CN103966533B - A kind of diamond heat-conducting composite and preparation method thereof - Google Patents
A kind of diamond heat-conducting composite and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of diamond heat-conducting composite and preparation method thereof.Specifically, the invention discloses a kind of diamond metal composite and preparation method thereof, described composite includes metallic matrix and is distributed in the diamond particles on described intrinsic silicon and/or surface, and the part or all of described diamond particles of at least a part of which is incorporated into described metallic matrix by nano whisker.This composite has high interfacial strength, the advantage such as high thermal conductivity, low thermal coefficient of expansion, is widely used.
Description
Technical field
The invention belongs to diamond heat-conducting field of compound material.In particular it relates to a kind of diamond heat-conducting is combined
Material and preparation method thereof.
Background technology
Along with developing rapidly of electronics industry, Electronic Packaging, the high density of assembling, high speedization integrated circuit are to encapsulation material
The performance of material proposes more strict requirements.At present, various novel encapsulated materials oneself become the focus that various countries competitively research and develop.Newly
Type microelectronic packaging material not only to have high thermal conductivity, but also must have the thermal expansion system matched with semi-conducting material
Number.Diamond is the known substance that in nature, thermal conductivity is the highest, and the thermal conductivity of high-quality single-crystal diamond can reach 2000W/
(m K), and under room temperature, diamond is insulator, also has features such as dielectric constant is low, thermal coefficient of expansion is low, but single gold
Hard rock is difficult to be fabricated to encapsulating material, and production cost is the highest.Preferably made metal-base composites.
Metallic copper has excellent electric conductivity and high heat conductivility, and its thermal coefficient of expansion (CTE) is 17 × 10-6K,
Thermal conductivity (TC) is 400W/ (m K), and diamond and copper are compounded to form diamond/copper composite, by regulation diamond
Volume fraction realizes highly thermally conductive and adjustable thermal expansion, fully meets the requirement of thermal management materials.
But the preparation difficult point of diamond-copper composite material is: diamond and the wettability extreme difference of copper.At 1150 DEG C
Diamond is 145 ° with the infiltration angle of copper, and between them, high temperature does not has solid state reaction to occur, and diamond and copper are difficult to sinter out cause
Close composite.People are in order to increase the interfacial bonding property of diamond particles and copper, and generally using is at diamond particles table
Face copper facing, or deposited metal carbide thin film manner completes, and the interface ultimately formed is still for the two-dimentional interface of surface-to-surface contact
Structure, the performance such as boundary strength is still weak.
Therefore, the composite of the research and development diamond that a kind of boundary strength is strong, hot property is excellent and metal is badly in need of in this area.
Summary of the invention
It is an object of the invention to provide a kind of boundary strength is strong, hot property is excellent diamond and the composite of metal.
It is a further object of the present invention to provide the preparation method of a kind of above-mentioned composite easy and simple to handle.
In first aspect present invention, it is provided that the diamond-metallic composite of a kind of highly thermally conductive performance, described answers
Condensation material includes metallic matrix and is distributed in the diamond particles on described intrinsic silicon and/or surface, at least a part of which part or
Whole described diamond particles are incorporated into described metallic matrix by nano whisker.
In another preference, described is combined into chemical bonds.
In another preference, described nano whisker is boron nano whisker or boron nitride nanometer whisker.
In another preference, the diamond-metallic composite of described high thermal conductivity has following a kind of or many
Kind feature:
A () density is 6-8.5g/cm3；And/or
(b) thermal conductivity >=400W/m K；And/or
(c) thermal coefficient of expansion≤15 μm/m K.
In another preference, described nano whisker has the feature that (i) a diameter of 1-5000nm；And/or (ii)
A length of 0.1 300 μm；And/or (iii) is 1 10000/μm in the density of diamond particle surfaces2。
In another preference, the particle diameter of described diamond particles is 0.1-1000 μm.
In another preference, the particle diameter of described diamond particles is 10 μm-400 μm；It is more preferably 50 μm-350 μm.
In another preference, described metallic matrix includes: copper, aluminum, silver or their alloy.
In another preference, described diamond-metallic composite prepares as follows:
(1) at diamond particle surfaces growth in situ nano whisker, thus diamond-nano whisker complex is formed；With
And
(2) diamond-nano whisker complex of step (1) is sintered with metallic matrix, thus forms institute
Diamond-the metallic composite stated.
In a second aspect of the present invention, it is provided that the preparation method of a kind of diamond-metallic composite, including step
Rapid:
(1) at diamond particle surfaces growth in situ nano whisker, thus diamond-nano whisker complex is formed；With
And
(2) diamond-nano whisker complex of step (1) is sintered with metallic matrix, thus forms this
Diamond-metallic composite described in invention first aspect.
In another preference, described metallic matrix includes: copper, aluminum, silver or their alloy；And/or described receiving
Meter Jing Xu is boron nano whisker or boron nitride nanometer whisker.
In another preference, described metallic matrix is powder.
In another preference, in step (2), by the gross weight of diamond-nano whisker complex Yu metallic matrix
Calculating, the mass fraction of metallic matrix is 10 90%.
In another preference, described step (1) includes step:
(1.1) offer comprises diamond particles, boron raw material and the mixture of metallic catalyst；
(1.2) in a vacuum or in hydrogen, argon or the reducing atmosphere of a combination thereof gas or inert atmosphere, will step
Suddenly the mixture of (1.1) carries out reacting by heating, thus forms diamond-boron nano whisker complex；And
The diamond that optionally step (1.2) is obtained by (1.3)-boron nano whisker complex enters in nitrogen or ammonia
Row reacting by heating, thus form diamond-boron nitride nanometer whisker complex；
Or described step (1) includes step:
(1-1) offer comprises diamond particles, boron raw material and the mixture of metallic catalyst；With
(1-2) in nitrogen or ammonia, the mixture of step (1-1) is carried out reacting by heating, thus formed diamond-
Boron nitride nanometer whisker complex.
In another preference, boron raw material used is powder or liquid；And/or boron raw material used includes pure boron
With boron compound (it is preferred that described boron compound includes boric acid).
In another preference, in described step (1.1) or step (1-1), calculate by total weight of the mixture, boron raw material
Mass fraction is 1-15wt%；Preferably 5-10wt%.
In another preference, described metallic catalyst is copper, gold, nickel, platinum or their alloy.
In another preference, in described step (1.1) or step (1-1), calculate by total weight of the mixture, metal catalytic
The mass fraction of agent is 10-90wt%；Preferably 20-85wt%；It is more preferably 30-75wt%.
In another preference, in each step above-mentioned,
Described reacting by heating is carried out at 800-1150 DEG C；And/or
Described reacting by heating is carried out under the atmosphere that pressure is 1Pa 120kPa.
In another preference, described step (2) is: at 800 1150 DEG C, under 10 150MPa, by step (1)
Diamond-nano whisker complex is sintered with metallic matrix, thus forms diamond-metallic composite.
In third aspect present invention, it is provided that a kind of goods, comprise the diamond-metal described in first aspect present invention
Composite.
In fourth aspect present invention, it is provided that the use of the diamond-metallic composite described in first aspect present invention
On the way, for machinework, composite or electronic devices and components.
In should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and having in below (eg embodiment)
Can be combined with each other between each technical characteristic that body describes, thus constitute new or preferred technical scheme.As space is limited, exist
This tires out the most one by one states.
Accompanying drawing explanation
The signal that Fig. 1 is combined with Copper substrate after showing the boron nitride nanometer whisker of diamond particle surfaces growth in situ
Figure.First grow boron nitride nanometer whisker in diamond particle surfaces pretreatment, improve the surface area of diamond particles,
Then growth have the diamond particles of boron nitride nanometer whisker and copper are mixed with diamond-copper composite material.
Fig. 2 is diamond particle surfaces growing boron nitride whisker scanning electron microscopy, and Fig. 2 A is diamond particle surfaces
5000 times of displaing micro pictures of boron nanowire；Fig. 2 B is 20000 times of displaing micro pictures of diamond particle surfaces boron nanowire.
Fig. 3 is that the transmission electron microscope figure (such as Fig. 3 A) of a boron nitride crystal whisker and corresponding electronogram are (such as figure
3B)。
Detailed description of the invention
The present inventor is through extensively in-depth study, it has unexpectedly been found that the diamond-metal of a kind of highly thermally conductive performance is multiple
Condensation material, it includes metallic matrix and is distributed in the diamond particles on described intrinsic silicon and/or surface, at least a part of which part
Or whole described diamond particles is incorporated into described metallic matrix by nano whisker.Wherein the existence of nano whisker significantly improves
The boundary strength of diamond and metal so that this composite has the advantages such as high thermal conductivity, thermal coefficient of expansion be controlled.Will be
On the basis of this, inventor completes the present invention.
Diamond-nano whisker complex
The diamond of the present invention-nano whisker complex includes diamond particles and combines (passing through chemical bonds)
Nano whisker in described diamond particle surfaces.
Nano whisker
As used herein, the nano whisker of the present invention includes: boron nano whisker and boron nitride nanometer whisker etc..
Preferably, the nano whisker of the present invention have the feature that (i) a diameter of 1-5000nm (preferably 1～
500nm；It is more preferably 5～100nm)；And/or (ii) a length of 0.1 300 μm (preferably 1～300 μm；It is more preferably 10
～100 μm) and/or (iii) be 1-10000/μm in the density of diamond particle surfaces2(preferably 10-5000/μm2
Or 10-2000/μm2)。
Diamond particles
Diamond particles used by the present invention is the substrate for nanowhisker growth of the present invention, is also diffused with boron atom simultaneously
Carrier.And in the present invention, diamond is the requisite carrier material of boron atoms permeating, does not has it cannot form boron and receive
Meter Jing Xu or boron compound nano whisker.Such as utilizing silicon, the material such as graphite replaces diamond, due to the difference of its lattice parameter
Different, all do not have the effect of boron atoms permeating carrier, it is impossible to form boron nano whisker or boron compound nano whisker.
The diamond particles of the present invention can be the granule of arbitrary dimension, it is preferred to use particle diameter is 0.1 μm-10000 μm
Diamond particles；The diamond particles preferably using particle diameter to be 10 μm-1000 μm；More preferably using particle diameter is 50 μm-1000 μ
The diamond particles of m.
Metallic matrix
As used herein, described metallic matrix includes: the metal that the thermal conductivitys such as Copper substrate, aluminum substrate, silver matrix are higher
Matrix.
Diamond-metallic composite
Diamond-the metallic composite of the present invention, wherein, described composite includes metallic matrix and is distributed in
Described intrinsic silicon and/or the diamond particles on surface, the part or all of described diamond particles of at least a part of which is by nanocrystalline
Must be in conjunction with (passing through chemical bonds) in described metallic matrix.Wherein, described " at least part of described diamond particles " refers to
Diamond particles (the diamond particles of preferably at least 50% of at least 30%；The diamond of more preferably at least 70%
Grain).
Preferably, described diamond-metallic composite has one or more features following: (a) density is 5 9g/
cm3(it is preferred that its density is 6 8.5g/cm3)；(b) thermal conductivity >=400W/m K (its thermal conductivity even >=700W/m K；Relatively
Goodly for 600-1000W/m K；It is more preferably 600-800W/m K)；C () thermal coefficient of expansion≤15 μm/m K is (preferably
4-12μm/m·K；It is more preferably 5-8 μm/m K).
Preferably, described nano whisker is boron nano whisker or boron nitride nanometer whisker.With boron nitride nanometer whisker it is
Example, in the diamond-metallic composite of the present invention, described diamond particles and metallic matrix (such as Copper substrate) are by height
The boron nitride nanometer whisker of intensity connects, and defines the Three-Dimensional contact interfacial structure of a kind of novelty.Boron nitride nanometer whisker reinforcement
Diamond and intermetallic wellability, simultaneously because nano whisker has huge specific surface, thus considerably increase and gold
The contact area belonged to.It addition, boron nitride itself is good Heat Conduction Material, the phonon in diamond enters with the phonon in boron nitride
Row coupling, then by the huge side surface of boron nitride nanometer whisker and the electronics coupled in metal, composite wood is greatly improved
The capacity of heat transmission of material.
Boron raw material
As used herein, described boron raw material can be powder or liquid.The most described boron raw material can be simple substance
Boron and boron compound (preferably, described boron compound includes boric acid).
Metallic catalyst
As used herein, described metallic catalyst preferably includes copper, gold, nickel, platinum, silver or their alloy；More preferably
For fine copper (the preferably copper of purity >=99.99%) or copper alloy (such as copper-iron alloy, chromiumcopper, corronil etc.).Described
Metallic catalyst can be the metal (alloy) of powder body or block.
In reacting by heating, described metallic catalyst can form nano-liquid droplet, and becomes boron nanowire or boride is received
The catalyst of nanowire growth.
Preparation method
The invention provides the preparation method of a kind of diamond-metallic composite, the most described method includes as follows
Step:
(1) diamond pre-treatment step:
At diamond particle surfaces growth in situ nano whisker, thus form diamond-nano whisker complex；
Preferably, described step (1) includes step:
(1.1) offer comprises diamond particles, boron raw material and the mixture of metallic catalyst；
(1.2) in a vacuum or in hydrogen, argon or the reducing atmosphere of a combination thereof gas or inert atmosphere, will step
Suddenly the mixture of (1.1) carries out reacting by heating, thus forms diamond-boron nano whisker complex；And
The diamond that optionally step (1.2) is obtained by (1.3)-boron nano whisker complex enters in nitrogen or ammonia
Row reacting by heating, thus form diamond-boron nitride nanometer whisker complex；
Or described step (1) includes step:
(1-1) offer comprises diamond particles, boron raw material and the mixture of metallic catalyst；With
(1-2) in nitrogen or ammonia, the mixture of step (1-1) is carried out reacting by heating, thus formed diamond-
Boron nitride nanometer whisker complex.
In each step above-mentioned, described reacting by heating is preferably carried out at 800-1150 DEG C；Described reacting by heating
Preferably carry out under the atmosphere that pressure is 1Pa 120kPa.
In another preference, in described step (1.1) or step (1-1), calculate by total weight of the mixture, boron raw material
Mass fraction is 1-15wt%；Preferably 5-10wt%.
In another preference, in described step (1.1) or step (1-1), calculate by total weight of the mixture, metal catalytic
The mass fraction of agent is 10-90wt%；Preferably 20-85wt%；It is more preferably 30-75wt%.
(2) diamond-metallic composite preparation process:
Diamond-nano whisker the complex of step (1) is sintered with metallic matrix, thus forms this
Bright diamond-metallic composite.
Preferably, described step (2) is: under 800 1150 DEG C (or 850-1000 DEG C), at 10 150MPa (preferably 10-
100MPa or 10-80MPa) under, the diamond-nano whisker complex of step (1) is sintered with metallic matrix,
Thus form diamond-metallic composite.
In step (2), calculate by the gross weight of diamond-nano whisker complex with metallic matrix, metallic matrix
Mass fraction is 10 90wt% (preferably 30-80wt% or 50-80wt%).
The capital equipment that the method is used is cheap, be easy to get, and uses general hot-press equipment, such as, includes: vacuum
Carbon shirt-circuiting furnace, discharge plasma sintering furnace or hot pressing furnace etc..
The preparation method of diamond-metallic composite that the present invention provides is by Modified Diamond growth in situ nanometer
Whisker combines with the preparation of super-high heat-conductive composite, by the atmosphere in regulation diamond surface preprocessing process, pressure
And temperature, at high temperature process diamond particle surfaces, growth in situ nano whisker, significantly improve between diamond and metal
Bond strength, thus reduce thermal resistance, improve thermal conductivity, and the Thermal expansion coefficient of composites prepared is controlled.
Now as a example by boron nitride nanometer whisker, illustrate that the preparation method of the present invention mainly includes advantages below:
(1) diamond particles passes through pre-treatment step, and diamond particle surfaces growth in situ goes out boron nitride nanometer whisker and (makees
Strengthen phase for boron nitride layer or interface), not only increase the contact area of diamond interface and metal (such as copper), and due to
Under high temperature, wettability between metal and boron nitride is fine, compared to metal and diamond directly in conjunction with, tied by boron nitride layer
Wetness degree between the diamond and the metal that close significantly improves, and boron nitride has the thermal conductivity of excellence, the thickness of boron nitride layer
Degree can be regulated by the temperature and temperature retention time that change pretreatment so that through the composite that Fast Sintering densification obtains
There is high thermal conductivity, and controlled thermal coefficient of expansion.And boron nitride layer (or interface enhancing phase) divides in metallic matrix
Cloth is uniform, and therefore the interface bond strength between diamond and metal is high.
(2) temperature of diamond pre-treatment step low (maximum temperature is about 1150 DEG C), the time is processed short, therefore, such as
Under the atmosphere such as nitrogen or ammonia, can greatly stop diamond graphitization.
Diamond-metallic composite the thermal conductivity using preparation method of the present invention to obtain is up to 700W/m K, thermal expansion
Less than 7.6 μm/m DEG C, consistency reaches more than 96%.
Application
The diamond of the present invention-metallic composite excellent performance, has in many-sides such as machinery, material, electronics very well
Application prospect, such as processing machinery goods, composite, electronic devices and components etc..
In another preference, described machinework includes: cutter, grinding tool, file, emery wheel, saw blade, drill bit etc..
In another preference, described electronic devices and components include: encapsulation base material, fin etc..
The present invention mainly has the advantage that
1. the invention provides a kind of diamond-metallic composite, this composite has three dimensional structure, and has boundary
The advantages such as face intensity is high, and thermal conductivity is high, thermal coefficient of expansion is low and controlled, compactness is good.
2. the present invention also provides for the preparation method of a kind of diamond-metallic composite, the method technique is simple, convenient,
Financial cost is low, is suitable for industrialization.
Below in conjunction with being embodied as, the present invention is expanded on further.Should be understood that these embodiments be merely to illustrate the present invention and
It is not used in restriction the scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, generally according to normal condition,
Or according to the condition proposed by manufacturer.Unless otherwise indicated, otherwise percentage ratio and number are calculated by weight.Unless said especially
Bright, the present invention is raw materials used or reagent the most commercially.Unless stated otherwise, the composite of the present invention is tested according to a conventional method
Density, thermal conductivity, the performance such as thermal coefficient of expansion.
The preparation of embodiment 1 diamond-copper composite material 1
The pretreatment of 1.1 diamond particles
By mean diameter respectively be about 300 μm and the diamond particles (mass ratio is 3:1) of about 80 μm, with high-purity copper powder and
A small amount of boron powder mix homogeneously, forms mixed-powder, wherein, calculates by the gross weight of mixed-powder, and copper powder mass fraction is 60%, B
The mass fraction of powder is 5%, puts in vacuum carbon tube furnace, and being evacuated to vacuum is 10-2Pa, then passes to nitrogen or ammonia, gas
Pressure is 1Pa 120kPa, and heating rate is that 150 DEG C/min is warming up to 1100 DEG C, is incubated 20min, then cools to room with the furnace
Temperature.Mixed-powder high-temperature process crossed takes out, and crosses 30 mesh, 60 mesh, 80 mesh, 100 mesh, 150 mesh sieves respectively, removes superfluous copper
Powder and boron powder, it is thus achieved that superficial growth has the diamond particles of boron nitride nanometer whisker.
Fig. 2 is the electron scanning micrograph that superficial growth has the diamond particles of boron nitride nanometer whisker, Qi Zhongsuo
Show that nanometer wire material is the boron nitride nanometer whisker of diamond surface growth in situ.
Fig. 3 is the transmission electron microscope photo (Fig. 3 A) of a boron nitride nanometer whisker and corresponding electronic diffraction photo
(Fig. 3 B).Electronic diffraction photo proves that nanometer wire material is the boron nitride crystal whisker of crystallization.Dark particles at whisker top
For copper granule.The boron nitride crystal whisker effect that copper plays in diamond surface growth course is to promote the growth of whisker forming core
Catalyst action, after whisker growth, copper is embedded in whisker top admittedly with the form of nano-particle.The solid embedding copper in whisker top
Granule, can promote the associativity of whisker and Copper substrate in the diamond-copper composite material synthesized subsequently further.
1.2 prepare diamond-copper composite material
To mix homogeneously, by mixed powder gross weight through the diamond particles of aforementioned step process is common with high-purity copper powder
Amount calculates, and copper powder mass fraction is 60%, by mixed powder in discharge plasma sintering furnace mould, with heating rate
150 DEG C/min is heated to 920 DEG C and is sintered, and temperature retention time is 6min, and sintering pressure is 50MPa；Then room is cooled to the furnace
Temperature, obtains diamond-copper composite material 1, and its density is 6.226g/cm3, thermal conductivity is 702W/m K, and thermal coefficient of expansion is
6.22μm/m·K。
The preparation of embodiment 2 diamond-copper composite material 2
The pretreatment of 2.1 diamond particles
It is that the diamond particles about 200 μm is mixed homogeneously with high-purity copper powder and a small amount of boric acid by mean diameter, makes slurry
Material, is calculated by slurry gross weight, and copper powder mass fraction is 60%, and the mass fraction of boric acid is 5%, and slurry is put into vacuum carbon tube furnace
In, being evacuated to vacuum is 10-2Pa, then passes to nitrogen or ammonia, and atmospheric pressure is 1Pa-120kPa, and heating rate is 150
DEG C/min is warming up to 1100 DEG C, it is incubated 20min, then cools to room temperature with the furnace.Mixed-powder high-temperature process crossed takes out, point
Do not cross 30 mesh, 60 mesh, 80 mesh, 100 mesh, 150 mesh sieves, remove superfluous copper powder, it is thus achieved that superficial growth has boron nitride nanometer whisker
Diamond particles.
2.2 prepare diamond-copper composite material
To mix homogeneously, by mixed powder gross weight through the diamond particles of aforementioned step process is common with high-purity copper powder
Amount calculate, copper powder mass fraction is 70%, by mixed powder in discharge plasma sintering furnace mould with heating rate
150 DEG C/min is heated to 950 DEG C and is sintered, and sintering pressure is 30MPa, obtains diamond-copper composite material 2, and its density is
7.01g/cm3, thermal conductivity is 667W/m K, and thermal coefficient of expansion is 7.254 μm/m K.
The preparation of embodiment 3 diamond-copper composite material 3
The pretreatment of 3.1 diamond particles
Being the diamond particle surfaces one layer of boron film of sputtering about 300 μm in mean diameter, thickness is 1-100 μm.Then
One layer of copper film of sputtering again, thickness is 0.1-100 μm.Diamond particles after plated film is put in vacuum carbon tube furnace, evacuation
It is 10 to vacuum-2Pa, then passes to nitrogen or ammonia, and atmospheric pressure is 1Pa 120kPa, and heating rate is that 150 DEG C/min heats up
To 1100 DEG C, it is incubated 20min, then cools to room temperature with the furnace, it is thus achieved that superficial growth has the diamond of boron nitride nanometer whisker
Grain.
3.2 prepare diamond-copper composite material
To mix homogeneously through the diamond particles of aforementioned step process is common with high-purity copper powder, total by mixed powder
Weight calculate, copper powder mass fraction is 60%, by mixed powder in vacuum hotpressing stove mould with 50 DEG C/min of heating rate
Being heated to 950 DEG C to be sintered, sintering pressure is 20MPa, prepares diamond-copper composite material 3, and its density is 7.12g/cm3,
Thermal conductivity is 672W/m K, and thermal coefficient of expansion is 6.844 μm/m K.
The preparation of embodiment 4 diamond-copper composite material 4
The pretreatment of 4.1 diamond particles
By mean diameter respectively be about 300 μm and the diamond particles (mass ratio is 3:1) of about 80 μm, with high-purity copper powder and
A small amount of boron powder mix homogeneously, forms mixed-powder, wherein, calculates by the gross weight of mixed-powder, and copper powder mass fraction is 60%, B
The mass fraction of powder is 5%, puts in vacuum carbon tube furnace, and being evacuated to vacuum is 10-2Pa, heating rate is 150 DEG C/min liter
Temperature, to 1100 DEG C, is incubated 20min, then cools to room temperature with the furnace.Mixed-powder high-temperature process crossed takes out, and crosses 30 respectively
Mesh, 60 mesh, 80 mesh, 100 mesh, 150 mesh sieves, remove superfluous copper powder and boron powder, it is thus achieved that superficial growth has the gold of boron nano whisker
Hard rock granule.
4.2 prepare diamond-copper composite material
To mix homogeneously, by mixed powder gross weight through the diamond particles of aforementioned step process is common with high-purity copper powder
Amount calculates, and copper powder mass fraction is 60%, by mixed powder in discharge plasma sintering furnace mould, with heating rate
150 DEG C/min is heated to 920 DEG C and is sintered, and temperature retention time is 6min, and sintering pressure is 50MPa；Then room is cooled to the furnace
Temperature, obtains diamond-copper composite material 4, and its density is 6.356g/cm3, thermal conductivity is 685W/m K, and thermal coefficient of expansion is
6.57μm/m·K。
The preparation of embodiment 5 diamond-copper composite material 5
The pretreatment of 5.1 diamond particles
By mean diameter respectively be about 300 μm and the diamond particles (mass ratio is 3:1) of about 80 μm, with high-purity copper powder and
A small amount of boron powder mix homogeneously, forms mixed-powder, wherein, calculates by the gross weight of mixed-powder, and copper powder mass fraction is 60%, B
The mass fraction of powder is 5%, puts in vacuum carbon tube furnace, and being evacuated to vacuum is 10-2Pa, then passes to nitrogen or ammonia, gas
Pressure is 1Pa 120kPa, and heating rate is that 150 DEG C/min is warming up to 1100 DEG C, is incubated 20min, then cools to room with the furnace
Temperature.Mixed-powder high-temperature process crossed takes out, and crosses 30 mesh, 60 mesh, 80 mesh, 100 mesh, 150 mesh sieves respectively, removes superfluous copper
Powder and boron powder, it is thus achieved that superficial growth has the diamond particles of boron nitride nanometer whisker.
5.2 prepare diamond-copper composite material
By the diamond particles uniform spreading through aforementioned step process on copper sheet, the then bortz powder after uniformly completing
Copper sheet one layer is placed in surface, is then placed in discharge plasma sintering furnace mould, is heated to 150 DEG C/min of heating rate
920 DEG C are sintered, and temperature retention time is 6min, and sintering pressure is 50MPa；Then cool to room temperature with the furnace, obtain diamond-copper
Composite 5, its density is 6.578g/cm3, thermal conductivity is 622W/m K, and thermal coefficient of expansion is 6.01 μm/m K.
Understand through conventional method test, a diameter of 1-5000nm of the nano whisker in above-described embodiment, a length of 0.1-
300 μm, and be 1-10000/μm in the density of diamond particle surfaces2。
The all documents mentioned in the present invention are incorporated as reference the most in this application, just as each document by individually
It is incorporated as with reference to like that.In addition, it is to be understood that after the above-mentioned teachings having read the present invention, those skilled in the art can
To make various changes or modifications the present invention, these equivalent form of values fall within the model that the application appended claims is limited equally
Enclose.
Claims (12)
1. diamond-the metallic composite of a highly thermally conductive performance, it is characterised in that described composite includes Metal Substrate
Body and be distributed in the diamond particles on described intrinsic silicon and/or surface, the part or all of described diamond of at least a part of which
Grain is incorporated into described metallic matrix by nano whisker；
Further, described nano whisker is boron nitride nanometer whisker；
Further, the thermal conductivity of described diamond-metallic composite >=700W/m K；
Further, described nano whisker has the feature that (i) a diameter of 1-5000nm；And/or (ii) a length of 0.1 300 μ
m；And/or (iii) is 1 10000/μm in the density of diamond particle surfaces2；
And described diamond-metallic composite is following preparation:
(1) at diamond particle surfaces growth in situ nano whisker, thus diamond-nano whisker complex is formed；And
(2) diamond-nano whisker complex of step (1) is sintered with metallic matrix, thus described in being formed
Diamond-metallic composite；
Further, described step (1) includes step:
(1-1) offer comprises diamond particles, boron raw material and the mixture of metallic catalyst；With
(1-2) in nitrogen or ammonia, the mixture of step (1-1) is carried out reacting by heating, thus forms diamond-nitridation
Boron nano whisker complex；
Further, described reacting by heating is carried out under the atmosphere that pressure is 1Pa 120kPa.
2. diamond-metallic composite as claimed in claim 1, it is characterised in that described boron nitride nanometer whisker is
Crystallization.
3. diamond-metallic composite as claimed in claim 1, it is characterised in that the Buddha's warrior attendant of described high thermal conductivity
Stone-metallic composite has one or more features following:
A () density is 6-8.5g/cm3；And/or
(b) thermal coefficient of expansion≤15 μm/m K.
4. diamond-metallic composite as claimed in claim 1, it is characterised in that the particle diameter of described diamond particles
For 0.1-1000 μm.
5. diamond-metallic composite as claimed in claim 1, it is characterised in that described metallic matrix includes: copper,
Aluminum, silver or their alloy.
6. the preparation method of diamond-metallic composite, it is characterised in that include step:
(1) at diamond particle surfaces growth in situ nano whisker, thus diamond-nano whisker complex is formed；And
(2) diamond-nano whisker complex of step (1) is sintered with metallic matrix, thus forms right and want
Seek the diamond-metallic composite described in 1；
Wherein, described nano whisker is boron nitride nanometer whisker；
Further, described step (1) includes step:
(1-1) offer comprises diamond particles, boron raw material and the mixture of metallic catalyst；With
(1-2) in nitrogen or ammonia, the mixture of step (1-1) is carried out reacting by heating, thus forms diamond-nitridation
Boron nano whisker complex；
Further, described reacting by heating is carried out under the atmosphere that pressure is 1Pa 120kPa.
7. preparation method as claimed in claim 6, it is characterised in that described metallic matrix includes: copper, aluminum, silver or they
Alloy.
8. preparation method as claimed in claim 6, it is characterised in that in step (2), be combined by diamond-nano whisker
Body calculates with the gross weight of metallic matrix, and the mass fraction of metallic matrix is 10 90%.
9. preparation method as claimed in claim 6, it is characterised in that
Described metallic catalyst is copper, gold, nickel, platinum or their alloy.
10. preparation method as claimed in claim 6, it is characterised in that described step (2) is: at 800 1150 DEG C,
Under 10 150MPa, the diamond-nano whisker complex of step (1) is sintered with metallic matrix, thus is formed
Diamond-metallic composite.
11. goods, it is characterised in that comprise the diamond-metallic composite described in claim 1.
The purposes of 12. diamond-metallic composites as claimed in claim 1, it is characterised in that for machinework, again
Condensation material or electronic devices and components.
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| EP3190613B1 (en) * | 2014-09-02 | 2019-05-15 | A.L.M.T. Corp. | Heat dissipation member and method for producing heat dissipation member |
| CN105463346B (en) * | 2015-10-12 | 2017-02-22 | 中南大学 | Spiral line reinforced metal matrix composite and manufacturing method thereof |
| GB201722318D0 (en) * | 2017-12-31 | 2018-02-14 | Element Six Ltd | Superhard constructions & methods of making sameq |
| GB201722321D0 (en) * | 2017-12-31 | 2018-02-14 | Element Six Uk Ltd | Superhard constructions & methods of making the same |
| KR102390361B1 (en) * | 2018-06-04 | 2022-04-25 | 세키스이가가쿠 고교가부시키가이샤 | Diamond Particles, Diamond Containing Compositions, and Methods of Making Diamond Particles |
| CN109371303B (en) * | 2018-11-07 | 2020-11-06 | 中国科学院宁波材料技术与工程研究所 | Heat-conducting composite material, preparation method thereof and heat dissipation piece |
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| US20100206941A1 (en) * | 2007-05-22 | 2010-08-19 | David Patrick Egan | Coated diamond |
| CN102383014B (en) * | 2011-11-11 | 2013-02-13 | 华中科技大学 | Method for preparing diamond-copper composite material by virtue of metallization of high-temperature blending surface |
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