2) then, metal substrate is soaked in fine diamond powder acetone suspension liquid ultrasonic vibration process 30min;
(2) adopt hot-wire chemical gas-phase deposition at the continuous fine and close diamond film of metal substrate surface deposition
Adopt the various chemical gaseous phase depositing process such as hot wire process, microwave plasma method, flame method, direct-current discharge method, DC arc plasma jet, low pressure radio frequency method, normal-pressure radio-frequency, electron cyclotron resonace method at two-dimensional metallic substrate surface depositing diamond, can obtain lining and support diamond chip, diamond film layer thickness is 0.005 ~ 0.5mm.After etching lining supports the flat substrates of diamond chip, sheet self-supporting diamond sheet can be obtained.
(3) self-supporting diamond sheet supports diamond chip surface modification treatment with lining
Any one plating mode in magnetron sputtering, vacuum-evaporation, electroless plating is adopted to prepare Ni film/Cu film (thickness is 30 ~ 100nm/3 ~ 10 μm) or NiCu alloy film (thickness is 3 ~ 10 μm) at sheet diamond surface; And then adopting chemical vapour deposition to prepare graphene film at Ni film/Cu film or NiCu alloy film surface, thickness is 1 ~ 50 μm.
(4) arrangement of modified diamond chip
Can stochastic distribution, can also evenly arrange
(5) high heat conduction metal-based filling and densification process
Thermal treatment or the densification processes such as hot pressed sintering, infiltration or founding
Embodiment one:
Select thickness be the tungsten paper tinsel of 0.05mm as metal substrate, first according to step (1) to metal substrate surface carry out early stage process; Then HF CVD depositing diamond film is adopted according to step (2), deposition process parameters: heated filament distance 6mm, substrate temperature 800 DEG C, hot-wire temperature 2200 DEG C, deposition pressure 3KPa, depositing time 40 hours, CH
4/ H
2volume flow ratio 1:99, obtains diamond film thickness 60 μm, namely obtains diamond wafers; (3) adopt magnetically controlled sputter method first to sputter layer of metal Ni film on belt carcass diamond wafers surface, sputtering power is 150W, pressure 0.4Pa, substrate temperature 300 DEG C, and argon flow amount 20sccm, Ni film thickness is 1.0 μm; Adopt chemical vapour deposition technique at Ni film surface deposition one deck graphene film again, thicknesses of layers 0.34nm; And then adopting electroplating technology at graphenic surface deposition layer of metal Cu film, thickness is about 5 μm; (4) the diamond wafers orientation of plated surface Ni/ Graphene/Cu be evenly arranged in mould, arrangement distance 1mm, arrangement mode is as Fig. 1 (a); Namely lamellar gold hard rock array backbone is obtained; (5) lamellar gold hard rock array backbone is fixedly put into mould, simultaneously by fine aluminium heat fused to 800 DEG C in crucible, melt is poured in mould, hydropress is adopted to exert pressure the pressure of 60Mpa, aluminum or aluminum alloy melt infiltration is forced to enter the gap location of diamond wire in skeleton, keep pressure 15 seconds, cooling and demolding, take out matrix material.The performance test results: thermal conductivity is 582W/ (mK).
Embodiment two:
Select thickness be the Copper Foil of 0.05mm as metal substrate, and be rolled into the cylindrical shape that diameter is 12mm, 10mm, 8mm.First according to step (1), process in early stage is carried out to metal substrate surface; Then adopt HF CVD to be deposited on each barrel-shaped metal substrate surfaces externally and internally depositing diamond film according to step (2), heated filament arrangement mode as shown in Figure 7.Deposition process parameters: heated filament distance 6mm, substrate temperature 850 DEG C, hot-wire temperature 2200 DEG C, deposition pressure 3KPa, depositing time 50 hours, CH4/H2 volume flow ratio 1:99, obtains diamond film thickness 100 μm, namely obtains band metal substrate diamond chip; (3) adopt magnetically controlled sputter method at diamond chip surfaces externally and internally sputtering layer of metal Cu film, sputtering power is 150W, pressure 0.4Pa, substrate temperature 300 DEG C, and argon flow amount 20sccm, Cu film thickness is 1.0 μm; Adopt chemical vapour deposition technique at Cu film surface deposition one deck graphene film again, thickness is about 1nm; And then adopting electroplating technology to deposit one deck Cu film at graphenic surface, thickness is about 10 μm; (4) be evenly arranged in mould with the mode orientation of concentric shafts by the diamond chip of the cylindrical shape of the band metal substrate of three plated surface Cu/ Graphene/Cu, arrangement distance 2mm, namely obtains lamellar gold hard rock array backbone; (5) lamellar gold hard rock array backbone is fixedly put into mould; 2 of diamond framework volume times of Al-Si alloys are placed on above skeleton; wherein the mass content of Si is 15%; then process furnace is put into; 900 DEG C of insulation 30min under high pure nitrogen protection; can obtain sheet diamond reinforced metal-base composite material, heat conductivity is 765W/ (mK).
Embodiment three:
Select thickness be 1.5mm silicon chip as flat substrates, first according to step (1) to silicon substrate surface carry out early stage process; Then HF CVD depositing diamond film is adopted according to step (2), deposition process parameters: heated filament distance 6mm, substrate temperature 900 DEG C, hot-wire temperature 2300 DEG C, deposition pressure 3KPa, depositing time 300 hours, CH
4/ H
2volume flow ratio 3:97, obtains diamond film thickness 600 μm, after etching sheet silicon base material, obtains sheet self-supporting diamond; (3) adopt magnetically controlled sputter method first to sputter layer of metal Ni film on diamond chip surface, sputtering power is 200W, pressure 0.3Pa, substrate temperature 350 DEG C, and argon flow amount 50sccm, Ni film thickness is 0.5 μm; Adopt chemical vapour deposition technique to prepare graphene film on Ni film surface again, thickness is 0.34nm, and then adopts electro-deposition techniques to prepare one deck Cu film at Graphene film surface, thicknesses of layers 5 μm; (4) the full diamond chip orientation of plated surface Ni/ Graphene/Cu is evenly arranged in mould, arranging distance 2mm; (5) gap location of diamond chip is filled pure aluminium powder and bortz powder mixed powder (Al powder purity is 99.9%, diamond particles pattern rule, particle size: 80 ~ 100 μm), diamond particles adopts vacuum evaporation technique to prepare Mo/Cu composite film on surface, molybdenum evaporation current is 32A, pressure 0.1Pa, substrate temperature 400 DEG C, chromium film thickness is 0.3 μm, the copper film of vacuum-evaporation layer of metal again, evaporation current is 30A, pressure 0.1Pa, substrate temperature 300 DEG C, thicknesses of layers 1.0 μm; Then sample is carried out hot pressed sintering, obtained lamellar gold hard rock reinforced aluminum matrix composites: sintering temperature is 650 DEG C, sintering pressure 60MPa, soaking time 90min, and atmosphere is vacuum.The most high heat conductance of the height adopting this technique obtained directed heat conduction sheet diamond framework reinforced aluminum matrix composites is respectively 1096W/ (mK).
The data obtained from above embodiment, the thermal conductivity of sheet diamond reinforced metal-base composite material obtained in this patent can reach 1096W/ (mK), strengthens the thermal conductivity (100 ~ 600W/ (mK)) of metal-base composites apparently higher than traditional diamond particles.
Claims (11)
1. a sheet diamond reinforced metal-base composite material, is characterized in that: described matrix material is provided with diamond wafers in matrix metal, and diamond wafers and matrix metal are metallurgical binding.
2. a kind of sheet diamond reinforced metal-base composite material according to claim 1, it is characterized in that: described diamond wafers is arranged in parallel in matrix metal, relative position is evenly arranged or random arrangement.
3. a kind of sheet diamond reinforced metal-base composite material according to claim 2, is characterized in that: described diamond wafers be selected from tabular, wave tabular, drum any one; Described diamond wafers is atresia thin slice or porous web plate.
4. a kind of sheet diamond reinforced metal-base composite material according to claim 3, is characterized in that: described diamond wafers is that self-supporting diamond thin slice or the lining comprising substrate support diamond wafers;
The substrate single or double that described lining supports diamond wafers is coated with diamond film fine and close continuously, substrate is metal, metal substrate cross sectional thickness is 0.005 ~ 1mm, the one that sheet metal substrate material is selected from a kind of in tungsten, molybdenum, copper, titanium, silver, gold or is selected from tungstenalloy, molybdenum alloy, copper alloy, titanium alloy, silver alloys, au-alloy.
5. a kind of sheet diamond reinforced metal-base composite material according to claim 1-4 any one, is characterized in that: described diamond wafers is surface modified diamond thin slice; Described surface modified diamond thin slice is that diamond wafers surface is provided with composite membrane; Described composite membrane between underlying metal film and facing metal film, has clamped graphene layer form; Described graphene film adopts chemical gaseous phase depositing process preparation, described underlying metal film or facing metal film are selected from the one in Ni film, Cu film, NiCu alloy film, wherein: underlying metal film thickness is 30 ~ 100nm, facing metal film thickness is 3 ~ 10 μm, and graphene layer thickness is 0 ~ 10nm.
6. a kind of sheet diamond reinforced metal-base composite material according to claim 5, it is characterized in that: described matrix metal is high conduction light heat metallic substance, specifically refer to the one in a kind of or aluminium alloy in metallic aluminium, copper, silver, copper alloy, silver alloys.
7. a kind of sheet diamond reinforced metal-base composite material according to claim 6, is characterized in that: in described metallic matrix, be also distributed with diamond particles, and diamond particles granularity is 1 ~ 200 μm; Described diamond particles and metallic matrix are metallurgical binding; Described diamond particles is surface modified diamond, and the percentage composition that described diamond particles accounts for total composite volume is 0 ~ 50%; Described surface modified diamond is at diamond particle surfaces metal lining rete; Described metallic diaphragm is the metallic film good with diamond wettability, is specifically selected from a kind of metallic film in chromium metal, tungsten, molybdenum, nickel, titanium; Or
Described metallic diaphragm is composite membrane, and described composite membrane is made up of bottom and surface layer, and described bottom is the metallic film good with diamond wettability, is specifically selected from a kind of metallic film in chromium metal, tungsten, molybdenum, nickel, titanium; Described surface layer is metallic membrane, and according to metallic matrix and underlying metal characteristic, the metallic membrane forming surface layer selects unitary film or multilayer film; The material of metallic membrane is selected from and the unitary film of at least one metal in matrix metal and/or the good vanadium metal of underlying metal wettability, tungsten, copper, titanium, molybdenum, nickel, cobalt, aluminium, silver or multilayer film.
8. a preparation method for sheet diamond reinforced metal-base composite material, is characterized in that: be first the stochastic distribution that is parallel to each other or equally distributed diamond framework by the arrangement of surface modified diamond thin slice; Then adopt a kind of technique in founding, infiltration, cold-rolled sintered, hot pressed sintering, plasma agglomeration, by matrix metal and diamond framework compound, obtain the sheet diamond reinforced metal-base composite material of diamond wafers and matrix metal metallurgical binding; Or
Adopt a kind of technique in founding, infiltration, cold-rolled sintered, hot pressed sintering, plasma agglomeration, to matrix metal and the diamond framework compound of surface modified diamond particle be comprised, obtain the sheet diamond reinforced metal-base composite material of diamond wafers and matrix metal metallurgical binding.
9. the preparation method of a kind of sheet diamond reinforced metal-base composite material according to claim 8, is characterized in that: surface modified diamond thin slice is that self-supporting diamond sheet or the lining comprising substrate support diamond chip;
Described self-supporting diamond sheet adopts chemical gaseous phase depositing process at a side depositing diamond of sheet metal substrate, and after etched substrate, obtain self-supporting diamond sheet, self-supporting diamond sheet thickness is 0.005 ~ 0.5mm; Or
Described lining supports diamond chip and adopts chemical gaseous phase depositing process at a side of sheet metal substrate or both sides depositing diamond, obtains lining and supports diamond chip, and it is 0.005 ~ 0.5mm that lining supports diamond film layer thickness in diamond chip;
Described chemical gaseous phase depositing process is selected from the one in heated filament auxiliary law, microwave plasma enhancing method, flame combustion process, direct-current discharge method, DC arc plasma jet, low pressure radio frequency method, normal-pressure radio-frequency method, electron cyclotron resonace method.
10. the preparation method of a kind of sheet diamond reinforced metal-base composite material according to claim 9, it is characterized in that: described lining supports diamond chip, before chemical vapour deposition diamond, carry out pre-treatment to metal substrate surface, pretreatment technology is:
For the sheet metal substrate that can form strong carbide, after the oil removing of sheet metal substrate, scale removal, electrochemical etching, be directly soaked in fine diamond powder suspension liquid, carry out the pre-treatment of ultrasonic oscillation plantation seed crystal;
The sheet metal substrate material that can form strong carbide is selected from the one in W, Mo, Ti, Cr, Ta, Si, Nb; Or
For the sheet metal substrate that can not form strong carbide, for improving the interface cohesion of diamond and core, after the oil removing of sheet metal substrate, scale removal, electrochemical etching, adopt physical vapor deposition or electro-deposition techniques can form the film of strong carbide in metal substrate surface preparation, and select individual layer, multilayer or alloy film according to the characteristic of substrate, then, be directly soaked in fine diamond powder suspension liquid and carry out the pre-treatment of ultrasonic oscillation plantation seed crystal;
The metal substrate material that can not form strong carbide is selected from the one in Cu, Ag, Au, Ni, Al, Co.
The preparation method of 11. a kind of sheet diamond reinforced metal-base composite materials according to claim 8, is characterized in that: surface modification lamellar gold hard rock and surface modified diamond particle adopt at least one plating mode in magnetron sputtering, vacuum-evaporation, plating, electroless plating to realize surface modification.
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