CN105239026A - One-dimensional diamond reinforced aluminum matrix composite material and preparing method thereof - Google Patents
One-dimensional diamond reinforced aluminum matrix composite material and preparing method thereof Download PDFInfo
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- CN105239026A CN105239026A CN201510659346.7A CN201510659346A CN105239026A CN 105239026 A CN105239026 A CN 105239026A CN 201510659346 A CN201510659346 A CN 201510659346A CN 105239026 A CN105239026 A CN 105239026A
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Abstract
The invention discloses a one-dimensional-diamond-reinforced aluminum matrix composite material and a preparing method. The composite material is characterized in that a diamond array composed of a plurality of one-dimensional diamond wires is distributed in an aluminum matrix, and the one-dimensional diamond wires are surface-modified diamond wires and are combined with the aluminum matrix in a metallurgical manner. The preparing method of the composite material includes the steps that after the surface-modified diamond wires are distributed in an array manner, the aluminum matrix or the aluminum matrix containing surface-modified diamond particles is compounded with the diamond wire array through one of a casting technology, an infiltration technology, a cold pressing sintering technology, a hot pressing sintering technology and a plasma sintering technology, and the one-dimensional-diamond-reinforced aluminum matrix composite material in which the one-dimensional diamond wires are combined with the aluminum matrix in the metallurgical manner is obtained. According to the one-dimensional-diamond-reinforced aluminum matrix composite material and the preparing method, the one-dimensional diamond wires are distributed in the aluminum matrix in the array manner, a series-parallel connection composite heat conduction structure is formed by adding the diamond particles, the heat conducting efficiency is further improved, the composite material can be used as an electronic packaging material, a heat sink material and the like, and packaging of high-temperature, high-frequency and high-power electronic devices is achieved.
Description
Technical field
The present invention relates to a kind of diamond composite, particularly relate to a kind of one dimension diamond reinforced aluminum matrix composites, the invention still further relates to the preparation method of this one dimension diamond reinforced aluminum matrix composites.
Background technology
Electronic Packaging is that all parts forming electron device or unicircuit is realized reasonable Arrangement, assembling, bonding, connection, the operating procedure of isolating with environment by the requirement of regulation; require that packaged material has high thermal conductivity; low thermal expansivity, the effect such as good mechanical support, physical protection, electrical connection, heat radiation protection against the tide, outer field shield, dimensional transitions and stable element parameter.Along with the fast development of electronic information technology, electronic machine forward high-performance, low cost, miniaturization, facilitation, the fast development of multifunctional integrated direction, electronic devices and components integrated level and travelling speed constantly raise, the heat causing integrated circuit (IC) products to send significantly increases, thus affects the stability of electron device.Although electronic package material experienced by 1st generation copper alloy at present, 2nd generation tungsten copper and molybdenum-copper, to the 3rd generation the alloy such as Al/SiC, Al/Si, these materials make great progress in density, but on heat conductivility, be also difficult to the demand meeting unicircuit and chip technology high speed development.
Diamond is occurring in nature heat conductivility best material, and the thermal conductivity under normal temperature can reach 2200W/ (mK), be 10 times of aluminium, and its thermal expansivity (CTE) only has 0.8 × 10
-6/ K, less than 1/20 of aluminium.The thermal conductivity of metallic aluminium is high, price is low, easily process, and is traditional electronic package material.Matrix material is made after special processing is carried out to aluminium and diamond, it is made to have aluminium and adamantine characteristic concurrently, as over-all propertieies such as high connductivity, high heat conduction, high strength, controlled thermal expansivity, lower density, overcome the shortcomings such as aluminium intensity is inherently low, wear-resisting difference, replacing the electronic package materials such as Cu, W-Cu, Al/SiC, AlN of current widespread use, is the study hotspot of current solution modern electronic devices heat dissipation problem.
Research for diamond/metal (Cu, Al and all kinds of alloy) matrix material starts to walk comparatively early abroad, mainly concentrate on the U.S., Japan and the developed country such as European, achievement in research is also more, and almost the overwhelming majority concentrates on diamond particles enhancing metal-base composites.With regard to diamond/aluminum matrix material, the Johnson of the U.S. etc. utilize pressureless infiltration diamond particles skeleton successfully to obtain diamond/aluminum matrix material, and the heat conductivity of preparation is 259W/ (mK); Prior powder metallurgy method is applied to the preparation of diamond/aluminum matrix material by Natishan etc., ites is desirable to realize the optimization to matrix material, but effect not obvious.2004, O.Beffort etc. adopted conventional pressure infiltration method to prepare diamond particles reinforced aluminum matrix composites, but heat conductivity only has 130W/ (mK).And for diamond/copper matrix material, nineteen ninety-five, SunMicrosystems company of the U.S. and LawrenceLivermore National Laboratory have developed jointly diamond particles/carbon/carbon-copper composite material, substrate as multi-chip module uses, thermal conductivity is 420W/ (mK), CTE when 25 ~ 200 DEG C is (5.48 ~ 6.5) × 10
-6k
-1, match with the CTE of GaAs, but preparation technology's more complicated, cost are also very high.
In theory, the thermal conductivity of diamond/metal-base composites between diamond and metallic matrix, will should improve the thermal conductivity of matrix material so greatly; But in fact, the thermal conductivity of diamond/aluminum is often less than 300W/ (mK), and the thermal conductivity of diamond/copper matrix material is often less than 400W/ (mK).This is because the wettability extreme difference of diamond and aluminium, copper, two combine closely can not cause a lot of textural defect and space, causes composite material interface place to define very large thermal resistance.
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 good heat conductivility.Such as: 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.In other words, reducing number of interfaces between diamond, form continuous print diamond heat-conducting passage, is one of most effective way improving diamond/copper matrix material heat conductivility.
The application of diamond in Electronic Packaging field is realized by cvd diamond self-supporting thick film the earliest, owing to requiring larger thickness, greatly improves use cost.Chemical vapour deposition technique can in the continuous fine and close High Quality Diamond Films of substrate surface preparation of complicated shape, can make to form continuous print passage of heat between diamond crystals, therefore have some scholars to utilize CVD to prepare diamond film/carbon/carbon-copper composite material in exploration always.
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 one dimension diamond reinforced aluminum matrix composites that can realize the directed heat conduction of high-performance.
Second technical problem to be solved by this invention provides a kind of preparation method realizing this high-performance directed heat conduction one dimension diamond reinforced aluminum matrix composites.
For solving above-mentioned first technical problem, one dimension diamond reinforced aluminum matrix composites of the present invention, comprise aluminum substrate, it is characterized in that: distribute the diamond array be made up of some one dimension diamond wires in described aluminum substrate, described one dimension diamond wire and aluminum substrate metallurgical binding.
One dimension diamond reinforced aluminum matrix composites of the present invention, the one dimension diamond wire in described diamond array is arranged in parallel in metal base, and relative position is evenly arranged or random arrangement.
One dimension diamond reinforced aluminum matrix composites of the present invention, described one dimension diamond wire is the line support diamond wire that self-supporting diamond Xian Huo center is provided with linear core, the diameter of self-supporting diamond line is 0.015 ~ 2.0mm, and the diameter that line supports diamond wire is 0.015 ~ 3.0mm; The filamentous silk material of the one in tungsten, molybdenum, copper, titanium, silver, gold, carbon fiber, silicon carbide fiber selected by described linear core; The diameter of described linear core is 0.014 ~ 2.0mm.
One dimension diamond reinforced aluminum matrix composites of the present invention, described one dimension diamond wire is surface modified diamond line, surface modified diamond line one dimension diamond wire surface is provided with metallic membrane carry out modification, the effect of metallic membrane is the wettability improved between diamond and matrix metal, therefore, the good film material of wettability should be selected between adjacent film layers; Described metallic membrane is selected from the one in titanium film, tungsten film/copper film, chromium film/copper film, wherein: titanium film thicknesses of layers is 0.1 ~ 1.0 μm, tungsten film/copper film thicknesses of layers is 0.02 ~ 0.2 μm/1.0 ~ 10.0 μm, and chromium film/copper film thicknesses of layers is 0.05 ~ 0.5 μm/2 ~ 20 μm.
One dimension diamond reinforced aluminum matrix composites of the present invention, the diamond particles of surface through molybdenum film/copper film modification is also distributed with in described aluminum substrate, diamond particles and aluminum substrate are metallurgical binding, diamond particles granularity is 1 ~ 200 μm, and the percentage composition that described diamond particles accounts for total composite volume is 0 ~ 50%; The thicknesses of layers of described molybdenum film/copper film is 0.05 ~ 0.5 μm/0.5 ~ 5.0 μm, and molybdenum film internal surface is combined with diamond surface, and copper film is coated on molybdenum film outer surface.
For solving above-mentioned second technical problem, the preparation method of one dimension diamond reinforced aluminum matrix composites of the present invention, first arranges as stochastic distribution or equally distributed diamond wire array by the one dimension diamond wire of surface modification; Then, adopt a kind of technique in founding, infiltration, cold-rolled sintered, hot pressed sintering, plasma agglomeration, by aluminum or aluminum alloy and diamond wire array compound, obtain the one dimension diamond reinforced aluminum matrix composites of one dimension diamond wire and aluminum substrate metallurgical binding; Or
Adopt a kind of technique in founding, infiltration, cold-rolled sintered, hot pressed sintering, plasma agglomeration, to aluminum or aluminum alloy and the diamond wire array compound of surface modified diamond particle be comprised, obtain the one dimension diamond reinforced aluminum matrix composites of one dimension diamond wire and aluminum substrate metallurgical binding.
The preparation method of one dimension diamond reinforced aluminum matrix composites of the present invention, surface modification one dimension diamond wire or surface modified diamond particle adopt one or more plating modes in magnetron sputtering, multi-arc ion coating, vacuum-evaporation, electroless plating, plating to realize surface modification.
The preparation method of one dimension diamond reinforced aluminum matrix composites of the present invention, described surface modification one dimension diamond wire is the line support diamond wire that self-supporting diamond Xian Huo center is provided with linear core.
The preparation method of one dimension diamond reinforced aluminum matrix composites of the present invention, described self-supporting diamond line preparation technology adopts heated filament auxiliary law, microwave plasma strengthens method, flame combustion process, direct-current discharge method, DC arc plasma jet, low pressure radio frequency method, normal-pressure radio-frequency method, a kind of chemical gaseous phase depositing process in electron cyclotron resonace method is at linear core or flat substrates surface deposition diamond, after etching linear core or flat substrates, obtain self-supporting one dimension diamond wire or sheet self-supporting diamond sheet, sheet self-supporting diamond sheet obtains self-supporting one dimension diamond wire through laser cutting, self-supporting one dimension diamond wire diameter is 0.015 ~ 2.0mm,
Described line supports diamond wire preparation technology and adopts heated filament auxiliary law, microwave plasma to strengthen a kind of chemical gaseous phase depositing process in 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 at linear core surfaces depositing diamond, diamond film layer thickness is 0.001 ~ 1mm, and the filamentous silk material of the one in tungsten, molybdenum, copper, titanium, silver, gold, carbon fiber, silicon carbide fiber selected by linear core; The diameter of described linear core is 0.014 ~ 2.0mm.
The preparation method of one dimension diamond reinforced aluminum matrix composites of the present invention, described line supports diamond wire, and at employing chemical gaseous phase depositing process before linear core surfaces depositing diamond, carry out pre-treatment to linear core surfaces, pretreatment technology is:
For the linear core that can form strong carbide, after core is carried out oil removing, scale removal, electrochemical etching successively, be directly soaked in fine diamond powder suspension liquid and carry out the pre-treatment of ultrasonic oscillation plantation seed crystal; The linear core that can form strong carbide is selected from the one in W, Mo, Ti, Cr, Ta, Si, Nb;
Or
For the linear core that can not form strong carbide, after core is carried out oil removing, scale removal, electrochemical etching successively, adopt physical vapor deposition or chemical Vapor deposition process can form the film of strong carbide in core surfaces preparation, film is the one in single thin film, multilayer film, alloy firm, then, be soaked in fine diamond powder suspension liquid and carry out the pre-treatment of ultrasonic oscillation plantation seed crystal; The linear core that can not form strong carbide is selected from the one in Cu, Ag, Au, Ni, Al, Co.
The preparation method of one dimension diamond reinforced aluminum matrix composites of the present invention, described founding is by containing modification diamond particles or do not put into graphite jig in the lump containing the aluminum or aluminum alloy of modification diamond particles and one dimension diamond array, then put it in vacuum melting furnace or atmosphere protection smelting furnace and be heated to 600 ~ 1000 DEG C of meltings, cooling and demolding, obtains one dimension diamond reinforced aluminum matrix composites; Or
First aluminum or aluminum alloy is heated to 600 ~ 800 DEG C in crucible, obtain melting aluminum or aluminum alloy, directly the one dimension diamond wire be arranged in array leaching is placed in liquid aluminum or aluminum alloy, or after adding modification diamond particles in melting aluminum or aluminum alloy, stirring, the one dimension diamond wire be arranged in array leaching is placed in liquid aluminum or aluminum alloy, cooling, obtains one dimension diamond reinforced aluminum matrix composites.
The preparation method of one dimension diamond reinforced aluminum matrix composites of the present invention, described infiltration is that the one dimension diamond wire be arranged in array 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 aluminum or aluminum alloy of the molten state of modification diamond particles, compound is carried out with diamond rod, the preheating temperature of diamond rod array controls 500 ~ 700 DEG C of scopes, the teeming temperature of molten state aluminium is 700 ~ 900 DEG C, infiltration pressure is 5 ~ 30MPa, soaking time is 0.5 ~ 3 hour, obtain one dimension diamond reinforced aluminum matrix composites.
The preparation method of one dimension diamond reinforced aluminum matrix composites of the present invention; described hot pressed sintering is by aluminium powder or Al alloy powder or after adding one dimension diamond array containing the aluminium powder of modification diamond particles or Al alloy powder; put into vacuum or protective atmosphere hot pressing furnace hot pressed sintering; sintering temperature is 550 ~ 655 DEG C; pressure is 5 ~ 200MPa; time is 30 ~ 240 minutes, cooling and demolding, obtains one dimension diamond reinforced aluminum matrix composites.
The preparation method of one dimension diamond reinforced aluminum matrix composites of the present invention, described plasma agglomeration is by aluminium powder or Al alloy powder or adds in one dimension diamond array containing the aluminium powder of modification diamond particles or Al alloy powder, after compacting, put into plasma agglomeration stove to sinter, pressure 5 ~ 70MPa, sintering process is: sintering temperature 500 ~ 700 DEG C, heat-up rate 10 ~ 300 DEG C/min, insulation 5 ~ 10min, atmosphere is vacuum.
Contriver according to occurring in nature " water pump " to the effect of current, dexterously " heat pump " concept is incorporated in diamond/copper matrix material, by diamond wire array of arranging in a metal, diamond wire and metal is made to form parallel-connection structure, as " water pump ", hot-fluid is constantly extracted out, heat in around copper is constantly sucked in the diamond wire of nearest neighbour and is quickly drawn out.The present invention utilizes process for modifying surface first at the one dimension diamond wire surface film that preparation is good with diamond wettability successively, the rete with base material aluminium with good wettability, effectively improves the wettability between diamond thin and aluminium; The modified diamond wire of effects on surface is arranged in advance, and then adopt the method such as high vacuum infiltration or protective atmosphere infiltration, hot pressed sintering, plasma agglomeration to prepare diamond wire reinforced aluminum matrix composites, facilitate the interfacial diffusion between diamond wire and matrix metal, improve interface cohesion condition, realize metallurgical binding, reduce interface thermal conductance, make " heat pump " effect further be effectively played; With the addition of the diamond particles through duplex surface modification in matrix material, further increase heat transfer efficiency.Overcome prior art Patent CN102244051A and there is the dissatisfactory defect of thermal conductivity.In other words, the present invention no matter in composite structure composition, or has made huge innovation and improvement in technology of preparing.
Compared with prior art, the present invention makes this matrix material have good directed heat conductivility in the direction by assembling some column diamond wire arrays with high heat conductance in aluminum substrate in the same way, realizes the directed heat conduction of high-performance.Wherein, all diamond wires are arranged in parallel in the same direction, and each root diamond wire becomes a quick conductive passage, and heat is constantly distributed rapidly along diamond column direction, the joint effect of all diamond wires, just makes this matrix material have good directed heat conductivility; By at the good metallic film of diamond wire coating surface one or more layers and diamond wettability, and then with base material aluminium, there is one or more layers film of good wettability in its most top layer preparation, again by different sintering and densification process, the metal of diamond surface or carbide etc. are to diamond and Al matrix generation interfacial diffusion or reaction, realize metallurgical binding, compound interface is combined obviously strengthened, the thermal conductivity of material can acquire the improvement of high degree; In matrix material preparation process, diamond particles after surface modification treatment is joined in aluminium powder or Al alloy powder, by densified sintering product metallization processes, make its Dispersed precipitate in aluminum substrate, the thermal conductivity of one dimension diamond reinforced aluminum matrix composites can be promoted further; Diamond has high thermal conductivity (1300 ~ 2200W/ (mK)), low thermal expansivity (0.8 × 10
-6~ 1.5 × 10
-6k
-1) and the premium properties such as high Young's modulus, the advantages such as aluminium has that density is low, thermal conductivity is high, cost is low, corrosion-resistant and easy mechanical workout, therefore, diamond is prepared into matrix material as reinforcement and aluminium, the characteristic of diamond and aluminium can be combined, acquisition has high heat conductance, low thermal coefficient of expansion and low-density packaged material, and this matrix material can be applicable to the fields such as military pocket computer, high-performance server, aerospace electronics, photonics and ion display.
Accompanying drawing explanation
Accompanying drawing 1 is one dimension diamond wire reinforced aluminum matrix composites preparation method schematic flow sheet.
Accompanying drawing 2 is the cross-sectional structure schematic diagram after belt carcass diamond wire surface modification.
Accompanying drawing 3 is the vertical profile TV structure schematic diagram of Fig. 2.
Accompanying drawing 4a is the cross-sectional view of a kind of array arrangement that after surface modification, belt carcass diamond wire is evenly arranged.
Accompanying drawing 4b is the another kind of array arrangement cross-sectional view that after surface modification, belt carcass diamond wire is evenly arranged.
Accompanying drawing 4c is the cross-sectional view of a kind of array arrangement of belt carcass diamond wire random arrangement after surface modification.
Accompanying drawing 4d is the another kind of array arrangement cross-sectional view of belt carcass diamond wire random arrangement after surface modification.
Accompanying drawing 5 is the longitudinal section of Fig. 4 a.
In accompanying drawing 2: 1-linear core 2-cvd diamond film 3-metallic diaphragm
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 wire or carbide silk material
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, silk material is soaked in fine diamond powder acetone suspension liquid ultrasonic vibration process 30min;
(2) adopt hot-wire chemical gas-phase deposition at silk or the continuous fine and close diamond film of flat substrates 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 linear core or flat substrates surface deposition diamond, diamond film layer thickness is 0.001 ~ 1.0mm.After etching linear core or flat substrates, obtain self-supporting one dimension diamond wire or sheet self-supporting diamond, sheet self-supporting diamond obtains self-supporting one dimension diamond wire through laser cutting, i.e. full diamond wire.
(3) belt carcass diamond wire or full diamond wire surface modification treatment
Adopt any one plating modes such as magnetron sputtering, multi-arc ion coating, vacuum-evaporation or electroless plating at one dimension diamond wire surface deposition simple substance or composite film.
(4) oriented alignment of modified belt carcass diamond wire
Can stochastic distribution, can also be uniformly distributed, evenly arrange
(5) aluminium is filled and densification process
Thermal treatment or the densification processes such as hot pressed sintering, infiltration or protective atmosphere melting
Embodiment one:
Select respectively diameter be the tungsten filament of 0.03mm and 0.4mm as core, first according to step (1) to core surfaces 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, CH4/H2 volume flow ratio 1:99, obtain diamond film thickness 60 μm, namely obtain belt carcass diamond filament; (3) adopt magnetically controlled sputter method first to sputter layer of metal tungsten film on belt carcass diamond wire surface, sputtering power is 150W, pressure 0.4Pa, substrate temperature 400 DEG C, and argon flow amount 20sccm, W film thickness is 0.2 μm; Sputter layer of metal copper film again, sputtering power is 100W, pressure 0.5Pa, substrate temperature 300 DEG C, argon flow amount 20sccm, thicknesses of layers 5.0 μm; (4) the belt carcass diamond wire orientation of plated surface W/Cu is evenly arranged in mould, arrangement distance 1mm; (4) the belt carcass diamond wire orientation of plated surface W/Cu be evenly arranged in mould, arrangement distance 1mm, namely obtains one dimension diamond array backbone; (5) one dimension diamond 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 respectively 630W/ (mK) (core is thin tungsten filament), 528W/ (mK) (core is thick tungsten filamen).
Embodiment two:
Select respectively diameter be 0.3 μm of copper wire, 0.3 μm of titanium silk as core, first according to step (1) to core surfaces 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 850 DEG C, hot-wire temperature 2200 DEG C, deposition pressure 3KPa, depositing time 50 hours, CH4/H2 volume flow ratio 1:99, obtain diamond film thickness 100 μm, namely obtain belt carcass diamond wire; (3) adopt vacuum vapor deposition method at belt carcass diamond wire surface layer of metal chromium film, evaporation current is 36A, pressure 0.1Pa, substrate temperature 400 DEG C, chromium film thickness is 0.5 μm, then vacuum-evaporation layer of metal copper film, evaporation current is 30A, pressure 0.1Pa, substrate temperature 300 DEG C, thicknesses of layers 2.0 μm; (4) the belt carcass diamond wire orientation of plated surface Cr/Cu be evenly arranged in mould, arrangement distance 2mm, namely obtains one dimension diamond array backbone; (5) one dimension diamond 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; high directed heat conduction one dimension diamond reinforced aluminum matrix composites can be obtained; heat conductivity is respectively 725W/ (mK) (core is copper wire), 689W/ (mK) (core is titanium silk).
Embodiment three:
Select respectively diameter be the thin molybdenum filament of 0.1mm, the thick molybdenum filament of 0.8mm as core, first according to step (1) to core surfaces carry out early stage process; Then HF CVD depositing diamond film is adopted according to step (2), deposition process parameters: heated filament distance 8mm, substrate temperature 900 DEG C, hot-wire temperature 2200 DEG C, deposition pressure 3KPa, depositing time 50 hours, CH4/H2 volume flow ratio 2:98, obtain diamond film thickness 100 μm, namely obtain belt carcass diamond filament; (3) adopt magnetically controlled sputter method first to sputter layer of metal titanium film on belt carcass diamond wire surface, sputtering power is 92W, pressure 0.5Pa, substrate temperature 300 DEG C, argon flow amount 20sccm, thicknesses of layers 500nm; (4) the belt carcass diamond wire orientation of plated surface Ti be evenly arranged in mould, arrangement distance 3mm, namely obtains one dimension diamond array backbone; (5) gap location of diamond wire 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; (6) be radially pressed, pressure is 120MPa, then the sample of compression moulding is carried out hot pressed sintering, obtained one dimension diamond reinforced aluminum matrix composites: sintering temperature is 550 DEG C, sintering pressure 30MPa, and temperature rise rate is, soaking time 5min, atmosphere is vacuum.The obtained height of this technique directed heat conduction one dimension diamond reinforced aluminum matrix composites thermal conductivity is adopted to be respectively 802W/ (mK) (core is thin molybdenum filament), 873W/ (mK) (core is thick molybdenum filament).
Embodiment four:
Select respectively diameter be 0.014 μm of spun gold, 0.03 μm of filamentary silver as core, first according to step (1) to core surfaces 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 850 DEG C, hot-wire temperature 2300 DEG C, deposition pressure 3KPa, depositing time 80 hours, CH
4/ H
2volume flow ratio 1:99, obtains diamond film thickness 100 μm, (3) adopt magnetically controlled sputter method first to sputter layer of metal chromium film on belt carcass diamond wire surface, sputtering power is 200W, pressure 0.3Pa, substrate temperature 350 DEG C, and argon flow amount 50sccm, Cr film thickness is 0.5 μm, sputter layer of metal copper film again, sputtering power is 150W, pressure 0.4Pa, substrate temperature 300 DEG C, argon flow amount 20sccm, thicknesses of layers 10.0 μm, (4) the belt carcass diamond wire orientation of plated surface Cr/Cu is evenly arranged in mould, arranging distance 2mm, (5) gap location of diamond wire 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 particle surfaces passes through and Mo/Cu surface modification treatment like embodiment three-phase), radially be pressed, pressure is 120MPa, then the sample of compression moulding is carried out discharge plasma sintering (SPS), obtained one dimension diamond reinforced aluminum matrix composites: sintering temperature is 550 DEG C, sintering pressure 30MPa, temperature rise rate is, soaking time 5min, atmosphere is vacuum.The most high heat conductance of the height adopting this technique obtained directed heat conduction one dimension diamond reinforced aluminum matrix composites is respectively 856W/ (mK) (core is spun gold), 928W/ (mK) (core is filamentary silver).
Embodiment five:
Select thickness be 1mm 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, and after etching sheet silicon base material, obtain sheet self-supporting diamond, then obtain self-supporting one dimension diamond wire through laser cutting, be i.e. full diamond wire, diameter is 0.5mm; (3) adopt magnetically controlled sputter method first to sputter layer of metal chromium film on full diamond wire surface, sputtering power is 200W, pressure 0.3Pa, substrate temperature 350 DEG C, and argon flow amount 50sccm, Cr film thickness is 0.5 μm; Sputter layer of metal copper film again, sputtering power is 150W, pressure 0.4Pa, substrate temperature 300 DEG C, argon flow amount 20sccm, thicknesses of layers 10.0 μm; (4) the full diamond wire orientation of plated surface Cr/Cu is evenly arranged in mould, arranging distance 2mm; (5) gap location of diamond wire 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 particle surfaces passes through and Mo/Cu surface modification treatment like embodiment three-phase), then sample is carried out hot pressed sintering, obtained one dimension diamond reinforced aluminum matrix composites: sintering temperature is 650 DEG C, sintering pressure 60MPa, soaking time 90min, atmosphere is vacuum.The most high heat conductance of the height adopting this technique obtained directed heat conduction one dimension diamond reinforced aluminum matrix composites is 980W/ (mK).
Therefore, the thermal conductivity of height obtained in this patent directed heat conduction one dimension diamond reinforced aluminum matrix composites can reach 980W/ (mK), apparently higher than the thermal conductivity (100 ~ 600W/ (mK)) of traditional diamond particles reinforced aluminum matrix composites.
Claims (10)
1. an one dimension diamond reinforced aluminum matrix composites, is characterized in that: distribute the diamond array be made up of some one dimension diamond wires in described aluminum substrate, described one dimension diamond wire and aluminum substrate metallurgical binding.
2. one dimension diamond reinforced aluminum matrix composites according to claim 1, is characterized in that: the one dimension diamond wire in described diamond array is arranged in parallel in metal base, and relative position is evenly arranged or random arrangement.
3. one dimension diamond reinforced aluminum matrix composites according to claim 2, it is characterized in that: described one dimension diamond wire is the line support diamond wire that self-supporting diamond Xian Huo center is provided with linear core, the diameter of self-supporting diamond line is 0.015 ~ 2.0mm, and the diameter that line supports diamond wire is 0.015 ~ 3.0mm; The filamentous silk material of the one in tungsten, molybdenum, copper, titanium, silver, gold, carbon fiber, silicon carbide fiber selected by described linear core; The diameter of described linear core is 0.014 ~ 2.0mm.
4. the one dimension diamond reinforced aluminum matrix composites according to claim 1-3 any one, it is characterized in that: described one dimension diamond wire is surface modified diamond line, surface modified diamond line one dimension diamond wire surface is provided with metallic membrane carry out modification; Described metallic membrane is selected from the one in titanium film, tungsten film/copper film, chromium film/copper film, wherein: titanium film thicknesses of layers is 0.1 ~ 1.0 μm, tungsten film/copper film thicknesses of layers is 0.02 ~ 0.2 μm/1.0 ~ 10.0 μm, and chromium film/copper film thicknesses of layers is 0.05 ~ 0.5 μm/2 ~ 20 μm.
5. one dimension diamond reinforced aluminum matrix composites according to claim 4, it is characterized in that: in described aluminum substrate, be also distributed with the diamond particles of surface through molybdenum film/copper film modification, diamond particles and aluminum substrate are metallurgical binding, diamond particles granularity is 1 ~ 200 μm, and the percentage composition that described diamond particles accounts for total composite volume is 0 ~ 50%; The thicknesses of layers of described molybdenum film/copper film is 0.05 ~ 0.5 μm/0.5 ~ 5.0 μm, and molybdenum film internal surface is combined with diamond surface, and copper film is coated on molybdenum film outer surface.
6. the preparation method of one dimension diamond reinforced aluminum matrix composites, is characterized in that: first arrange as stochastic distribution or equally distributed diamond wire array by the one dimension diamond wire of surface modification; Then, adopt a kind of technique in founding, infiltration, cold-rolled sintered, hot pressed sintering, plasma agglomeration, by aluminum or aluminum alloy and diamond wire array compound, obtain the one dimension diamond reinforced aluminum matrix composites of one dimension diamond wire and aluminum substrate metallurgical binding; Or
Adopt a kind of technique in founding, infiltration, cold-rolled sintered, hot pressed sintering, plasma agglomeration, to aluminum or aluminum alloy and the diamond wire array compound of surface modified diamond particle be comprised, obtain the one dimension diamond reinforced aluminum matrix composites of one dimension diamond wire and aluminum substrate metallurgical binding.
7. the preparation method of one dimension diamond reinforced aluminum matrix composites according to claim 6, is characterized in that: surface modification one dimension diamond wire or surface modified diamond particle adopt one or more plating modes in magnetron sputtering, multi-arc ion coating, vacuum-evaporation, electroless plating, plating to realize surface modification.
8. the preparation method of one dimension diamond reinforced aluminum matrix composites according to claim 7, is characterized in that: described surface modification one dimension diamond wire is the line support diamond wire that self-supporting diamond Xian Huo center is provided with linear core.
9. the preparation method of one dimension diamond reinforced aluminum matrix composites according to claim 8, it is characterized in that: described self-supporting diamond line preparation technology adopts heated filament auxiliary law, microwave plasma strengthens method, flame combustion process, direct-current discharge method, DC arc plasma jet, low pressure radio frequency method, normal-pressure radio-frequency method, a kind of chemical gaseous phase depositing process in electron cyclotron resonace method is at linear core or flat substrates surface deposition diamond, after etching linear core or flat substrates, obtain self-supporting one dimension diamond wire or sheet self-supporting diamond sheet, sheet self-supporting diamond sheet obtains self-supporting one dimension diamond wire through laser cutting, self-supporting one dimension diamond wire diameter is 0.015 ~ 2.0mm,
Described line supports diamond wire preparation technology and adopts heated filament auxiliary law, microwave plasma to strengthen a kind of chemical gaseous phase depositing process in 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 at linear core surfaces depositing diamond, diamond film layer thickness is 0.001 ~ 1mm, and the filamentous silk material of the one in tungsten, molybdenum, copper, titanium, silver, gold, carbon fiber, silicon carbide fiber selected by linear core; The diameter of described linear core is 0.014 ~ 2.0mm.
10. the preparation method of one dimension diamond reinforced aluminum matrix composites according to claim 8, it is characterized in that: described line supports diamond wire, at employing chemical gaseous phase depositing process before linear core surfaces depositing diamond, carry out pre-treatment to linear core surfaces, pretreatment technology is:
For the linear core that can form strong carbide, after core is carried out oil removing, scale removal, electrochemical etching successively, be directly soaked in fine diamond powder suspension liquid and carry out the pre-treatment of ultrasonic oscillation plantation seed crystal; The linear core that can form strong carbide is selected from the one in W, Mo, Ti, Cr, Ta, Si, Nb;
Or
For the linear core that can not form strong carbide, after core is carried out oil removing, scale removal, electrochemical etching successively, adopt physical vapor deposition or chemical Vapor deposition process can form the film of strong carbide in core surfaces preparation, film is the one in single thin film, multilayer film, alloy firm, then, be soaked in fine diamond powder suspension liquid and carry out the pre-treatment of ultrasonic oscillation plantation seed crystal; The linear core that can not form strong carbide is selected from the one in Cu, Ag, Au, Ni, Al, Co.
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