CN103924119B - A kind of super-high heat-conductive graphite flakes/carbon/carbon-copper composite material and preparation method thereof - Google Patents
A kind of super-high heat-conductive graphite flakes/carbon/carbon-copper composite material and preparation method thereof Download PDFInfo
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- CN103924119B CN103924119B CN201410163989.8A CN201410163989A CN103924119B CN 103924119 B CN103924119 B CN 103924119B CN 201410163989 A CN201410163989 A CN 201410163989A CN 103924119 B CN103924119 B CN 103924119B
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Abstract
A kind of high conductive graphite scale strengthens Cu-base composites and preparation method, belongs to high-performance electronic encapsulation function Material Field.Matrix material is made up of wild phase height conductive graphite scale two portions of matrix copper or copper alloy and plating, and the volume fraction of the graphite flakes wherein after plating is 20%-80%.Material preparation process is: first carry out surface modification to graphite flakes, the coating of metal titanium, chromium, molybdenum, tungsten or its associated carbon compound on the plated surface of graphite flakes; Then the graphite flakes after surface modification and metallic matrix powder are joined in the solvent containing binding agent, plastic agent, mix and obtain mixed slurry, slurry is put into press molds and carry out orientation and extrude, slough binding agent subsequently and obtain presintering thin slice.Sintering after sheet lamination is obtained matrix material.In matrix material prepared by the present invention, scale wild phase is combined with matrix well, and scale realizes aligning in the base, has the thermal conductivity of superelevation, controlled thermal expansivity and good processibility.
Description
Technical field
The invention belongs to high-performance electronic encapsulation function Material Field, relate to the preparation method that a kind of high conductive graphite scale strengthens Cu-base composites.
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, relied on the thermal conductivity of superelevation, adjustable thermal expansivity, being described as is third generation New Materials for Electric Packing.But from existing market situation, do not obtain large-scale application.Poor and the cost of the workability of its diamond reinforced metal-base composite material is higher is the major cause limiting its widespread use.
Graphite is as the another kind of allotropic substance of carbon, and by means of its high heat conduction on graphite flake layer direction, low-expansion coefficient and good processing characteristics have started to be attempted in the compound with metal, becomes the new trend of metal-base composites used for electronic packaging research and development.The high heat conduction of graphite flakes to be mainly derived from the netted plane layer of graphite hexagonal the lattice arrangement of firmly covalent bonds and high-sequential between carbon atom.Research shows, the thermal conductivity of graphite flakes on its graphite flake layer direction of high quality ordered arrangement can reach 1000-2000Wm
-1k
-1.Therefore graphite flakes is used to be hopeful as the Copper substrate matrix material carried out prepared by compound of wild phase and high thermal conductance the thermal conductivity obtaining superelevation.Simultaneously graphite flakes/carbon/carbon-copper composite material has very low thermal expansivity, the advantage that cheap and processibility is good concurrently, is applicable to very much and does electronic package material.
But prepare the problem that high performance graphite flakes/carbon/carbon-copper composite material needs solution two crucial: 1, graphite flakes only has higher thermal conductivity on lamella direction, and sheet inter-layer bonding force is weak, and its theoretical heat conductivity value is only 6Wm
-1k
-1.Therefore utilize high heat conductance in graphite flake layer two dimensional surface make its obtain in the base preferentially to align be obtain the key of high-heat-conductive composite material.Even if 2, carbon-copper system is at high temperature also nonwetting, how making graphite flakes fully contact with copper, obtain uniform distribution and good combination, is the important factor improving heat conductivity.
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 550Wm
-1k
-1.But the ratio of scale oriented alignment is in the base not high, and scale has the phenomenon of larger bending to occur, and the high heat conductance on graphite flakes lamella direction fails to play a role completely.
Summary of the invention
A kind of graphite flakes being used in the super-high heat-conductive carrying out thermodiffusion conduction in two dimensional surface is the object of the present invention is to provide to strengthen copper matrix electronic packaging composite material and preparation method thereof.
A kind of high performance graphite scale strengthens Cu-base composites, and in described matrix material, the graphite flakes reinforcement of coated titanium, chromium, molybdenum, tungsten or its associated carbon compound and matrix copper mix, and wherein the volume fraction of graphite flakes is between 20%-80%; The mean diameter of graphite flakes is 50 μm-1500 μm, and length-to-diameter ratio is between 10-100; The degree of graphitization of graphite flakes is between 88%-99%; X-ray diffraction graphite flakes is used to carry out the spacing d measuring its (002) crystal face
002value is between 0.3345-0.3360nm.
Selected matrix copper is the electrolytic copper powder mixing of mean particle size size 5 μm-80 μm, or uses mean diameter to be 5 μm-20 μm, and length-to-diameter ratio is that the flake copper of 20-50 is as body material.
Graphite flakes oriented alignment is in the base made for arriving, and and Copper substrate between the object of combining closely, the present invention adopts and carries out surface modification to graphite flakes, extrusion molding is used to prepare graphite-copper mixed slurry subsequently, the organic composition of going out in sintering process in slurry subsequently, and compacting sintering becomes matrix material block.It is characterized in that comprising following operation:
(1) use any one plating modes such as salt bath plating, the micro-evaporation plating of vacuum or sol-gel method, the coating of metal titanium, chromium, molybdenum, tungsten or its associated carbon compound on the plated surface of graphite flakes, its thickness is between 0.1 μm-2 μm.Graphite after surface modification and the wetting angle of copper reduce, and bonding force becomes strong Chemical bond from original weak mechanical bond.
(2) graphite flakes after above-mentioned surface modification is used, the electrolytic copper powder mixing that mean particle size size is 5 μm-80 μm, also mean diameter can be used to be 5 μm-20 μm, length-to-diameter ratio be the flake copper of 20-50 as body material, after mixing, its volume fraction of graphite flakes is 20-80%.Add the slurry of component configuration by a certain percentage during mixing, the composition of slurry comprises tackiness agent, softening agent and solvent.
Tackiness agent comprises: the binding agent that the association area such as PVA, β-dimethyl-aminoethylmethacrylate is conventional, and add-on is every 100g solvent 1-20g.
Softening agent comprises: whiteruss, polyoxyethylene glycol, glycerine etc., add-on is every 100g solvent 1-5ml.Solvent can be water, ethylene glycol, alcohol, normal heptane or its mixture.Slurries need select one or several components in binding agent, softening agent, solvent to allocate flexibly according to the size of graphite flakes, volume fraction.Its objective is that the compound making gained is even, stable, good fluidity.
(3) pour in the mould extruding shaping after fully being mixed by above-mentioned mixed powder slurry and carry out orientation and extrude, mould extrusion is long strip shape, and opening is wide is 0.1mm-2mm.Scale directional profile in matrix metal is obtained, the thin slice of thickness between 0.1-2mm by extruding shaping.
Flake sintering precursor can use any technological methods known in the art such as heating or decompression to slough slurry medium in advance, in the process of hot pressed sintering, also suitably can regulate temperature rise rate, while sintering, slough slurry medium.
(4) finally the thin slice sloughing slurry to be aligned and stacked, as in graphite jig, adopt shielding gas or the unidirectional pressure sintering of vacuum heating-press sintering method fine and close.
The technology of the present invention object is to prepare the graphite flakes/carbon/carbon-copper composite material of excessive heat conductance on two dimensional surface direction.This object is by scale surface modification in advance and follow-up extrude orthoplasy to realize.
Graphite flakes after surface modification, the interfacial state between itself and metallic matrix obtains good improvement, greatly reduces interface resistance, is conducive to the conduction of hot-fluid in interface; Through extruding forming technology, scale presents good directional profile.The graphite flakes adopting this legal system standby/carbon/carbon-copper composite material excellent performance, its advantage comprises:
1) perpendicular to the thermal conductivity of the superelevation on pres planes two-dimensional directional;
2) regulatable thermal expansivity;
3) good processability;
4) raw materials cost relative moderate;
5) applicable and large-scale production.
Accompanying drawing explanation
Fig. 1 is the schema of this technique
Fig. 2 is the tissue topography figure of matrix material in embodiment 1
Embodiment
Below with reference to example, technical solution of the present invention is described in further detail:
Embodiment 1
In this example, the thickness of graphite flakes is 20 microns, and mean diameter is 800 microns.By graphite flakes, TiH
2with TiCl
3powder is placed in plater for the ratio of 100:15:2 in mass ratio, and initial depression is 10
-3pa, in plating, vacuum degree control is at 1 ~ 10Pa, and plating temperature is 850 DEG C, and the time is 2h, at this process TiCl
3volatilize and and TiH
2react the gas phase Ti restored and deposit to graphite flakes surface.After cooling, screening materials carrying obtains titanizing graphite flakes.
Get the graphite flakes after above-mentioned surface modification, flakey copper powder that thickness is 5 μm of mean diameters 50 microns, 5% polyvinyl alcohol solution, ethylene glycol solution the mixing of 40:40:10:10 by volume.Then composite granule slurry is put into directed press molds to carry out orientation and extrude, mould extrusion width is 0.5mm, extrudes pressure 10MPa, obtains the thin slice that thickness is 0.5mm.Subsequently, dry in tube furnace, bake out temperature 200 DEG C, be incubated 3 hours.Sheet lamination is put into mould, carries out vacuum heating-press sintering subsequently.Sintering temperature is 980 DEG C, and pressure is 40MPa, and furnace cooling after insulation 30min, obtains graphite flakes/carbon/carbon-copper composite material.
Embodiment 2
In this example, the thickness of graphite flakes is 10 microns, and mean diameter is 1000 microns.First the coating surface molybdenum carbide coating of method at graphite flakes of salt bath plating is adopted.Concrete technology is that use three is oxidized to molybdenum source, and mol ratio is the NaCl-KCl mixing salt of 1:1 is melting salt.By graphite flakes, molybdic oxide, mixing salt in mass ratio 1:2:1 put in corundum crucible after mixing; cover crucible cover; corundum crucible is put into tube furnace, under the protection of high-purity argon gas, rises to 1000 DEG C with the temperature rise rate of 10 DEG C/min, be incubated and cool to room temperature with the furnace after 1 hour.Powdered sample adds the ultrasonic 20min of deionized water, repeatedly evaporate to dryness after rinsing, re-uses Vibration Screen and remove undesired impurities after taking out from tube furnace, and graphite flakes after the plating needed for obtaining finally, its surface is the molybdenum carbide coating of 0.4 micron thickness.
Get the graphite flakes after above-mentioned surface modification, granularity be 5 μm copper powder, 8% polyvinyl alcohol solution, ethylene glycol solution the mixing of 32:48:10:10 by volume.Then composite granule slurry is put into directed press molds to carry out orientation and extrude, mould extrusion width is 0.5mm, extrudes pressure 12MPa, obtains the thin slice that thickness is 0.5mm.Subsequently, dry in tube furnace, bake out temperature 200 DEG C, be incubated 3 hours.Sheet lamination is put into mould, carries out vacuum heating-press sintering subsequently.Sintering temperature is 980 DEG C, and pressure is 40MPa, and furnace cooling after insulation 30min, obtains graphite flakes/carbon/carbon-copper composite material.
Embodiment 3
In this example, the thickness of graphite flakes is 10 microns, and mean diameter is 1000 microns.Selected matrix is mean diameter 50 microns, and thickness is the flake copper of 5 μm.
Get graphite flakes, flakey copper powder, 8% polyvinyl alcohol solution, ethylene glycol solution the mixing of 32:48:10:10 by volume.Then composite granule slurry is put into directed press molds to carry out orientation and extrude, mould extrusion width is 1mm, extrudes pressure 12MPa, obtains the thin slice that thickness is 1mm.Subsequently, dry in tube furnace, bake out temperature 200 DEG C, be incubated 3 hours.Sheet lamination is put into mould, carries out vacuum heating-press sintering subsequently.Sintering temperature is 980 DEG C, and pressure is 40MPa, and furnace cooling after insulation 30min, obtains graphite flakes/carbon/carbon-copper composite material.
Embodiment 4
In this example, the thickness of graphite flakes is 1 micron, and mean diameter is 50 microns.Selected matrix 1000 order pure copper powder.
Get graphite flakes, pure copper powder, 8% polyvinyl alcohol solution, ethylene glycol solution the mixing of 48:32:10:10 by volume.Then composite granule slurry is put into directed press molds to carry out orientation and extrude, mould extrusion width is 1mm, extrudes pressure 12MPa, obtains the thin slice that thickness is 1mm.Subsequently, dry in tube furnace, bake out temperature 200 DEG C, be incubated 3 hours.Sheet lamination is put into mould, carries out SPS sintering subsequently.Sintering temperature is 890 DEG C, and pressure is 30MPa, and insulation 3min, obtains graphite flakes/carbon/carbon-copper composite material.
Claims (3)
1. the preparation method of super-high heat-conductive graphite flakes/carbon/carbon-copper composite material, it is characterized in that, in described matrix material, the graphite flakes reinforcement of coated titanium, chromium, molybdenum, tungsten or its associated carbon compound and matrix copper mix, and wherein the volume fraction of graphite flakes is between 20%-80%; The mean diameter of graphite flakes is 50 μm-1500 μm, and length-to-diameter ratio is between 10-100; The degree of graphitization of graphite flakes is between 88%-99%; X-ray diffraction graphite flakes is used to carry out the spacing d measuring its (002) crystal face
002value is between 0.3345-0.3360nm; Concrete preparation process is:
(1) use salt bath plating, the micro-evaporation plating of vacuum or any one plating mode of sol-gel method, the coating of metal titanium, chromium, molybdenum, tungsten or its associated carbon compound on the plated surface of graphite flakes, thickness of coating is between 0.1 μm-2 μm;
(2) preparation of composite granule slurry: the graphite flakes taken in proportion, copper powder matrix are joined in the slurry of certain proportion component preparation and mix; The composition of slurry comprises tackiness agent, softening agent and solvent; Tackiness agent is: PVA, β-dimethyl-aminoethylmethacrylate, and add-on is every 100g solvent 1-20g; Softening agent is: whiteruss, polyoxyethylene glycol, glycerine, and add-on is every 100g solvent 1-5ml; Solvent is water, ethylene glycol, alcohol, normal heptane or its mixture;
(3) presintering preparation of sections: pour in the mould extruding shaping after being mixed by described for step (2) composite granule slurry and carry out orientation and extrude, mould extrusion is long strip shape, and opening is wide is 0.1mm-2mm; Scale directional profile in matrix metal is obtained, the thin slice of thickness between 0.1-2mm by extruding shaping; Slough wherein slurry medium and obtain presintering thin slice;
(4) the presintering thin slice sloughing slurry to be aligned and stacked, is placed in graphite jig, adopt shielding gas or the unidirectional pressure sintering of vacuum heating-press sintering method fine and close.
2. according to the preparation method of a kind of super-high heat-conductive graphite flakes/carbon/carbon-copper composite material according to claim 1, it is characterized in that: selected matrix copper is the electrolytic copper powder mixing of mean particle size size 5 μm-80 μm, or using mean diameter to be 5 μm-20 μm, length-to-diameter ratio is that the flake copper of 20-50 is as body material.
3., according to the preparation method of a kind of super-high heat-conductive graphite flakes/carbon/carbon-copper composite material according to claim 1, it is characterized in that: in sintering process, temperature is 850-1000 DEG C, pressure is 20-50MPa.
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| CN106916985A (en) * | 2015-12-28 | 2017-07-04 | 北京有色金属研究总院 | The preparation method of high heat conduction graphite/aluminium composite material |
| CN107502767B (en) * | 2016-06-14 | 2019-03-19 | 宁波晨鑫维克工业科技有限公司 | A kind of orientation super-high heat-conductive, high strength graphite-carbon/carbon-copper composite material and its preparation method and application |
| CN106521230B (en) * | 2016-12-06 | 2018-03-09 | 湖南科技大学 | A kind of graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission and preparation method thereof |
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| CN107245595B (en) * | 2017-05-31 | 2018-09-25 | 北京科技大学 | A method of it prepares with negative thermal expansion coefficient crystalline flake graphite/Cu composite materials |
| CN107955890A (en) * | 2017-12-13 | 2018-04-24 | 湖南科技大学 | Graphite-composite material of molybdenum and copper used for electronic packaging and preparation method thereof |
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| CN110453101B (en) * | 2019-08-08 | 2020-09-01 | 长春工业大学 | Metal-copper-flake-sandwiched graphite reinforced copper-based composite material and preparation method and application thereof |
| CN111733386B (en) * | 2020-05-21 | 2021-11-26 | 南京航空航天大学 | Diamond particle vacuum micro-evaporation molybdenum plating method |
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| CN113860903B (en) * | 2021-09-23 | 2023-01-24 | 中国电子科技集团公司第五十四研究所 | Preparation method of high-thermal-conductivity graphite-copper composite board |
| CN113683087B (en) * | 2021-09-30 | 2022-03-04 | 昆明理工大学 | Surface modification method for expanded graphite in-situ deposition of nano metal particles |
| CN114480905B (en) * | 2022-01-28 | 2022-09-27 | 荣成市宏程新材料有限公司 | Powder metallurgy preparation method of metal matrix composite material |
| CN114921682B (en) * | 2022-06-28 | 2023-03-28 | 北京科技大学广州新材料研究院 | High-thermal-conductivity isotropic graphite nodule-copper-based composite material and preparation method thereof |
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